CN101935126B - Combined treatment method for electro-deposition and membrane separation of zinc-containing heavy metal waste water - Google Patents
Combined treatment method for electro-deposition and membrane separation of zinc-containing heavy metal waste water Download PDFInfo
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- CN101935126B CN101935126B CN2010102780902A CN201010278090A CN101935126B CN 101935126 B CN101935126 B CN 101935126B CN 2010102780902 A CN2010102780902 A CN 2010102780902A CN 201010278090 A CN201010278090 A CN 201010278090A CN 101935126 B CN101935126 B CN 101935126B
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Abstract
The invention discloses a combined treatment method for electro-deposition and membrane separation of zinc-containing heavy metal waste water, which is combined treatment of electro-deposition and two-level membrane separation. The method comprises the following steps of: electro-deposition: enabling waste water to enter a reuse water groove, a multi-medium filter-1, a flat-panel electro-deposition device and a three-dimension electro-deposition device; recycling metal zinc in the waste water, and purifying to obtain metal zinc; and two-level membrane separation: enabling the waste water subjected to the electro-deposition to pass through a pH regulating tank, a regulating tank and a multi-media filter-2 to enter an ultra-filtration membrane system and a low pressure reverse osmosis membrane system, making concentrated solution generated by the membrane system enter the regulating tank, a reaction tank and a sedimentation tank; and then returning to the multi-medium filter-1, making the concentrated solution pass through two electro-deposition devices, and recycling the metal zinc in the concentrated solution generated by the membrane system, wherein only one port is used for recycling the waste water. The invention has the advantages that by utilizing the combined process of electro-deposition and membrane separation, the problem existing in the prior art is solved, virtuous circle of production and treatment is realized, the reuse ratio of the waste water is high, the operation cost is low, and the complete recycling of the heavy metal pollutant and zero emission are substantially realized.
Description
Technical field
The present invention relates to a kind of process for treating industrial waste water, specifically, relate to contain the galvanic deposit and the membrane sepn combination treatment method of zinc heavy metal wastewater thereby.
Background technology
Heavy metal wastewater thereby is to environment and the great pollutent of human health risk; Appearance along with a series of enviromental protection laws and standard; To heavy metal wastewater thereby treatment requirement also increasingly stringent, heavy metal wastewater thereby results from numerous industries and industrial sectors such as metallurgy, plating, chemical industry, electronics, machinofacture and processing.Efficiently when removing heavy metal ions in wastewater, realize that recovery is the developing direction of heavy metal containing wastewater treatment from now on to waste water recycling with heavy metal.The method of the waste water of conventional process heavy metal comprises: method of chemical treatment, biological treatment, electrochemical treatment method; But during the chemical Treatment heavy metal-containing waste water; Owing to contain a large amount of organic complexs in many heavy metal wastewater therebies; Limited the chemical settling process, the waste water heavy metal content after causing handling exceeds standard; Cost is low though biological treatment has, and the advantage of convenient processing owing to receive the influence of wastewater toxicity, be difficult to extensive the realization, and the efficient of handling is low, and effect is relatively poor; In Applied Electrochemistry method processing in the past, when heavy metal concentration in the waste water reduces, exist energy consumption big, the problem that treatment effect is relatively poor.
The trade effluent of domestic main zinc smelting and electroplating enterprise, it is up to standard to adopt traditional heavy metal precipitation art breading heavy metal wastewater thereby to be difficult to, and effluxes the back serious environment pollution; The waste water reclamation rate is low, reclaims water quality inferiority, and heavy metal contaminants can't reclaim; The waste resource; Cause the present situation of secondary pollution easily, the new heavy metal contaminants of the present invention's exploitation can be realized reclaiming and zero release the novel process of water resources complete-reclaiming fully basically.
Summary of the invention
The objective of the invention is to overcome the weak point that exists in the prior art, and the galvanic deposit-two-stage membrane sepn treatment combination technology of the electrolytic zinc poaching wastewater of a kind of less investment, high efficiency is provided.
Technical scheme of the present invention is: contain the galvanic deposit and the membrane sepn combination treatment method of zinc heavy metal wastewater thereby, this method is two steps of combined treatment that waste water carries out galvanic deposit, two-stage membrane sepn:
First step: galvanic deposit
It is poor that waste water gets into reuse water, regulate pH4～5 in-1 be added to reuse water poor in, after this waste water gets into more medium filter-1; Get into flat electric deposition device, three-dimensional electric deposition device again; After the metallic zinc, proceed metal processing and purify in the recovery waste water, obtain metallic zinc;
Galvanic deposit refers to flat electric deposition device and three-dimensional electric deposition device;
Second step: two-stage membrane sepn
Waste water after the galvanic deposit; Through adjusting-2, equalizing tank, the more medium filter-2 of pH3.5～5.5, get into ultrafiltration membrane system, low pressure reverse osmosis film system, through two-stage film separating system gained liquid concentrator; Get into equalizing tank, reaction tank, settling tank; Get back to then in the more medium filter-1, pass through flat electric deposition device, three-dimensional electric deposition device again, reclaim metallic zinc;
The two-stage membrane sepn refers to that ultrafiltration membrane system separates with low pressure reverse osmosis film system;
And waste water reclamation has only 1 mouth, from the low pressure reverse osmosis system.
Metallic zinc retrieve to come from two parts, a part is to derive from the electrodeposition process that contains the zinc heavy metal wastewater thereby, recovery be the metallic zinc that contains in the zinc heavy metal wastewater thereby; A part derives from the waste water after the galvanic deposit in addition, is back to the electrodeposition process behind the electric deposition device through the liquid concentrator that produces behind the two-stage membrane sepn, recovery be the metallic zinc in the liquid concentrator that the film system produces in this combination treatment method.
The processing condition of following each parts of stated and function:
PH regulator-1:pH is 4～5;
The Zn of flat electric deposition device
2+Minimum concentration reduce and to reach 100mg/L;
The condition of said three-dimensional electrodeposition process zinc-containing water is: solution is carried out stirring at normal temperature, and electrode materials is selected graphite anode/stainless steel cathode counter-electrodes for use, and bath voltage is 4.0V, and electrolysis time is 60min; Three-dimensional galvanic deposit is granular or other fragmental working electrode material of filling between the conventional two-dimensional electrolytic tank electrode, and makes the granular electrode material surface of filling charged, becomes a new utmost point (the 3rd utmost point), in working electrode material surface energy generation electrochemical reaction; Zn after three-dimensional electric deposition device is handled
2+Minimum concentration be lower than 10mg/L, the clearance of zine ion reaches more than 95%;
Said the working pressure of use is controlled at 0.6～0.9MPa in low pressure reverse osmosis LPRO sepn process, Zn in the water outlet
2+Concentration reduces 0.1-0.5mg/L, and the average removal efficient of zine ion is 85%, goes out water power and leads and be reduced to 50 μ S/cm; 25 ℃～35 ℃ of waste water working temperatures, wastewater pH regulates 3.5～5.5; Low pressure reverse osmosis membrane process producing water ratio is 75%～85%, and average rejection is produced water water quality and is superior to the industrial circulating water water quality standard 92%～95%, can be back to industrial cycle water system or water quality requirement high use water spot;
More medium filter-1, more medium filter-2 all are the suspended substances of removing in the water, reduce the turbidity of water, satisfy the ultrafiltration water inlet and require (turbidity is less than 1.0NTU);
PH regulator pond-2:pH is 3.5～5.5;
Equalizing tank: be used for retaining, stationary flow;
Ultrafiltration membrane system is to remove materials such as suspended substance, colloid in the water, and water quality reaches feed water by reverse osmosis requirement (be mainly SDI (alluvial index)＜3.0, turbidity is less than 0.10); Average removal efficient at ultrafiltration UF (Ultrafiltration) sepn process zine ion is 50% to 70%, adds the micelle reinforced additive sodium laurylsulfonate of 0.1g/L SDS, and the removal efficient of zine ion reaches 99%;
Waste water after the above-mentioned processing carries out ultrafiltration membrane treatment technology earlier, carries out low pressure reverse osmosis film LPRO again and separates, and with the water outlet effect of assurance r-o-, and practices thrift the required energy of reverse osmosis equipment;
The two-stage membrane separation process produces 20%～25% liquid concentrator, gets into equalizing tank, reaction tank, settling tank again through circulation, gets back to again in the more medium filter-1; Pass through electric deposition device again; After reclaiming metallic zinc, and the water that is at this moment produced carries out reuse; Can realize that so whole technology has only the discharge reuse outlet of a clear water, and heavy metal contaminants can be realized basically reclaiming fully and zero release.
Said membrane sepn process; Handle through ultra-filtration membrane and low pressure reverse osmosis film; Fully heavy metal in the concentrating spent liquor makes the concentration of metal ions in the liquid concentrator obtain bigger raising, is applicable to galvanic deposit recovery heavy metal; The water power that goes out of low pressure reverse osmosis sepn process is led and is reduced to 50 μ S/cm, and is easy to realize the cycling and reutilization of water outlet.
The present invention compared with prior art has following advantage:
First; Utilize the newest fruits of galvanic deposit and membrane sepn treatment technology; Combine electro-deposition techniques and membrane separation treating process, give full play to the advantage of electrochemical reduction and membrane separation technique in the galvanic deposit, solved the problem that electrochemical reduction processing mode in the past exists.
The second, the purification of waste water reuse of heavy metal containing wastewater treatment and heavy metal reclaim simultaneously and accomplish, and have realized the benign cycle of producing and handling.
The 3rd, disclose process mechanism from microscopic scale, develop the analysis of mass transfer model and the equation of heavy metal electrodeposition process, and mass transfer rule and the separating dynamics of heavy metal ion in the membrane sepn process made research.
The 4th, to the waste water of different concns and composition corresponding treatment process mode is proposed, for the appropriate design of device and the optimization of operating process provide theoretical direction.
This spent process water reclamation rate of the present invention high (can reach 75%-80%), running cost are low, and whole technology has only the discharge reuse outlet of a clear water, and heavy metal contaminants can be realized reclaiming fully and zero release basically.
Advantage according to galvanic deposit and two-stage membrane separation technique; Can reach minimum working cost and optimal separating efficiency, when realizing the qualified discharge of water, heavy metal resources in the efficient recovery waste water; In efficient recovery waste water, in the heavy metal, realize recycling of water.
Description of drawings
Fig. 1 contains the galvanic deposit and the membrane sepn combination treatment method schema of zinc heavy metal wastewater thereby for the present invention
Embodiment
Enumerate 1 embodiment below,, the present invention is further specified, but the present invention is not only limited to this embodiment in conjunction with accompanying drawing.
The inventive method step adopts the process combination of flat electric deposition device-three-dimensional electric deposition device-ultrafiltration membrane system-low pressure reverse osmosis film system, and concrete technical process is following:
First step: galvanic deposit
Waste water at first is collected in the reuse tank, regulates waste water with pH4, and waste water carries out preliminary filtration treatment to former water after getting into the disc type more medium filter, to remove the fouling deposition that some macrobead suspended substances and inorganic salts are separated out.According to the concentration situation of waste water heavy metal ion, waste water gets into flat electric deposition device and three-dimensional electric deposition device, after the metallic zinc, proceeds metal processing and purifies in the recovery waste water, obtains metallic zinc;
Second step: two-stage membrane sepn
The waste water that galvanic deposit is come out, temperature are controlled at 25 ℃～35 ℃, pH value to 5.5; Through equalizing tank, more medium filter-2, remove the suspended substance in the water, the turbidity that reduces water is to satisfy the ultrafiltration water inlet; Get into ultrafiltration membrane system, materials such as the suspended substance in the removal water, colloid get into low pressure reverse osmosis film system, equalizing tank, reaction tank, settling tank again; The liquid concentrator that comes out by settling tank then; Get back in the more medium filter-1, pass through flat electric deposition device, three-dimensional electric deposition device again, reclaim metallic zinc.
And waste water reclamation has only 1 mouth, from the low pressure reverse osmosis system.And heavy metal contaminants can be realized reclaiming fully and zero release basically.
Claims (3)
1. the galvanic deposit and the membrane sepn combination treatment method that contain the zinc heavy metal wastewater thereby is characterized in that this method is two steps of combined treatment that waste water carries out galvanic deposit, two-stage membrane sepn:
First step: galvanic deposit
It is poor that waste water gets into reuse water, regulate pH4～5 in-1 be added to reuse water poor in, after this waste water gets into more medium filter-1; Get into flat electric deposition device, three-dimensional electric deposition device again; After the metallic zinc, proceed metal processing and purify in the recovery waste water, obtain metallic zinc;
Galvanic deposit refers to flat electric deposition device and three-dimensional electric deposition device;
Second step: two-stage membrane sepn
Waste water after the galvanic deposit; Through adjusting-2, equalizing tank, the more medium filter-2 of pH3.5～5.5, get into ultrafiltration membrane system, low pressure reverse osmosis film system, through two-stage film separating system gained liquid concentrator; Get into equalizing tank, reaction tank, settling tank; Get back to then in the more medium filter-1, pass through flat electric deposition device, three-dimensional electric deposition device again, reclaim metallic zinc;
The two-stage membrane sepn refers to that ultrafiltration membrane system separates with low pressure reverse osmosis film system;
And waste water reclamation has only 1 mouth, from the low pressure reverse osmosis system;
Metallic zinc retrieve to come from two parts, a part is to derive from the electrodeposition process that contains the zinc heavy metal wastewater thereby, recovery be the metallic zinc that contains in the zinc heavy metal wastewater thereby; A part derives from the waste water after the galvanic deposit in addition, is back to the electrodeposition process behind the electric deposition device through the liquid concentrator that produces behind the two-stage membrane sepn, recovery be the metallic zinc in the liquid concentrator that the film system produces in this combination treatment method.
2. galvanic deposit and the membrane sepn combination treatment method that contains the zinc heavy metal wastewater thereby as claimed in claim 1; It is characterized in that: the condition of said three-dimensional electrodeposition process zinc-containing water is: solution is carried out stirring at normal temperature; Electrode materials is selected graphite anode/stainless steel cathode counter-electrodes for use; Bath voltage is 4.0V, and electrolysis time is 60min.
3. galvanic deposit and the membrane sepn combination treatment method that contains the zinc heavy metal wastewater thereby as claimed in claim 1 is characterized in that: said in the sepn process of low pressure reverse osmosis film system, the working pressure of use is controlled at 0.6～0.9MPa, Zn in the water outlet
2+Concentration reduces 0.1-0.5mg/L, and the average removal efficient of zine ion is 85%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102432123A (en) * | 2011-11-03 | 2012-05-02 | 北京大学 | Reproducible heavy metal complexing agent and application method thereof |
| CN102491568A (en) * | 2011-11-25 | 2012-06-13 | 北京大学 | Method for treating wastewater of electrolytic zinc rinsing technology |
| CN103663803A (en) * | 2012-09-17 | 2014-03-26 | 武汉环材科技有限公司 | Efficient electro-deposited heavy metal cleaning system |
| CN106045139A (en) * | 2016-06-17 | 2016-10-26 | 红板（江西）有限公司 | Device and process for composite electrochemical reaction pretreatment and recycling of board surface cleaning water in circuit board industry |
| CN106082508A (en) * | 2016-08-09 | 2016-11-09 | 成都虹华环保科技股份有限公司 | A kind of device processing hydrometallurgy heavy metal wastewater thereby and processing method |
| CN106673285B (en) * | 2016-11-29 | 2018-03-23 | 环境保护部华南环境科学研究所 | A kind of recycling recoverying and utilizing method containing golden electroplating wastewater |
| CN107352708B (en) * | 2017-07-03 | 2018-08-07 | 界首市菁华科技信息咨询服务有限公司 | A kind of processing method of lead smelting wastewater |
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| 吴彦军，张林楠，李振山.重金属废水无害化处理技术最新进展.《工业水处理》.2009,第29卷(第3期),第2页第2栏最后一段至第3页结尾，图2. * |
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