CN106430709A - Copper-containing wastewater treatment method and device - Google Patents

Copper-containing wastewater treatment method and device Download PDF

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Publication number
CN106430709A
CN106430709A CN201610911165.3A CN201610911165A CN106430709A CN 106430709 A CN106430709 A CN 106430709A CN 201610911165 A CN201610911165 A CN 201610911165A CN 106430709 A CN106430709 A CN 106430709A
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copper
containing wastewater
membrane
mechanically stirred
stirred reactor
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CN201610911165.3A
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CN106430709B (en
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顾平
武耘羽
张光辉
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Tianjin University
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Tianjin 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
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/62—Heavy metal 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
    • C02F1/44—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

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention relates to a copper-containing wastewater treatment method and device. The method includes the steps thatradioactivecopper-containing wastewater, a basic cupric carbonateseed crystal and sodium carbonate in a mechanical stirring reactor react chemically through mechanical stirring, and a precipitate is deposited on the surface of seed crystal basic cupric carbonate to form large-particle dense crystal particles which fast precipitate on the bottom of the mechanical stirring reactor to remove most of copper ions; a small-particle precipitate and a seed crystal enter a membrane separator along with a supernate, and particulate matter is separated through a hollow fiber membrane to further remove the copper ions, so that the copper content of outlet water is substantially reduced. The particulate matter formed in the method is large in particle size, compact in structure and high in settling property, effectively overcomes the defects that a chemical precipitation method is large in sludge output and precipitates are poor in settling property, and increases the concentration multiple of copper treatment without causing serious membrane pollution, and the copper-containing wastewater treatment method is economical and practical.

Description

A kind of processing method and processing device of copper-containing wastewater
Technical field
The present invention relates to the treatment technology of a kind of copper-containing wastewater, be exactly removal copper ion from waste water.
Background technology
The distribution on earth of copper resource is very wide, and the application in the industry of copper metal is a lot.In the last few years, with copper mine The development of the industries such as exploitation, intermetallic composite coating, machine-building, the industrial wastewater of the industrial activity of sharp increase and a large amount of discharge result in ring The pollution aggravation of heavy metal copper in border.Copper can enter water body, in soil and then harm all can be produced to ecological environment and human body.People Class excessively takes in copper can cause serious MMi and corrosion, has a stomach upset and ulcer, liver and injury of kidney, chronic copper poisoning and Brain damage.No matter from the point of view of the angle to ecological environment security or health, copper is all the heavy metal with harmfulness. It is thus desirable to remove copper from the waste water of source, with the health of the safety preserved the ecological environment and human body.
Chemical precipitation method refer to by introduce suitable anion in water with Cu2+Form precipitation, recycle separation of solid and liquid The method that sediment is separated from water by means.Conventional precipitating reagent has lime, sulfide, sodium carbonate etc..Chemical precipitation method technique Flow process is simple, and easy to operate, operating cost is low, it is adaptable to the process of general copper-containing wastewater；But, it is heavy that chemical precipitation method is formed Shallow lake thing CuS grain diameter is tiny, separates difficulty from water body；Cu(OH)2For flock, settling property difference, and Cu (OH)2Mud Yield is big, and cycles of concentration (the waste water cumulative volume of process and the ratio of the sludge volume of generation) is low.
In both precipitation method BSW body separate all relatively difficult, and utilize induction crystallisation introduce crystal seed can Improve the solid-liquor separation characteristic forming precipitation in both technique.Induction crystalline deposit method is directed in water body add mineral grain As crystal seed, make Cu2+Sediment separate out at its surface crystallization and reach to increase precipitation particle size and improve settling property Purpose.Quartz sand would generally be added as crystal seed, add sodium carbonate as precipitating reagent, but the throwing amount of sodium carbonate is to a certain degree On determine the clearance of copper, sodium carbonate throwing amount is too low, does not has enough carbonates and copper reaction, and copper removal effect is bad, throwing amount Too high, cause pH value to raise and then have the generation of flocculent deposit Kocide SD.
Current great majority research, although (in reaction, sodium carbonate is dense can to have controlled the mol ratio of sodium carbonate and copper Degree and the ratio of concentration of copper ion) make to generate crystal completely in induction crystallization reaction at certain value and improve sediment performance, But water outlet still can not reach China drinking water standard 1.0mg/L (GB5749-2006).
Content of the invention
For problems of the prior art, the present invention proposes the method for mechanical agitation combination Middle hollow fiber membrane Remove the copper ion in waste water.Using mechanical agitation and UF membrane combination, simple to operation, automaticity is high, is suitable for Large-scale engineeringization is applied.The present invention is pre-processed by mechanical agitation, can make the copper ion in waste water and sodium carbonate and alkali formula Copper carbonate crystal seed forms big particle diameter, the particulate matter that structure is closely knit, settling property is good, effectively slow down hollow fiber film assembly Pollute speed, extend the service life of film, significantly improve removal effect and the sludge condensation multiple of copper simultaneously, decrease dirt Mud amount.
Technical scheme is as follows：
The processing method of a kind of copper-containing wastewater, step is as follows：
1) crystal seed is added：Disposably add basic copper carbonate crystal seed to mechanically stirred reactor, before reactor emptying no longer Add crystal seed；
2) mechanical agitation pretreatment：Add excessive sodium carbonate to mechanically stirred reactor, in mechanical agitation, waste water Copper ion and basic copper carbonate crystal seed, sodium carbonate react the big particle diameter compact grain thing of generation, precipitation makes particulate matter deposit subsequently Bottom mechanically stirred reactor；React CO after completing3 2-Excessive；
3) membrane separation：Mechanical agitation pretreated copper-containing wastewater supernatant enters membrane separator, in aeration agitation Effect is lower continues reaction generation particulate matter, water outlet after Middle hollow fiber membrane.
Described disposable addition basic copper carbonate crystal seed is 0.5-1.0g/L.
Described step 2) in copper-containing wastewater after mechanical agitation pretreatment completes, excessive in mechanically stirred reactor CO3 2-No less than 50mg/L.
Described step 2) in the time of staying in mechanically stirred reactor for the copper-containing wastewater be 15-30min, wherein stir Time is no less than 10min no less than 5min, sedimentation time.
The time of staying in membrane separator for the described copper-containing wastewater is 30-45 minute.
The processing means of the copper-containing wastewater of the present invention, is that waste water connects entering of mechanically stirred reactor 2 top through intake pump 1 Mouthful, the supernatant pipeline of mechanically stirred reactor 2 is through the import on elevator pump 3 junctional membrane separator 4 top, in membrane separator 4 Hollow-fibre membrane 5 by outlet pipe and motor-driven valve 6 and go out water pump 7 and be connected；Medicine storing drum 8 is connected to machinery through dosing pump 9 and stirs Mixing the feeding opening on reactor 2 top, mechanical agitator 10 and liquid level gauge 11 are arranged in mechanical agitator 2, and air blast 12 connects Air inlet bottom membrane separator 4, liquid level gauge 13 is arranged in membrane separator 4.
Described hollow-fibre membrane is conventional microfiltration membranes or milipore filter during water is processed.
The method, by adding a certain amount of basic copper carbonate crystal seed in reactor, then adds a certain amount of carbon in former water Acid sodium is as precipitating reagent, and is allowed to mix and carry out chemical reaction, i.e. copper ion and sodium carbonate at water by mechanical agitation Middle formation basic copper carbonate and basic copper carbonate seed surface deposition, form the closely knit crystal grain thing of big particle diameter and quickly sink Form sediment bottom mechanical agitator, to remove most copper ion；Short grained basic carbonate copper crystal enters film with supernatant and divides From device, particulate matter removes copper ion after Middle hollow fiber membrane further, makes the copper concentration of water outlet be greatly lowered.
The copper-containing wastewater processing means of the present invention uses auto-controll operation.
The beneficial effects of the present invention is：The enforcement of the present invention, can significantly improve the sedimentation of copper mud in copper-containing wastewater Performance and cycles of concentration, improve the removal effect of copper ion in water simultaneously, decreases the potential hazard to environment and the public for the copper. Can be designed to fixed or wheeled apparatus as required based on the reactor of the method, design scale also can select flexibly Take, it is adaptable to general copper-containing wastewater process, have a extensive future, obvious environment benefit.
Brief description
Fig. 1：For apparatus of the present invention figure.
In figure：1-elevator pump；2-mechanically stirred reactor；3-elevator pump；4-membrane separation reactor；5-hollow-fibre membrane； 6-motor-driven valve；7-goes out water pump；8-medicine storing drum；9-dosing pump；10-mechanical agitator；11-liquid level gauge；12-air blast；13-liquid level Meter.
Detailed description of the invention
Below in conjunction with accompanying drawing, embodiments of the present invention are illustrated.It should be noted that the present embodiment is narrative , rather than determinate, do not limit protection scope of the present invention with this embodiment.
The device of present example is shown in accompanying drawing.Wastewater storage tank size Φ × H=1100 × 2150mm；Mechanically stirred reactor For cylinder, Φ × H=240 × 347mm；Membrane separator Φ × H=120 × 1500mm, equipped with 1 hollow fiber microfiltration membrane group Part, nominal pore size is 0.22 μm, and effective area is 0.5m2, intake pump and to go out water pump be elevator pump, dosing pump and film go out water pump and are Peristaltic pump, water flow is calculated as spinner flowmeter.Device uses PLC (Programmable Logic Controller) control, fully automatic operation, and PLC adopts Program with current techique.Device be every day 24h run continuously, wherein mechanically stirred reactor is batch-type Inlet and outlet water, UF membrane Device is interval water outlet, in the circulation of every 10 minutes, water outlet 9 minutes, empty aeration 1 minute.
Specific operation process is：When device starts, disposably add basic copper carbonate crystal seed to mechanically stirred reactor 2. Under PLC control, during liquid level 11 low liquid level, intake pump 1 aspirates copper-containing wastewater, and current are entered mechanically stirred reactor 2 by top, During liquid level gauge 11 high level close intake pump 1, start agitator 10, simultaneously start dosing pump 9 by the sodium carbonate in medicine storing drum 7 by Top adds mechanically stirred reactor 2, and copper-containing wastewater, crystal seed and sodium carbonate stir device effect 10 times mutually collisions, reactions at machinery, Form big particle diameter, the particulate matter that closely knit, settling property is good, be gradually deposited to the bottom of mechanically stirred reactor 2.Liquid level gauge 13 is low During liquid level, the boosted pump of supernatant 3 in mechanical agitator 2 enters membrane separator 4；Elevator pump is closed during liquid level gauge 13 high level 4, open out water pump 7 simultaneously；For slowing down the pollution of doughnut mocromembrane 5, air blast 12 to membrane separator 4 aeration to provide air Stirring；Under going out water pump 7 swabbing action, water outlet after doughnut mocromembrane 5 and motor-driven valve 6, close during liquid level gauge 13 low liquid level Go out water pump 7, stop water outlet, be then turned on elevator pump 3 and intake in membrane separator 4, circulate successively.
Embodiment 1：The process water yield of device is 15L/h, and the time of staying of mechanically stirred reactor is (stirring 5 in 15 minutes Minute, precipitation 10 minutes), the hydraulic detention time of membrane separator is 30 minutes.Utilizing this device to process pH value is 6.1-6.2, Cupric concentration is the simulated wastewater of 20mg/L.Experiment adds 0.5g/L basic copper carbonate in mechanically stirred reactor when starting brilliant Kind；In experiment, sodium carbonate dosage controls when 104mg/L, and water outlet copper mass concentration is stable at below 1mg/L, and with processing The growth of the water yield is gradually decrease to 0.4mg/L, and removal efficiency reaches 98%；Water outlet carbon acid ion concentration is 50-55mg/L.? Under the conditions of this, the cycles of concentration of this technique is 7982.Membrane specific flux is from initial 57L/ (m2H m) it is down to 33L/ (m2·h· M), can recover after Chemical cleaning to 51L/ (m2·h·m).
Embodiment 2：The process water yield of device is 15L/h, and the time of staying of mechanically stirred reactor is (stirring 5 in 15 minutes Minute, precipitation 10 minutes), the hydraulic detention time of membrane separator is 45 minutes.Utilizing this device to process pH value is 6.2-6.4, Cupric concentration is the simulated wastewater of 20mg/L.Experiment adds 0.5g/L basic copper carbonate in mechanically stirred reactor when starting brilliant Kind；In experiment, sodium carbonate dosage controls when 104mg/L, and water outlet copper mass concentration is stable at below 2mg/L, processes the water yield and reaches After 800L, water outlet copper concentration is stable at 0.07mg/L, and clearance reaches 99%；Water outlet carbon acid ion concentration is 50- 55mg/L.The cycles of concentration of this technique is 3175 with this understanding.Membrane specific flux is from initial 62.2L/ (m2H m) it is down to 34.7L/(m2H m), can recover after Chemical cleaning to 57L/ (m2·h·m).
Embodiment 3：The process water yield of device is 20L/h, and the time of staying of mechanically stirred reactor is (stirring 5 in 30 minutes Minute, precipitation 16 minutes), the hydraulic detention time of membrane separator is 30 minutes.Utilizing this device to process pH value is 6.1-6.2, Cupric concentration is the simulated wastewater of 50mg/L.Experiment adds 1g/L basic copper carbonate in mechanically stirred reactor when starting brilliant Kind；In experiment, sodium carbonate dosage controls when 180mg/L, and water outlet copper mass concentration is stable at about 0.5mg/L, and clearance reaches To 99%；Water outlet carbon acid ion concentration is 50-60mg/L.Membrane specific flux is from initial 46.9L/ (m2H m) it is down to 29.6L/(m2H m), can recover after Chemical cleaning to 46.2L/ (m2·h·m).
Embodiment 4：The process water yield of device is 20L/h, and the time of staying of mechanically stirred reactor is (stirring 5 in 30 minutes Minute, precipitation 16 minutes), the hydraulic detention time of membrane separator is 45 minutes.Utilizing this device to process pH value is 6.0-6.1, Cupric concentration is the simulated wastewater of 50mg/L.Experiment adds 1g/L basic copper carbonate in mechanically stirred reactor when starting brilliant Kind；In experiment, sodium carbonate dosage controls when 140mg/L, and water outlet copper mass concentration is stable at about 1mg/L, and clearance reaches 98%；Water outlet carbon acid ion concentration is 50-60mg/L.The cycles of concentration of this technique is 2032 with this understanding.Membrane specific flux From initial 47.5L/ (m2H m) it is down to 39.3L/ (m2H m), can recover after Chemical cleaning to 47.6L/ (m2· h·m).

Claims (7)

1. a processing method for copper-containing wastewater, is characterized in that step is as follows：
1) crystal seed is added：Disposably add basic copper carbonate crystal seed to mechanically stirred reactor, no longer add before reactor emptying Crystal seed；
2) mechanical agitation pretreatment：Add excessive sodium carbonate to mechanically stirred reactor, after mechanical agitation, in waste water Copper ion and basic copper carbonate crystal seed, sodium carbonate react the big particle diameter compact grain thing of generation, staticly settle subsequently and make particulate matter sink Amass bottom mechanically stirred reactor；React CO after completing3 2-Excessive；
3) membrane separation：Mechanical agitation pretreated copper-containing wastewater supernatant enters membrane separator, in aeration agitation effect Lower continuation reacts generation particulate matter, water outlet after Middle hollow fiber membrane.
2. the method for claim 1, is characterized in that described disposable addition basic copper carbonate crystal seed is 0.5-1.0g/ L.
3. the method for claim 1, is characterized in that described step 2) in copper-containing wastewater pre-processed in mechanical agitation Cheng Hou, CO excessive in mechanically stirred reactor3 2-No less than 50mg/L.
4. the method for claim 1, is characterized in that described step 2) in copper-containing wastewater in mechanically stirred reactor The time of staying is 15-30min, and the mechanical agitation time is no less than 10min no less than 5min, sedimentation time.
5. the method for claim 1, is characterized in that the time of staying in membrane separator for the described copper-containing wastewater is 30- 45 minutes.
6. realize the processing means of the copper-containing wastewater of claim 1, it is characterized in that waste water connects mechanic whirl-nett reaction through intake pump The import on device top, the supernatant pipeline of mechanically stirred reactor is through the import on elevator pump junctional membrane separator top, and film divides Hollow-fibre membrane in device is by outlet pipe and motor-driven valve and goes out water pump and is connected；Medicine storing drum is connected to machinery through dosing pump and stirs Mixing the feeding opening on reactor top, mechanical agitator and liquid level gauge are arranged in mechanical agitator, and air blast is connected to UF membrane Air inlet bottom device, liquid level gauge is arranged in membrane separator.
7. device as claimed in claim 6, it is characterized in that described hollow-fibre membrane be during water is processed conventional microfiltration membranes or Milipore filter.
CN201610911165.3A 2016-10-19 2016-10-19 Method and device for treating copper-containing wastewater Expired - Fee Related CN106430709B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109205829A (en) * 2018-09-08 2019-01-15 天津大学 The method of film assisting crystallisation technique MAC selective removal and the copper in recycle-water
CN111170354A (en) * 2019-12-31 2020-05-19 东莞市广华化工有限公司 Purification device for recovering basic copper carbonate from acidic etching waste liquid and use method thereof
CN115784408A (en) * 2022-08-31 2023-03-14 哈尔滨工业大学 Method for removing phosphorus, fluorine and heavy metals in wastewater by using modified seed crystal for induced crystallization

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WO2015014546A1 (en) * 2013-07-31 2015-02-05 Krones Ag Method and device for material-oriented water treatment for mines
CN105948366A (en) * 2016-07-15 2016-09-21 武汉尚远环保股份有限公司 Treatment method for copper-containing wastewater

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109205829A (en) * 2018-09-08 2019-01-15 天津大学 The method of film assisting crystallisation technique MAC selective removal and the copper in recycle-water
CN111170354A (en) * 2019-12-31 2020-05-19 东莞市广华化工有限公司 Purification device for recovering basic copper carbonate from acidic etching waste liquid and use method thereof
CN115784408A (en) * 2022-08-31 2023-03-14 哈尔滨工业大学 Method for removing phosphorus, fluorine and heavy metals in wastewater by using modified seed crystal for induced crystallization
CN115784408B (en) * 2022-08-31 2023-09-12 哈尔滨工业大学 Method for removing phosphorus, fluorine and heavy metals in wastewater by utilizing modified seed crystal induced crystallization

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