CN104671611B - The process of heavy metal in a kind of process electroplating wastewater up to standard recycle-water - Google Patents
The process of heavy metal in a kind of process electroplating wastewater up to standard recycle-water Download PDFInfo
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Abstract
The invention discloses the process of heavy metal in a kind of process electroplating wastewater up to standard recycle-water, including Individual pretreatment step, the method is further comprising the steps of: a): removes and reclaims heavy metal: utilize electrocoagulation to drift along heavy metal that method and coagulation membrane filter technique remove after Individual pretreatment in electroplating wastewater, and heavy metal out of electroplating wastewater product is reclaimed；B): the removal of residual hardly degraded organic substance: adopt oxidation technology, organism fluidization technology and adsorption technology remove the hardly degraded organic substance of residual in electroplating wastewater and low concentration electroplating wastewater is enriched with further successively to step a has removed electroplating wastewater that reclaim plurality of heavy metal, isolate the waste water up to standard that can directly discharge eluting output high-concentration electroplating wastewater；C): concentration wastewater to reach standard processes: adopt the alpha limit set film-forming system high-concentration electroplating wastewater to being enriched with in step b to carry out desalting processing, the concentrated solution up to standard that can directly discharge and the standard recovery liquid of the direct recycling up to standard of energy are isolated.
Description
Technical field
The present invention relates to electroplating waste water treatment technology field, particularly relate to the process of heavy metal in a kind of process electroplating wastewater up to standard recycle-water.
Background technology
Electroplating industry is the processing industry that China is important, at present with zinc-plated, copper facing, chromium plating and nickel plating equal distribution at machine manufacture, light industry, electronics, aviation and instrument industry；It is reported, the annual emissions of whole nation electroplating technology waste water, more than 400,000,000 tons, causes serious environmental pollution.Since formally implementing along with new " plating pollutant emission standard " (GB21900-2008), electroplating industry pollution emission control requires further strict.According to the preliminary statistics, the electroplating enterprise in the whole nation about 60% needs that treatment facility is transformed or increased treatment facility further and can be only achieved new standard-required.
Electroplating waste water treatment technology is also varied, generally can be divided into four classes: chemical method, Physical, physical-chemical process, biochemical process etc..The eighties in 20th century based on multiplexed combination technology, at present external Electroplating Wastewater Treatment 90% chemical method used above.The application percentage of domestic various waste water treatment process is followed successively by chemical method, ion exchange, electrolysis from big to small.These techniques all exist certain not enough in actual applications:
1, usual heavy metal out of electroplating wastewater content is relatively low, and water treating capacity is big, causes that added amount of chemical is big, easily causes secondary pollution；
2, process equipment floor space is big, and running cost is high, fixed investment is bigger；
3, operational process of craft is more complicated, and operation easier is bigger；
4, existing technique to the processing procedure of electroplating wastewater mostly can not low-concentration metallic in efficient recovery waste water, can not effectively realize the Treatment for Reuse of electroplating wastewater simultaneously, cause comparatively serious secondary pollution；
5, newly electroplating the issuing and implementation of pollutant emission standard (GB21900-2008) so that discharge standard for pollutants from electroplating industry increasingly stringent, domestic existing electroplating waste water treatment technology part cannot meet New emission standard requirement.
Summary of the invention
The technical problem to be solved is the present situation for above-mentioned prior art, and provide method simple, efficiently, cost low, and Pollutants in Wastewater can be made stably to reduce discharging and the process of heavy metal in the process electroplating wastewater a kind of up to standard of resource recycling recycle-water.
This invention address that the technical scheme that above-mentioned technical problem adopts is: the process of heavy metal in a kind of process electroplating wastewater up to standard recycle-water, include the Individual pretreatment step to electroplating wastewater, the method is further comprising the steps of:
: remove and reclaim heavy metal: utilize electrocoagulation to drift along heavy metal that method and coagulation membrane filter technique remove after Individual pretreatment in electroplating wastewater, and heavy metal out of electroplating wastewater product is reclaimed a)；
B): the removal of residual hardly degraded organic substance: adopt oxidation technology, organism fluidization technology and adsorption technology remove the hardly degraded organic substance of residual in electroplating wastewater and low concentration electroplating wastewater is enriched with further successively to step a has removed electroplating wastewater that reclaim plurality of heavy metal, isolate the waste water up to standard that can directly discharge eluting output high-concentration electroplating wastewater；
C): concentration wastewater to reach standard processes: adopt the alpha limit set film-forming system high-concentration electroplating wastewater to being enriched with in step b to carry out desalting processing, the concentrated solution up to standard that can directly discharge and the standard recovery liquid of the direct recycling up to standard of energy are isolated.
For optimizing technique scheme, the measure taked also includes:
In above-mentioned step a, the electrocoagulation method of drifting along is that the heavy metal ion in electroplating wastewater separates cohesion under electrochemical reaction effect from water, and carries out flotation precipitation under bubble, removes the heavy metal that in water, proportion is bigger；Coagulation membrane filter technique is that the electroplating wastewater having removed part heavy metal under previous reaction effect is taken out filter membrane after coagulation, and the metal ion in waste water is removed further.
In above-mentioned step a, heavy metal product reclaims and comprises the following steps:
D): solid-liquid separation: by precipitation or centrifugation, precipitate or separator are reclaimed；
E): high-temperature calcination: adopt high-temperature calcination technique to reclaim the material containing metal ion the precipitate in step d or separator.
The process conditions temperature of above-mentioned high-temperature calcination is 700-900 DEG C.
Oxidation technology in above-mentioned steps b is the catalytic ozonation technology that the electroplating wastewater after step a is processed by the Strong oxdiative ability utilizing ozone to have carries out ozone catalytic process；
The electroplating wastewater that organism fluidization technology in above-mentioned steps b is after adopting spiral-flow type biological fluidized bed ozone catalytic to be processed removes the spiral-flow type organism fluidization bed technique of hardly degraded organic substance in electroplating wastewater further with cyclone mode entrance eddy flow biological fluidized bed efficient biochemical process；
Adsorption technology in above-mentioned steps b be electroplating wastewater after adopting adsorbent resin to be processed by efficient biochemical through adsorbent resin adsorption reaction remove further in electroplating wastewater still cannot the resin absorption technology of degradation of organic substances, described adsorbent resin is the Polar Adsorbent Resin adopting pretreatment.
Above-mentioned Polar Adsorbent Resin is process the polarity Na type resin containing heavy metal-containing electroplating effluent.
Above-mentioned adsorbent resin carries out the method for pretreatment: takes 80ml resin and is placed in resin column, a certain amount of 3-5%HCl solution is passed into the flow velocity of 5BV/h, pass into ultra-pure water until water outlet pH is in neutrality, then a certain amount of 3-5%NaOH solution is passed into the flow velocity of 5BV/h, and soak 2 hours, pass into ultra-pure water until water outlet pH is in neutrality.
Above-mentioned electroplating wastewater is dynamic adsorption through adsorbent resin adsorption reaction: first measures 80ml wet resin with graduated cylinder and loads in adsorption column, after fixing, at 25 DEG C of temperature, the electroplating wastewater containing metal is made to flow through adsorption column with certain constant flow rate, collect effluent and measure its corresponding metal concentration, until resin reaches adsorption equilibrium, the now metal concentration in the close water inlet of metal concentration in effluent.
Above-mentioned alpha limit set film-forming system includes supermicro filtration membrane system and desalination membrane system；This alpha limit set film-forming system utilizes the limit Design of recycle-water pretreatment system, and the concentrated solution making membrance separation can direct qualified discharge.
Above-mentioned supermicro filtration membrane system includes supermicro filtration membrane, the high-concentration electroplating wastewater of eluting output in step b is passed through the further separating treatment of supermicro filtration membrane by this supermicro filtration membrane system, remove the polluter in high-concentration electroplating wastewater, high-concentration electroplating wastewater after removing polluter is screened further by desalination membrane system by separating film, makes the concentrated solution qualified discharge of membrance separation.
Compared with prior art, the present invention utilizes the effect of electrocoagulation-sink-float and coagulation sucking filtration that the electroplating wastewater containing heavy metal is processed, and heavy metal recycled, the response rate is up to 80%, not only avoid heavy metal and secondary pollution that chemical agent brings, but also add the added value of production.
The present invention passes through concerted catalysis oxidation and the adsorption of ozone-cyclone fluidized bed-adsorbent resin, it is achieved the qualified discharge of electroplating wastewater；Adopt Integrated Films system membrane separation concentration waste water is processed so that it is can qualified discharge, without advanced treating again, the electroplating waste-water reutilizing of more than 60% can be made, it is achieved that resource recycle.
The technology of the present invention highly versatile, cost is low, and efficiency is high, can effectively reduce secondary pollution, is adapted at plating, electron trade extensive use.
Accompanying drawing explanation
Fig. 1 is the process chart of present example.
Detailed description of the invention
Below in conjunction with accompanying drawing, embodiments of the invention are described in further detail.
Fig. 1 is the process flow diagram of the present invention.
The process of heavy metal in the process electroplating wastewater a kind of up to standard of the present invention recycle-water, includes the early stage Individual pretreatment step to electroplating wastewater, and the method is further comprising the steps of:
: remove and reclaim heavy metal: utilize electrocoagulation to drift along heavy metal that method and coagulation membrane filter technique remove after Individual pretreatment in electroplating wastewater, and heavy metal out of electroplating wastewater product is reclaimed a)；
B): the removal of residual hardly degraded organic substance: adopt oxidation technology, organism fluidization technology and adsorption technology remove the hardly degraded organic substance of residual in electroplating wastewater and low concentration electroplating wastewater is enriched with further successively to step a has removed electroplating wastewater that reclaim plurality of heavy metal, isolate the waste water up to standard that can directly discharge eluting output high-concentration electroplating wastewater；Step a has been removed the further oxidation removal of hardly degraded organic substance of residual in the electroplating wastewater reclaiming plurality of heavy metal by the present invention, low concentration electroplating wastewater is enriched with further, it is achieved the qualified discharge of waste water.
C): concentration wastewater to reach standard processes: adopt the alpha limit set film-forming system high-concentration electroplating wastewater to being enriched with in step b to carry out desalting processing, the concentrated solution up to standard that can directly discharge and the standard recovery liquid of the direct recycling up to standard of energy are isolated.
In the step a of the present invention, the electrocoagulation method of drifting along is that the heavy metal ion in electroplating wastewater separates cohesion under electrochemical reaction effect from water, and carries out flotation precipitation under bubble, removes the heavy metal that in water, proportion is bigger；Membrane filter technique is that the electroplating wastewater having removed part heavy metal under previous reaction effect is taken out filter membrane after coagulation, and the metal ion in waste water is removed further.
The present invention utilizes the effect of electrocoagulation-sink-float and coagulation sucking filtration that the electroplating wastewater containing heavy metal is processed, and heavy metal recycled, the response rate, up to 80%, not only avoid heavy metal and secondary pollution that chemical agent brings, but also adds the added value of production.
In above-mentioned step a, heavy metal product reclaims and comprises the following steps:
D): solid-liquid separation: by precipitation or centrifugation, precipitate or separator are reclaimed；
E): high-temperature calcination: adopt high-temperature calcination technique to reclaim the material containing metal ion the precipitate in step d or separator.
The present invention utilizes the electroplating wastewater containing heavy metal after electrocoagulation-effect of drifting along process Individual pretreatment, utilizes coagulation membrane filtration to reclaim heavy metal product, and reclaims heavy metal substance by high-temperature calcination.
The process conditions temperature of above-mentioned high-temperature calcination is 700-900 DEG C.
Oxidation technology in above-mentioned steps b is the catalytic ozonation technology that the electroplating wastewater after step a is processed by the Strong oxdiative ability utilizing ozone to have carries out ozone catalytic process；
The electroplating wastewater that organism fluidization technology in above-mentioned steps b is after adopting spiral-flow type biological fluidized bed ozone catalytic to be processed removes the spiral-flow type organism fluidization bed technique of hardly degraded organic substance in electroplating wastewater further with cyclone mode entrance eddy flow biological fluidized bed efficient biochemical process；The present invention adopts spiral-flow type organism fluidization bed technique that with eddy flow, the electroplating wastewater after ozone Oxidation Treatment is entered biological fluidized bed, it is achieved rapidly and efficiently biodegradation, removes the Organic substance of difficult degradation in waste water further.
Adsorption technology in above-mentioned steps b be electroplating wastewater after adopting adsorbent resin to be processed by efficient biochemical through adsorbent resin adsorption reaction remove further in electroplating wastewater still cannot the resin absorption technology of degradation of organic substances, adsorbent resin is the Polar Adsorbent Resin adopting pretreatment.After the present invention makes ozone catalytic-efficient biochemical process by resin absorption technology, the residual organic matter still cannot degraded in electroplating wastewater, process through polar resin adsorption reaction, it is ensured that final outflow water meets emission request.
Above-mentioned Polar Adsorbent Resin is process the polarity Na type resin containing heavy metal-containing electroplating effluent.
Above-mentioned adsorbent resin carries out the method for pretreatment: takes 80ml resin and is placed in resin column, a certain amount of 3-5%HCl solution is passed into the flow velocity of 5BV/h, pass into ultra-pure water until water outlet pH is in neutrality, then a certain amount of 3-5%NaOH solution is passed into the flow velocity of 5BV/h, and soak 2 hours, pass into ultra-pure water until water outlet pH is in neutrality.
Above-mentioned electroplating wastewater is dynamic adsorption through adsorbent resin adsorption reaction: first measures 80ml wet resin with graduated cylinder and loads in adsorption column, after fixing, at 25 DEG C of temperature, the electroplating wastewater containing metal is made to flow through adsorption column with certain constant flow rate, collect effluent and measure its corresponding metal concentration, until resin reaches adsorption equilibrium, the now metal concentration in the close water inlet of metal concentration in effluent.
Above-mentioned alpha limit set film-forming system includes supermicro filtration membrane system and desalination membrane system；This alpha limit set film-forming system utilizes the limit Design of recycle-water pretreatment system, makes the concentrated solution energy directly qualified discharge of membrance separation, without carrying out advanced treating again.
Above-mentioned supermicro filtration membrane system includes supermicro filtration membrane, the high-concentration electroplating wastewater of eluting output in step b is passed through the further separating treatment of supermicro filtration membrane by this supermicro filtration membrane system, remove the polluter in high-concentration electroplating wastewater, high-concentration electroplating wastewater after removing polluter is screened further by above-mentioned desalination membrane system by separating film, makes the concentrated solution qualified discharge of membrance separation.
Adopting the ozone secondary cycle of the utilization ratio being improved ozone to utilize technology in catalytic ozonation technology of the present invention, ozone utilization rate is more than 90%；And in conjunction with AOPs technology, accelerate O3Decompose, to improve catalytic organism reaction rate.
The spiral-flow type biological fluidized bed of the present invention utilizes effective fluidisation of absorbent charcoal carrier and the swirl jet of waste water, improves O3Contact with Organic substance uniformly and reaction probability, and prevent catalysis to be in operation compacting, increase running resistance.
The present invention utilizes the electroplating wastewater containing heavy metal after electrocoagulation-effect of drifting along process Individual pretreatment, utilizes coagulation membrane filtration to reclaim heavy metal product, and reclaims heavy metal substance by high-temperature calcination；Utilize the concerted catalysis oxidation of ozone-cyclone fluidized bed-adsorbent resin and adsorption to process by removing the hardly degraded organic substance remained in the electroplating wastewater of plurality of heavy metal, make adsorbent resin water outlet to discharge by stably reaching standard；The high-concentration electroplating wastewater that adsorbent resin eluting is enriched with by limit of utilization Integrated Films system carries out desalting processing so that it is can directly qualified discharge or recycling, it is not necessary to carry out advanced treating again.The technique of the present invention has that cost is low, efficiency is high and the feature such as highly versatile, can heavy metal in high efficiente callback electroplating wastewater, reduce secondary pollution, be adapted at plating, electron trade extensive use.
Claims (6)
1. a process for heavy metal in process electroplating wastewater up to standard recycle-water, includes the Individual pretreatment step to electroplating wastewater, it is characterized in that: the method is further comprising the steps of:
: remove and reclaim heavy metal: utilize electrocoagulation to drift along heavy metal that method and coagulation membrane filter technique remove after Individual pretreatment in electroplating wastewater, and heavy metal out of electroplating wastewater product is reclaimed a)；The described electrocoagulation method of drifting along is that the heavy metal ion in electroplating wastewater separates cohesion under electrochemical reaction effect from water, and carries out flotation precipitation under bubble, removes the heavy metal that in water, proportion is bigger；Described coagulation membrane filter technique is that the electroplating wastewater having removed part heavy metal under previous reaction effect is taken out filter membrane after coagulation, and the metal ion in waste water is removed further；
B): the removal of residual hardly degraded organic substance: adopt oxidation technology, organism fluidization technology and adsorption technology remove the hardly degraded organic substance of residual in electroplating wastewater and low concentration electroplating wastewater is enriched with further successively to step a has removed electroplating wastewater that reclaim plurality of heavy metal, isolate the waste water up to standard that can directly discharge eluting output high-concentration electroplating wastewater；Described oxidation technology is the catalytic ozonation technology that the electroplating wastewater after step a is processed by the Strong oxdiative ability utilizing ozone to have carries out ozone catalytic process；The electroplating wastewater that described organism fluidization technology is after adopting spiral-flow type biological fluidized bed ozone catalytic to be processed removes the spiral-flow type organism fluidization bed technique of hardly degraded organic substance in electroplating wastewater further with cyclone mode entrance eddy flow biological fluidized bed efficient biochemical process；Described adsorption technology be adopt adsorbent resin by the electroplating wastewater after biochemical treatment through adsorbent resin adsorption reaction remove further in electroplating wastewater still cannot the resin absorption technology of degradation of organic substances, described adsorbent resin is adopt the Polar Adsorbent Resin through pretreatment；Described adsorbent resin carries out the method for pretreatment: takes 80ml resin and is placed in resin column, a certain amount of 3-5%HCl solution is passed into the flow velocity of 5BV/h, pass into ultra-pure water until water outlet pH is in neutrality, then a certain amount of 3-5%NaOH solution is passed into the flow velocity of 5BV/h, and soak 2 hours, pass into ultra-pure water until water outlet pH is in neutrality；Described electroplating wastewater is dynamic adsorption through adsorbent resin adsorption reaction: first measures 80ml wet resin with graduated cylinder and loads in adsorption column, after fixing, at 25 DEG C of temperature, the electroplating wastewater containing metal is made to flow through adsorption column with certain constant flow rate, collect effluent and measure its corresponding metal concentration, until resin reaches adsorption equilibrium, the now metal concentration in the close water inlet of metal concentration in effluent；
C): concentration wastewater to reach standard processes: adopt the alpha limit set film-forming system high-concentration electroplating wastewater to being enriched with in step b to carry out desalting processing, the concentrated solution up to standard that can directly discharge and the standard recovery liquid of the direct recycling up to standard of energy are isolated.
2. the process of heavy metal in a kind of process electroplating wastewater up to standard according to claim 1 recycle-water, is characterized in that: in described step a, heavy metal product reclaims and comprises the following steps: d): solid-liquid separation: by precipitating or precipitate or separator are reclaimed by centrifugation；E): high-temperature calcination: adopt high-temperature calcination technique to reclaim the material containing metal ion the precipitate in step d or separator.
3. the process of heavy metal in a kind of process electroplating wastewater up to standard according to claim 2 recycle-water, is characterized in that: the process conditions temperature of described high-temperature calcination is 700-900 DEG C.
4. the process of heavy metal in a kind of process electroplating wastewater up to standard according to claim 3 recycle-water, is characterized in that: described Polar Adsorbent Resin is process the polarity Na type resin containing heavy metal-containing electroplating effluent.
5. the process of heavy metal in a kind of process electroplating wastewater up to standard according to claim 4 recycle-water, is characterized in that: described alpha limit set film-forming system includes supermicro filtration membrane system and desalination membrane system；This alpha limit set film-forming system utilizes the limit Design of recycle-water pretreatment system, and the concentrated solution making membrance separation can direct qualified discharge.
6. the process of heavy metal in a kind of process electroplating wastewater up to standard according to claim 5 recycle-water, it is characterized in that: described supermicro filtration membrane system includes supermicro filtration membrane, the high-concentration electroplating wastewater of eluting output in step b is passed through the further separating treatment of supermicro filtration membrane by this supermicro filtration membrane system, remove the polluter in high-concentration electroplating wastewater, high-concentration electroplating wastewater after removing polluter is screened further by described desalination membrane system by separating film, makes the concentrated solution qualified discharge of membrance separation.
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| CN106630392B (en) * | 2016-11-29 | 2019-04-16 | 江苏澳光电子有限公司 | A kind of method of bioanalysis degradation electroplating wastewater |
| CN107188261A (en) * | 2017-06-02 | 2017-09-22 | 北京中科康仑环境科技研究院有限公司 | A kind of recycling treatment process of molybdenum-containing acid wastewater |
| CN109502878B (en) * | 2017-09-15 | 2022-03-08 | 上海江柘环境工程技术有限公司 | Electroplating wastewater treatment system and treatment method thereof |
| CN109250867A (en) * | 2018-10-19 | 2019-01-22 | 江门市崖门新财富环保工业有限公司 | A kind of same thinking controlled of electroplating wastewater muddy water |
| CN109928559A (en) * | 2019-04-29 | 2019-06-25 | 苏州无为环境科技有限公司 | A kind of electroplating effluent treatment method |
| CN110921949B (en) * | 2019-11-05 | 2022-03-29 | 四川美富特环境治理有限责任公司 | Electroplating wastewater recycling treatment method |
| CN111170582A (en) * | 2020-01-19 | 2020-05-19 | 昆明金泽实业有限公司 | Treatment process for standard-reaching discharge and recovery of electroplating wastewater |
| CN112340874A (en) * | 2020-10-20 | 2021-02-09 | 江苏中远稀土新材料有限公司 | Method for pretreating electroplating wastewater by catalyzing persulfate through iron-containing acid solution |
| CN113582446B (en) * | 2021-07-28 | 2022-06-03 | 南京大学盐城环保技术与工程研究院 | Electroplating park comprehensive wastewater treatment method |
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| CN1686870A (en) * | 2005-03-31 | 2005-10-26 | 苏州市环境工程有限责任公司 | Technique for processing reclamation of industrial wastewater from printing electronic circuit board |
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