CN100396627C - Clean production method for treating electroplating waste water by nano filtering process - Google Patents
Clean production method for treating electroplating waste water by nano filtering process Download PDFInfo
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- CN100396627C CN100396627C CNB2006100961339A CN200610096133A CN100396627C CN 100396627 C CN100396627 C CN 100396627C CN B2006100961339 A CNB2006100961339 A CN B2006100961339A CN 200610096133 A CN200610096133 A CN 200610096133A CN 100396627 C CN100396627 C CN 100396627C
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- electroplating
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Abstract
The invention is a clean producing method of processing electroplating waste water by nano filtration, belonging to the electroplating waste water processing technical field, comprising preprocessing and nano filtering condensing processes, where the entrapped ratio of bivalent ions is larger than 99%, the feed liquid can be condensed to 17000mg/L, and the concentrate is used in the plating bath; in the condensing course, the concentration of bivalent ions in 87.5% of the penetrating liquid is lower than 1.0mg/L, and that in 9.62% of the penetrating liquid is lower than 2.3mg/L, where the two parts of penetrating liquid are directly used in the potcher, and that in 2.88% of the penetrating liquid is lower than 15 mg/, where this part of penetrating liquid can be fed with the feed liquid. And it implements zero-effluent clean producing process; and keeps higher flux of membrane, and especially applies to industrial application of electronickelling.
Description
Technical field
A kind of clean preparation method for the treatment of electroplating waste water by nano filtering process belongs to electroplating wastewater and administers technical field.The present invention adopts
Type nanofiltration membrane, single stage method are handled and are concentrated electroplating wastewater.See through the liquid complete-reclaiming in rinse tank, the concentrated solution direct reuse has reclaimed water resources and heavy metal resources fully in plating tank, truly accomplishes the process for cleanly preparing of process zero release.
Background technology
In electronickelling industry rinse cycle, can produce a large amount of nickel-containing waste waters, Ni
2+Can generate water-soluble salt with multiple inorganics, organism complexing, human body is produced harm, aquatic organism is also had tangible toxic action.Simultaneously, if the enrichment effectively of the nickel in these nickel-containing waste waters, rinsing liquid just might be recycled.China's integrated wastewater discharge standard (GB8978-2005) regulation Ni
2+The highest permissible discharge concentration be 1.0mg/L.Handling at present with the main method that reclaims heavy metal has: the chemical reduction precipitation, absorption, little electrolysis, method [[1] Hatfield T L such as evaporation and ion-exchange, Kleven T L, Pierce D T.Electrochemical remediation of metal-bearing waste waters.Part 1:Copperremoval form simulated drainage waters[J] .Journal of Applied Electrochemical, 1996,26:567-574.[2] Tu Zhenmi, Li Deyu, Li Ning, Pan Li, Zhang Jingshuan. present situation and progress [J] that chemical nickle-plating wastewater is handled. electroplate and environmental protection, 2003,23 (2): 1-5.[3] DKNY Na, Ma Shaojian. cobalt in the waste material, the recovery of nickel [J]. coloured mining and metallurgy, 2005,21 (7): 113-114.], there are the following problems in these traditional technologies: (1) needs heavy dose of chemical substance; (2) eliminated the possibility of the heavy metal ion that directly is recycled; (3) needing the mud of processing to contain a large amount of organism and heavy metal, form new solid pollutant, also is quite difficult during processing.
In recent years, adopt membrane separation technique to handle electroplating wastewater and obtain extensive studies, especially nanofiltration (NF) technology, since coming out, received people's very big concern always, and [[4] Petersen R J.Composite reverse osmosis and nanofiltration membrane[J] the .J MembrSci that is widely used rapidly, 1993,83:81.[5] Rautenbach R, Groschl A.Separation potential ofnanofiltration membranes[J] .Desalination, 1990,77:73-84.].Nanofiltration membrane has following distinguishing feature in application: sieve effect is held back or held back to (1) physics, can hold back less dissolved constituent effectively; (2) charge [[6] Wang X L, Tsuru T, Nakao S, et al.Electrolytetransport through nanofiltration membranes by the Space-charge model and thecomparison with Teorell-Meyer-Sievers model[J] .J Membr Sci, 1995,103:117-133.], be that selectivity is held back, rejection to univalent ion lower (40%～80%) [[7] Ding Huanru, Du Fangzheng, Wang Lihai. application present situation and the prospect [J] of membrane technique in China's water treatment of power plant. Shanghai University Of Electric Power's journal, 2002,18 (3): 271.], rejection to divalence and polyvalent ion is then higher, so can hold back most of heavy metal ion, realizes the enrichment of heavy metal ion, can replace the desalination in traditional engineering, a plurality of steps such as concentrate, so both economical; (3) to compare working pressure low with reverse osmosis, see through big [[8] the Xu Y Z of flow rate, Lebrun R E.Comparison of nanofiltration properties of twomembranes using electrolyte and non-electrolyte solutes[J] .Desalination, 1999,122:95-106.].(4) compare with the treatment process that method of evaporation or other have " mutually " to become, embrane method do not have " phase " to become, thereby energy consumption is low to the treating processes of electroplating wastewater; (5) nano filtering process treatment facility floor space is little, facility compact, easily automatic control, but operate continuously.
Utilize membrane separating method to handle the method for Electroplating Production waste water at present, as Chinese patent application number be 03157655.9 " membrane separating method of electroplating wastewater processing zero release ", disclose the method that a kind of electroplating wastewater is administered, this method will be passed through the one-level nanofiltration again through pretreated electroplating wastewater, the condensed water that obtains after the nanofiltration continues to concentrate through secondary brackish water reverse osmosis membrane, condensed water is separated concentrated at last through three grades of seawater reverse osmosis membranes, and provide the example of an electronickelling wastewater treatment, operate at normal temperatures through total system, electronickelling waste water has been concentrated about 100 times.This technology has overcome the deficiency of traditional method, but for industrial application complicated operation, the production cost height, technology is loaded down with trivial details.
So the present invention adopts a step Nanofiltering membrane handle to concentrate electroplating wastewater, it is simple to have technology, invests for a short time, and production cost is low, and recycle-water and heavy metal ion resource fully reach the process for cleanly preparing of process zero release.
Summary of the invention
The object of the invention is intended to overcome the deficiencies in the prior art, providing a kind of utilizes a new step nano filtering process to handle the method that concentrates electroplating wastewater, both can save the electroplating industry water resources, can make full use of heavy metal again, eliminate the production cost of pollution on the environment and reduction electroplating industry, realize the cleaner production of electroplating industry.
The present invention is based on the application of nanofiltration, its theoretical foundation is: sieve effect is held back or held back to (1) physics, can hold back less dissolved constituent effectively; (2) charge, promptly selectivity is held back, and to the rejection lower (40%～80%) of univalent ion, to the rejection of divalence and polyvalent ion then higher (more than 90%), so can hold back most of metal ion, realizes the enrichment of metal ion.
Technical scheme of the present invention, this method is:
1), the pre-treatment of electroplating wastewater
Earlier with strainer (comprising cloth envelop collector, fabric filter, micro-filtration, sand filtration etc.) the filtering anode sludge and debris particle impurity; Then with the organism in the activated carbon adsorption filtered wastewater; Use the suspended substance in the ultra-filtration membrane filtering waste water again.
2), nanofiltration membrane concentrating and separating
Will be through the pretreated waste water TFC that holds back relative molecular mass 80Da～120Da
-S type nanofiltration membrane is carried out concentrating and separating, working pressure is that 1.4MPa～2.6MPa (best is 1.8MPa～2.2MPa), is less than or equal to the feed liquid of 30mg/L for bivalent ions concentration, reach and concentrate 600 times, extremely bivalent ions concentration is 17700mg/L, and concentrated solution is got back to plating tank and used; To bivalent ions rejection greater than 99%, 87.5% quality see through in the liquid divalent ion concentration less than 1.0mg/L, 9.62% quality see through in the liquid divalent ion concentration less than 2.3mg/L, see through liquid and can be used as the rinse water reuse, 2.88% quality see through that divalent ion concentration is mixed into nanofiltration with feed liquid and handles less than 15mg/L in the liquid.Handled electroplating wastewater is that plated metal ion valence link is 2 or 3 waste water, as electroplated Ni
2+, Zn
2+, Cu
2+Or Cr
3+Waste water.
Compared with prior art, beneficial effect of the present invention is embodied in:
1, because the relative molecular mass of holding back of this nanofiltration membrane reaches 120Da, thus whole organism can be held back substantially, and through checking, it can hold back the divalent ion greater than 99%; In the operating process, need not to add chemical substance, do not have phase transformation; Seeing through liquid can complete-reclaiming, can not cause secondary pollution; And flow process is simple, less investment, equipment take up an area of little, process cost is low.
2, system adopts the method for nanofiltration, electronickelling waste water can be concentrated 600 times, concentrated solution is directly got back to plating tank, see through liquid as the rinse water reuse, for providing a kind of waste chemicals, reclaims electroplating industry, the process for cleanly preparing of factory effluent reuse has reduced the pollution of producing environment, realizes the zero release of electroplating wastewater.
3, after the inventive method was handled, total reclamation rate of water was greater than 99% in the electronickelling waste water, and the rate of recovery of heavy metal resources is greater than 99%.
Description of drawings
Fig. 1 process flow diagram.
Fig. 2 process unit synoptic diagram.
Embodiment
Below in conjunction with accompanying drawing the specific embodiment of the present invention is elaborated.
Figure 1 shows that the technical process of the embodiment of the invention, as shown in Figure 1, comprise pre-treatment, nanofiltration membrane separation, concentrated solution and see through the liquid reuse.
Embodiment 1 handles electroplated Ni
2+Waste water
1, pre-treatment
At first with Ni
2+Concentration be that the electronickelling waste water of 30mg/L is through 5 μ m cloth envelop collectors, with the big suspended impurity elimination of the anode sludge in the waste water, fragment etc.; Then adopt the most of organism in the active carbon adsorption absorption waste water, alleviate the pollution of organism membrane module; Pass through ultra-filtration equipment again, under 0.1MPa, waste water is further separated, remove suspended substance tiny in the waste water, thus the effect of playing the protective membrane element, prolonging its work-ing life.
2, nanofiltration membrane separation
Enter the nanofiltration membrane concentrating unit through pretreated waste water by topping-up pump, stage pump under 2.0MPa pressure and separate, this nanofiltration membrane is the TFC that U.S. KOCH company produces
-S type nanofiltration membrane, the aperture is a nano level, and it is 80 (dalton) that its relative molecular mass is held back scope, nanofiltration membrane surface lotus positive electricity, ion to different electric charges and different valence state has different Donnan current potentials, and the exclusive surface characteristic and the aperture of nanofiltration membrane have determined its particular performances.It is lower to the monovalent ion rejection, and divalent ion is had higher rejection, promptly the metal ion of different valence state is had selectivity and holds back.The nanofiltration membrane that native system adopts is at 2.0MPa pressure, and is lower to the rejection of sodium-chlor, have only about 20%, and can be up to more than 99% to bivalent ions rejection.Most sodium-chlor sees through membrane element, and Ni
2+Be trapped concentratedly, do to produce and use so the solution after concentrating can directly be got back to plating tank.Also available method of evaporation reclaims heavy metallic salt, or reclaims heavy metal with electrolytic process.Nanofiltration membrane is lower than reverse osmosis membrane pressure, flux big, investment is little.In order to alleviate the pollution of face, prolong the work-ing life of film, regularly device to be cleaned, the flux recovery is good.Through after the nanofiltration system, waste water is concentrated about 600 times, Ni
2+Concentration reaches 17700mg/L, to Ni
2+Rejection greater than the Ni in the liquid that sees through of 99%, 87.5% quality
2+Concentration is less than 1.0mg/L, 9.62% quality see through Ni in the liquid
2+Concentration is less than 2.3mg/L, these two portions see through liquid can fully recovering in electroplating rinse water.2.88% quality see through Ni in the liquid
2+Concentration is less than 15mg/L, can with the feed liquid combination treatment.
The method of the embodiment of the invention has certain for property.Directly be suitable for as electroplating wastewater, as electroplating Zn for other divalence or trivalent metal ion
2+, Cu
2+Or Cr
3+Waste water.
Embodiment 2 handles and electroplates Cr
3+Waste water
1, pre-treatment
At first with Cr
3+Concentration be that the chromium-electroplating waste water of 70mg/L carries out pre-treatment, operation is with embodiment 1.
2, nanofiltration membrane separation
Under 1.6MPa pressure, enter the nanofiltration membrane concentrating unit through pretreated waste water by topping-up pump, stage pump and separate, use TFC
-S type nanofiltration membrane is carried out nanofiltration and is concentrated, after treatment, and Cr in the concentrated solution
3+Concentration reaches 18000mg/L, to Cr
3+Rejection greater than seeing through liquid and can be back to electroplating rinse water more than 99%, 90%, remaining sees through the Cr in the liquid
3+Concentration is at 5～15mg/L, can with the feed liquid combination treatment.
Claims (4)
1. the clean preparation method of a treating electroplating waste water by nano filtering process is characterized in that:
1), the pre-treatment of electroplating wastewater
Earlier with the strainer filtering anode sludge and debris particle impurity; Then with the organism in the activated carbon adsorption filtered wastewater; Use the suspended substance in the ultra-filtration membrane filtering waste water again;
2), nanofiltration membrane concentrating and separating
To carry out concentrating and separating with the nanofiltration membrane of holding back relative molecular mass 80Da～120Da through pretreated waste water, working pressure is 1.4MPa～2.6MPa, the feed liquid that is less than or equal to 30mg/L for bivalent ions concentration, reach and concentrate 600 times, extremely bivalent ions concentration is 17700mg/L, and concentrated solution is got back to plating tank and used; To bivalent ions rejection greater than 99%, 87.5% quality see through in the liquid divalent ion concentration less than 1.0mg/L, 9.62% quality see through in the liquid divalent ion concentration less than 2.3mg/L, see through liquid as the rinse water reuse, 2.88% quality see through that divalent ion concentration is mixed into nanofiltration with feed liquid and handles less than 15mg/L in the liquid.
2. method according to claim 1, the working pressure that it is characterized in that the nanofiltration membrane concentrating and separating is 1.8MPa～2.2MPa.
3. method according to claim 1 is characterized in that handled electroplating wastewater is 2 or 3 waste water for the plated metal ionic valence condition.
4. method according to claim 3 is characterized in that handled electroplating wastewater is an electroplated Ni
2+, Zn
2+, Cu
2+Or Cr
3+Waste water.
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| CNB2006100961339A CN100396627C (en) | 2006-09-20 | 2006-09-20 | Clean production method for treating electroplating waste water by nano filtering process |
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| CN100396627C true CN100396627C (en) | 2008-06-25 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100443423C (en) * | 2007-04-27 | 2008-12-17 | 济南晶恒有限责任公司 | Electroplating wastewater treatment reclaiming technique |
| CN101811798A (en) * | 2010-03-23 | 2010-08-25 | 中国市政工程华北设计研究总院 | Method for improving security of water quality by utilizing microorganism-membrane compound technology |
| CN101792218A (en) * | 2010-03-30 | 2010-08-04 | 江西金达莱环保研发中心有限公司 | Electroplate rinsing wastewater online recycling method and device |
| CN102432123A (en) * | 2011-11-03 | 2012-05-02 | 北京大学 | Reproducible heavy metal complexing agent and application method thereof |
| CN103253798B (en) * | 2013-06-08 | 2014-09-10 | 国家海洋局天津海水淡化与综合利用研究所 | Zero discharge treatment and recycling method for chromium ions in electroplating wastewater and device of method |
| CN105461131B (en) * | 2014-12-25 | 2020-12-15 | 江苏泉之源环境技术有限公司 | Method for treating concentrated water of electroplating rinse water |
| CN105435653B (en) * | 2015-12-18 | 2018-02-06 | 贵阳时代沃顿科技有限公司 | A kind of composite nanometer filtering film to divalent ion removing with high selectivity and preparation method thereof |
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| WO2002101115A1 (en) * | 2001-06-08 | 2002-12-19 | Henkel Kommanditgesellschaft Auf Aktien | Preventing a membrane from blocking up during the treatment of waste water during phosphatization |
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| JP2005081226A (en) * | 2003-09-08 | 2005-03-31 | Institute Of Physical & Chemical Research | Nanofiltration membrane and production method therefor |
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2006
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Patent Citations (4)
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| US5959240A (en) * | 1996-12-04 | 1999-09-28 | Ngk Insulators, Ltd. | Thermoelectric converter for heat-exchanger |
| WO2002101115A1 (en) * | 2001-06-08 | 2002-12-19 | Henkel Kommanditgesellschaft Auf Aktien | Preventing a membrane from blocking up during the treatment of waste water during phosphatization |
| CN1590322A (en) * | 2003-09-05 | 2005-03-09 | 国家海洋局杭州水处理技术研究开发中心 | Membrane separation method of zero discharge of electroplating waste water treatment |
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Non-Patent Citations (2)
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Application publication date: 20070328 Assignee: Jiangsu Boda Environmental Protection Co., Ltd. Assignor: Jiangnan University Contract record no.: 2013320000302 Denomination of invention: Clean production method for treating electroplating waste water by nano filtering process Granted publication date: 20080625 License type: Exclusive License Record date: 20130407 |
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