CN100488899C - Diaphragm separation electrolyzing integrated treatment method for waste water containing heavy metal copper - Google Patents
Diaphragm separation electrolyzing integrated treatment method for waste water containing heavy metal copper Download PDFInfo
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- CN100488899C CN100488899C CNB200710056689XA CN200710056689A CN100488899C CN 100488899 C CN100488899 C CN 100488899C CN B200710056689X A CNB200710056689X A CN B200710056689XA CN 200710056689 A CN200710056689 A CN 200710056689A CN 100488899 C CN100488899 C CN 100488899C
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Abstract
The invention discloses a method used membrane separating-electrolyzing integration to process heavy metal copper containing waste water. It includes the following step: gravity setting, micron filtering, and membrane separating. The concentrated solution is poured into the electrolytic reactor after pH value regulating to deposit heavy metal copper on its negative pole board by energizing to reduce. The residual liquid can be reused in the production technology. The invention can reclaim the metal copper from the heavy metal copper containing waste water, realize water resource reuse. In addition, it has simple device, convenient operation, high recovery ratio, comprehensive utilization ratio, good economic benefit.
Description
Technical field
The present invention relates to the method that the integrated processing of a kind of membrane sepn-electrolysis contains heavy metal copper waste water, belong to the heavy metal-containing wastewater treatment technology.
Background technology
Contain waste water, especially electroplating industry that heavy metal copper waste water is mainly discharged from enterprises such as smelting, plating, chemical industry, dyestuff, ink manufacturing, papermaking, process hides, pharmacy, weaving, fertilizer, oil refining, it is big to contain the heavy metal copper wastewater discharge.It is acid or alkaline that electro-coppering waste water generally is, and contains and be difficult to biodegradable heavy metal copper ion and organic additive, serious to environment and biological hazard.The method that conventional process contains heavy metal copper waste water mainly contains Coagulation Method, absorption method, chemical precipitation method, electrolytic process, ion exchange method and membrane separation process etc.
Coagulation Method is to add flocculation agent in copper-containing wastewater, makes cupric ion and flocculation agent form cotton-shaped particulate matter and precipitates.Flocculation agent commonly used is aluminium salt and molysite, and such inorganic flocculating agent as settling is dealt with improperly, can cause aluminium to discharge in a large number to environment owing to add a large amount of aluminium salt, and soil, water body aluminium content are increased, and causes secondary pollution.
Absorption method comes down to the adsorbent activity surface adsorbs cupric ion, and the most frequently used sorbent material is a gac.The charcoal absorption capacity is big, but price is more expensive, and work-ing life is short, needs regeneration, and the process cost height.
Chemical precipitation method is to add chemical precipitation agent in copper-containing wastewater, and chemical reaction takes place, and makes cupric ion generate the sedimentable matter of indissoluble.Chemical precipitation method equipment is simple, and is easy to operate, but the expense height, sludge quantity is big, if mud is not done suitable aftertreatment, can cause secondary pollution.
Treatment with electrolytic method is to use electrolytic ultimate principle, makes that cupric ion is reduced into metallic copper in the waste water, in the negative electrode enrichment, reclaims metallic copper then.Electrolytic process need not add reagent treatment, and technical process is simple.But the electrolytic process treatment capacity is little, and it is big that processing is contained low-concentration heavy metal ionic waste water current consumption.
Ion exchange method is cupric ion and ion exchange resin generation ion-exchange, removes the copper in the waste water.Ion exchange method is a kind of improvement method of heavy metal-containing waste water preferably.The processing capacity is big, and effluent quality is good, and recyclable water and heavy metal resources are to the environment non-secondary pollution.But resin vulnerable to pollution or oxidation deactivation, regeneration is frequent, the process cost height.
The membrane separation process utilization has the specific semi-permeable membrane of high crown_interception to hold back cupric ion in the waste water to cupric ion, thereby reaches the separation purpose.Membrane separation process separation efficiency height, energy consumption is low, and equipment is simple, and less investment can not cause secondary pollution, can't dispose but the problem that exists is the concentrated solution that membrane separation process produces.
Summary of the invention
The object of the present invention is to provide the integrated processing of a kind of membrane sepn-electrolysis to contain the method for heavy metal copper waste water, utilize this method not only can reclaim the metallic copper that contains in the heavy metal copper waste water, and realize the utilization again of water resources.
The present invention is realized that by the following technical programs the integrated processing of a kind of membrane sepn-electrolysis contains the method for heavy metal copper waste water, it is characterized in that comprising following process:
1. contain the pre-treatment of heavy metal copper waste water: be the waste water adding slurry tank of 10mg/L～1000mg/L with copper concentration, under 20～25 ℃, gravity settling 12～24 hours, get supernatant liquor, remove the fine solid particle particle and the copper chip that suspend in the supernatant liquor with the micron filter of aperture 5～15 μ m and get filtrate;
2. the filtrate that step 1 is obtained is carried out membrane sepn: with pump filtrate is squeezed into membrane separation apparatus, film in the membrane separation apparatus is polyvinyl alcohol and poly-piperazine amide mixed type composite nanometer filtering film or polyamide-based complex reverse osmosis membrane, retaining molecular weight 150～300 dalton, membrane flux 15～35L/m
2H, flow of filtrate 1～3L/min, under 20～35 ℃ and 0.6～1.0MPa pressure, membrane sepn is after 15～24 hours, and heavy metal copper ion rejection reaches more than 90% in the filtrate, sees through liquid behind the membrane sepn and is used further to production technique;
3. the concentrated solution electrolytic reaction behind the membrane sepn: the concentrated solution behind the membrane sepn that step 2 obtains, use 1mol/LH
2SO
4Or 1mol/L NaOH solution to regulate its pH value be 2～3, then this concentrated solution is squeezed into electrolysis reactor with pump, cathode material in the electrolysis reactor is a stainless steel plate, anode material is the titanium plate of iridium oxide coating, barrier film is the porous water-permeable membrane, mould material is a polysulfones, and the aperture is 0.20～0.45 μ m, at concentrated solution circular flow 1.5～2.5L/h, cathode current density 50～100A/m
2, temperature is to carry out electrolysis procedure under 20～35 ℃ of conditions, electrolysis is after 1～3 hour, and enriched in metals copper on the electrolysis reactor negative plate, residual electrolyte is used further to production technique.
The present invention combines membrane sepn with electrolysis tech, processing unit is simple, the operational condition gentleness, need not introduce other chemical agent in the treating processes, non sludge produces, and has avoided secondary pollution, the metallic copper total yield reaches more than 80%, waste water recycling after the processing has been avoided the environmental pollution and the wasting of resources in other production technique, and is good in economic efficiency.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
1 is slurry tank among the figure, and 2 is topping-up pump, and 3 is micron filter, and 4 is high-pressure pump, and 5 is membrane separation apparatus, and 6 is topping-up pump, and 7 is electrolysis reactor
Embodiment
To contain Cu concentration is the waste water 2L adding slurry tank 1 of 16.24mg/L, and under 20 ℃, gravity settling 24 hours is got supernatant liquor, and supernatant liquor adds micron filters 3 (aperture 5 μ m) through topping-up pump 2.Filtrate filtered is squeezed into membrane separation apparatus 5 through high-pressure pump 4, and the film in the membrane separation apparatus is the DL of GE company polyvinyl alcohol and poly-piperazine amide mixed type composite nanometer filtering film, retaining molecular weight 150～300Dalton (dalton), membrane flux 28L/m
2H, flow of filtrate 1L/min, under 20 ℃ and 0.6MPa condition, behind the membrane sepn 15 hours, record that Cu concentration is 137.83mg/L in the concentrated solution, see through that Cu concentration is 6mg/L in the liquid, the Cu cycles of concentration is 8.49 times, this nanofiltration membrane, sees through liquid and is used further to production technique greater than 90% the rejection of Cu behind the membrane sepn.Concentrated solution after membrane separation apparatus is handled is used 1mol/L H
2SO
4It is 3 that solution is regulated its pH value, this concentrated solution is squeezed into electrolysis reactor 7 through pump 6, the electrolysis reactor anode material is an iridium oxide coated titanium plate, cathode material is a stainless steel plate, and two-plate spacing 16mm, barrier film are the porous water-permeable membrane, mould material is a polysulfones, the aperture is 0.22 μ m, at concentrated solution circular flow 2.0L/h, cathode current density 80A/m
2, temperature is to carry out electrolysis procedure under 25 ℃ of conditions, electrolysis is after 2 hours, records that Cu concentration is 20.67mg/L in the concentrated solution, and the electrolytic reaction Cu rate of recovery 90%, raffinate is used further to production technique after the electrolysis.
The present embodiment method is specifically investigated the effect of different nanofiltration membrane treatment waste water with embodiment 1.
To contain Cu concentration is the waste water 2L adding slurry tank 1 of 16.24mg/L, and under 20 ℃, gravity settling 24 hours is got supernatant liquor, and supernatant liquor enters micron filter 3 (aperture 5 μ m) through topping-up pump 2.Filtrate filtered is squeezed into membrane separation apparatus 5 through high-pressure pump 4, and the film in the membrane separation apparatus is the DK of GE company polyvinyl alcohol and poly-piperazine amide mixed type composite nanometer filtering film, retaining molecular weight 150～300Dalton (dalton), membrane flux 18L/m
2H, flow of filtrate 1L/min, under 20 ℃ and 0.6MPa condition, behind the membrane sepn 15 hours, record that Cu concentration is 119.46mg/L in the concentrated solution, see through that Cu concentration is 3mg/L in the liquid, the Cu cycles of concentration is 7.36 times, this nanofiltration membrane, sees through liquid and is used further to production technique greater than 91% the rejection of Cu behind the membrane sepn.Concentrated solution after membrane separation apparatus is handled is used 1mol/L H
2SO
4It is 3 that solution is regulated its pH value, this concentrated solution is squeezed into electrolysis reactor 7 through pump 6, the electrolysis reactor anode material is an iridium oxide coated titanium plate, cathode material is a stainless steel plate, and two-plate spacing 16mm, barrier film are the porous water-permeable membrane, mould material is a polysulfones, the aperture is 0.22 μ m, at concentrated solution circular flow 2.0L/h, cathode current density 80A/m
2, temperature is to carry out electrolysis procedure under 25 ℃ of conditions, electrolysis is after 2 hours, records that Cu concentration is 19.11mg/L in the concentrated solution, and the electrolytic reaction Cu rate of recovery 90%, raffinate is used further to production technique after the electrolysis.
Claims (1)
1. the integrated processing of membrane sepn-electrolysis contains the method for heavy metal copper waste water, it is characterized in that comprising following process:
1) pre-treatment of heavy metal copper waste water: with copper concentration is the waste water adding slurry tank of 10mg/L～1000mg/L, under 20～25 ℃, gravity settling 12～24 hours, get supernatant liquor, remove the fine solid particle particle and the copper chip that suspend in the supernatant liquor with the micron filter of aperture 5～15 μ m and get filtrate;
2) filtrate that obtains of step 1) is carried out membrane sepn: with pump filtrate is squeezed into membrane separation apparatus, film in the membrane separation apparatus is polyvinyl alcohol and poly-piperazine amide mixed type composite nanometer filtering film or polyamide-based complex reverse osmosis membrane, retaining molecular weight 150～300 dalton, membrane flux 15～35L/m
2H, flow of filtrate 1～3L/min, under 20～35 ℃ and 0.6～1.0MPa pressure, membrane sepn is after 15～24 hours, and heavy metal copper ion rejection reaches more than 90% in the filtrate, sees through liquid behind the membrane sepn and is used further to production technique;
3) the concentrated solution electrolytic reaction after the separation: the concentrated solution behind the membrane sepn that step 2) obtains, use 1mol/L H
2SO
4Or 1mol/L NaOH solution to regulate its pH value be 2～3, then concentrated solution is squeezed into electrolysis reactor with pump, cathode material in the electrolysis reactor is a stainless steel plate, anode material is the titanium plate of iridium oxide coating, barrier film is the porous water-permeable membrane, and mould material is a polysulfones, and the aperture is 0.20～0.45 μ m, at concentrated solution circular flow 1.5～2.5L/h, cathode current density 50～100A/m
2, temperature is to carry out electrolysis procedure under 20～35 ℃ of conditions, electrolysis is after 1～3 hour, and enriched in metals copper on the electrolysis reactor negative plate, raffinate is used further to production technique after the electrolysis.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB200710056689XA CN100488899C (en) | 2007-02-01 | 2007-02-01 | Diaphragm separation electrolyzing integrated treatment method for waste water containing heavy metal copper |
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| CNB200710056689XA CN100488899C (en) | 2007-02-01 | 2007-02-01 | Diaphragm separation electrolyzing integrated treatment method for waste water containing heavy metal copper |
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| CN101024533A CN101024533A (en) | 2007-08-29 |
| CN100488899C true CN100488899C (en) | 2009-05-20 |
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Assignee: ZHAOQING FEINAN METAL CO., LTD. Assignor: Tianjin University Contract record no.: 2010440001147 Denomination of invention: Method of diaphragm separation electrolyzing integrated treatment of wate, water containing heavy metal copper Granted publication date: 20090520 License type: Exclusive License Open date: 20070829 Record date: 20100813 |
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