CN101544435B - Method for treating electroplating wastewater containing cyanogen and silver and and device thereof - Google Patents
Method for treating electroplating wastewater containing cyanogen and silver and and device thereof Download PDFInfo
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- CN101544435B CN101544435B CN2009101116396A CN200910111639A CN101544435B CN 101544435 B CN101544435 B CN 101544435B CN 2009101116396 A CN2009101116396 A CN 2009101116396A CN 200910111639 A CN200910111639 A CN 200910111639A CN 101544435 B CN101544435 B CN 101544435B
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- cyanogen
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- argentiferous
- negative electrode
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Abstract
The invention discloses a method for treating electroplating wastewater containing cyanogen and silver and a device thereof, relates to a method and a device for treating electroplating wastewater, and provides a method and a device for reclaiming the silver and decomposing the cyanogen from low-concentration electroplating wastewater containing the cyanogen and the silver by adopting a pulse power supply and a static electrode technique. The treatment device comprises an electrolysis bath, a power supply, a circulating pump, an aerator, an electrode group, a tubular liquid distributor and an aeration pipe; the electrode group, the tubular liquid distributor and the aeration pipe are fixed on the bottom of the electrolysis bath respectively; the tubular liquid distributor is arranged on a cathode side of the electrode group, and a liquid inlet is connected with the circulating pump; an anode side of the electrode group is provided with at least one aeration pipe, and a gas inlet is connected with the aerator; an inlet end of the circulating pump is communicated with the electrolysis bath; and the power supply adopts the pulse power supply. The reclaiming rate of the silver is over 99 percent, the purify of electrolytic silver can reach over 99.5 percent, in addition, the decomposing rate of cyanide reaches over 83 percent; and the required energy consumption in the whole process is low, the time is short, the treating efficiency is high, and the cost is low.
Description
Technical field
The present invention relates to a kind of method of electroplating wastewater treatment and device, especially relate to a kind of cyanogen argentiferous method of electroplating wastewater treatment and device thereof of containing.
Background technology
Silver is important precious metal, has good electrical conductivity, ductility, photosensitivity and chemical stability, has been widely used in fields such as electronics, chemical industry, photographic material, medicine and aerospace.Plating is the important means that obtains metal silver surface, electroconductibility is silver-plated and in various light industrial products ornamental silver-plated in that electrical equipment, instrument etc. is carried out, what produce contains cyanogen argentiferous electroplate rinsing wastewater in a large number, the mass concentration of silver is in 0.5～3g/L scope, and the mass concentration of total cyanogen is in 0.5～6g/L scope.Mainly contain ion exchange method, zinc substitution method etc. to containing cyanogen argentiferous method of electroplating wastewater treatment at present.In recent years; in order more reasonably to utilize resource; the protection environment; adopt electrochemical process more effectively from electroplating wastewater, to reclaim precious metal; decompose prussiate and become one of this area research focus; its emphasis is that the design of electrolyzer and electrode makes it more to help improving mass-transfer efficiency and stability; fluidized-bed electrolyzer as Britain BEWT; the fluidized-bed electrolyzer of the Industrial Technology Research Institute of Taiwan and the flat electrolyzer of disturbed flow type negative electrode; the concavo-convex thin plate electrolysis device of France and ECO electrolyzer etc.; these devices can reclaim certain precious metal from electroplating wastewater; but treatment effect is still undesirable, and can not directly carry out solid-liquid separation.
Publication number is that the application for a patent for invention of CN1609011A discloses a kind of electrolyzer that is used to handle the high density cyanide waste liquor, anode is made up of with a plurality of granular graphite at least one electrically conductive graphite rod, its negative electrode is made up of at least one metal bar, there is the porous insulation thing to contact with each other preventing between anode and the negative electrode, the porous insulation thing is a tubulose, be looped around each metal bar periphery, electrolyzer has delivery pipe to discharge the noble metal powder that electrolysis is separated out in this electrolyzer.This electrolyzer can be handled the electroplating wastewater that total cyanogen content is 3～6g/L, but has complex structure, investment problem such as big, difficult in maintenance, and the metal of its recovery is Powdered.
U.S. Pat 4028199 discloses a kind of rotor cathode assembly with scraper, though this device can carry out continuous electrolysis production, but when electrode rotates, electrolytic solution forms the rotation cylinder, make ectonexine ionogen handover mass transfer difficulty, therefore, it is low to be used for dilute solution recovery metal efficient, and power consumption is big.In addition, direct supply is all adopted in existing most of electrolysis researchs, and it will make electrode produce " polarizing effect " and wear out gradually, influence the performance of electrolyzer greatly, reduce work-ing life.
Summary of the invention
Purpose of the present invention is intended to provide a kind of cyanogen argentiferous method of electroplating wastewater treatment and device thereof of containing.
Technical scheme of the present invention is to adopt the pulse power and static electrode technology, contains from lower concentration and reclaims silver the cyanogen argentiferous electroplating wastewater and decompose cyanogen.
The cyanogen argentiferous electroplating waste processing equipment that contains of the present invention is provided with electrolyzer, power supply, recycle pump, oxygenating machine, electrode group, tubular liquid sparger and aeration tube; Electrode group, tubular liquid sparger and aeration tube are individually fixed in bottom of electrolytic tank, and the electrode group comprises anode and negative electrode, and electrode is communicated with power supply; At least one tubular liquid sparger is located at the cathode-side of electrode group, and the tubular liquid sparger is a hollow tube, and tube wall one side is established at least one liquid exit, and body top liquid-inlet is connected with circulating-pump outlet; The anode side of electrode group is established at least one aeration tube, and the aeration tube top connects pin shower nozzle or core aeration head, and the aeration tube bottom is gas feed, and gas feed is connected with oxygenating machine; The pump inlet end is communicated with electrolyzer.
A plurality of electrode groups and supporting tubular liquid sparger, aeration tube can be set in the electrolyzer.
Anode and negative electrode preferably are arranged in co-axial alignment, and the distance between anode and the negative electrode is preferably 45～50mm.Described liquid exit is towards negative electrode.Power supply is preferably the pulse power, and both ends of power preferably is provided with reometer and voltmeter.
The cyanogen argentiferous method of electroplating wastewater treatment that contains of the present invention may further comprise the steps:
1) the pending cyanogen argentiferous electroplating wastewater that contains is added in the electrolyzer, regulate the pH value 8.5～9.5;
2) open recycle pump, the Control Circulation flow velocity is opened oxygenating machine at 50～150ml/min, and control aeration speed is 1.0～3.0L/min;
3) behind the system stability, open electrolysis power, the setting pulse power parameter: dutycycle is 40%～60%, and pulse-repetition is 800～1200Hz, and electrolysis voltage is 0.9～1.5V;
4) in reaction process, anode carries out the reaction of prussiate decomposing oxidation, and negative electrode carries out argent and separates out reduction reaction, and detect a waste water silver content and contain the cyanogen amount every 30min, after silver content is less than 10mg/L, termination reaction;
5) pull down negative electrode, after cleaning with distilled water, at air drying, peel the electrolysis silver layer then, the electrolytic silver that obtains reclaiming.
Compare with existing plating silver waste water treatment process, because the present invention adopts the pulse power, its peak point current intensity is much larger than average current intensity, in interpulse period, pass through stirring action, silver ions around the negative electrode obtains replenishing rapidly, make current efficiency reach 99.9%, the rate of recovery of silver is more than 99%, make the impurity component that is adsorbed on the negative electrode be broken away from cathode surface simultaneously, improve the purity of electrolytic silver, the purity of electrolytic silver can reach more than 99.5%, and reclaiming silver is solid, separates easy.In addition, pulse dc power can reduce " polarizing effect " to greatest extent, guarantees that the electrolyzer output performance is stable, and electrode life improves greatly.Owing to adopt the pump circulation of liquid distributor, the mode in conjunction with continuous aeration around the anode promotes effectively that when increasing substantially mass-transfer efficiency anode carries out the oxidizing reaction of prussiate, and the rate of decomposition of prussiate reaches more than 83%.The required energy consumption of whole process is low, and is with short production cycle, the processing efficiency height, and the production run cost is low, is a kind of wastewater processing technology that can be applicable to prussiate decomposition or silver recovery.Potential application is that cyanogen such as nickeliferous, copper, zinc, gold and silver, lead, cadmium are electroplating wastewater.
Description of drawings
Fig. 1 is the treatment unit synoptic diagram of electroplating wastewater of the present invention.
Fig. 2 is the bottom of electrolytic tank vertical view.
Fig. 3 is a tubular liquid sparger synoptic diagram.
Fig. 4 is scanning electronic microscope (SEM) photo of the silver that pulse electrolysis is reclaimed among the embodiment 1.
Fig. 5 is powder x-ray diffraction (XRD) collection of illustrative plates of the silver that pulse electrolysis is reclaimed among the embodiment 1.In Fig. 5, X-coordinate be diffraction angle 2 θ (°), ordinate zou is relative diffracted intensity Intensity; 5 feature diffraction of simple substance silver crystalline absorption peak is respectively (111), (200), (220), (311), (222).
Embodiment
The invention will be further described below in conjunction with accompanying drawing.
Referring to Fig. 1～3, it is electrolyzer 1 that the treatment unit of electroplating wastewater adopts rectangular parallelepiped tetrafluoroethylene groove, is anode 7 with cylindric Graphite Electrodes, is negative electrode 8 with cylindric stainless steel electrode, anode 7 and negative electrode 8 are arranged in co-axial alignment and are fixed on electrolyzer 1 bottom, and pole span R is 50mm; Tubular liquid sparger 9 is fixed in negative electrode 8 limits, is evenly distributed with 4 aeration tubes 10 around anode 7; Tubular liquid sparger 9 is a hollow tube, and tube wall one side is established more than one liquid exit 91, and body top liquid-inlet is connected with recycle pump 5, and liquid exit 91 is towards negative electrode; Aeration tube 10 tops connect the pin shower nozzle, and the bottom is that gas feed is connected with oxygenating machine 6; Recycle pump 5 entrance ends are communicated with electrolyzer 1; Power supply 2 adopts the pulse power, and both ends of power is connected with anode 7 and negative electrode 8 with voltmeter 4 by reometer 3.
Get the pending cyanogen argentiferous electroplating wastewater that contains of 1.5L and join in the electrolyzer, wherein silver ion content is 1000mg/L, and total cyanogen content is 2000mg/L, waste water ph is regulated and is stabilized in 9; Open recycle pump and oxygenating machine, control waste water circulation velocity is 100ml min
-1, aeration speed is 1.5L min
-1Setting pulse power parameter in the electrolytic process: dutycycle is 60%, and pulse-repetition is 800Hz, and electrolysis voltage is 1.5V; Measure silver content and total cyanogen amount of waste water every 30min.Behind the electrolysis 1.5h, the waste water silver content is 10mg/L, and containing the cyanogen amount is 80mg/L, stopped reaction.Silver raising recovery rate is 99%, and the prussiate rate of decomposition is 94%.Reaction is pulled down negative electrode after finishing, and after cleaning with distilled water, at air drying, peels the electrolysis silver layer then, obtains the silver that pulse electrolysis is reclaimed.The silver-colored SEM photo that reclaims is seen Fig. 4, silver-colored even particle size, compact crystallization, the about 4.5 μ m of particle diameter.Corresponding XRD figure spectrum is seen Fig. 5,5 feature diffraction of tangible simple substance silver crystalline absorption peak occurred in (111), (200), (220), (311), (222), does not find the characteristic peak that desilver is outer, shows electrolytic recovery silver purity height, greater than 99.5%.
Adopt treatment unit and electroplating wastewater among the embodiment 1, the pH value is controlled at 9.0, circulation velocity stuck-at-00ml min
-1, aeration speed stuck-at-.5L min
-1, change pulse power parameter, repeat implementation procedure among the embodiment 1.In reaction times under the different electrical power parameter, silver raising recovery rate and cyanogen rate of decomposition see Table 1.
Table 1
Claims (7)
1. contain cyanogen argentiferous electroplating waste processing equipment, it is characterized in that being provided with electrolyzer, power supply, recycle pump, oxygenating machine, electrode group, tubular liquid sparger and aeration tube; Electrode group, tubular liquid sparger and aeration tube are individually fixed in bottom of electrolytic tank, and the electrode group comprises anode and negative electrode, and electrode is communicated with power supply; At least one tubular liquid sparger is located at the cathode-side of electrode group, and the tubular liquid sparger is a hollow tube, and tube wall one side is established at least one liquid exit, and body top liquid-inlet is connected with circulating-pump outlet; The anode side of electrode group is established at least one aeration tube, and the aeration tube top connects pin shower nozzle or core aeration head, and the aeration tube bottom is gas feed, and gas feed is connected with oxygenating machine; The pump inlet end is communicated with electrolyzer;
Described power supply is a pulse dc power.
2. the cyanogen argentiferous electroplating waste processing equipment that contains as claimed in claim 1 is characterized in that being provided with in the electrolyzer at least one electrode group and supporting tubular liquid sparger, aeration tube.
3. the cyanogen argentiferous electroplating waste processing equipment that contains as claimed in claim 1 is characterized in that anode and negative electrode are arranged in co-axial alignment.
4. the cyanogen argentiferous electroplating waste processing equipment that contains as claimed in claim 3 is characterized in that the distance between anode and the negative electrode is 45～50mm.
5. the cyanogen argentiferous electroplating waste processing equipment that contains as claimed in claim 1 is characterized in that described liquid exit is towards negative electrode.
6. the cyanogen argentiferous electroplating waste processing equipment that contains as claimed in claim 1 is characterized in that both ends of power is provided with reometer and voltmeter.
7. contain cyanogen argentiferous method of electroplating wastewater treatment, it is characterized in that, adopt to contain cyanogen argentiferous electroplating waste processing equipment according to claim 1, the treating method comprises following steps:
1) the pending cyanogen argentiferous electroplating wastewater that contains is added in the electrolyzer, regulate the pH value 8.5～9.5;
2) open recycle pump, the Control Circulation flow velocity is opened oxygenating machine at 50～150ml/min, and control aeration speed is 1.0～3.0L/min;
3) behind the system stability, open electrolysis power, setting pulse direct supply parameter: dutycycle is 40%～60%, and pulse-repetition is 800～1200Hz, and electrolysis voltage is 0.9～1.5V;
4) in reaction process, anode carries out the reaction of prussiate decomposing oxidation, and negative electrode carries out argent and separates out reduction reaction, and detect a waste water silver content and contain the cyanogen amount every 30min, after silver content is less than 10mg/L, termination reaction;
5) pull down negative electrode, after cleaning with distilled water, at air drying, peel the electrolysis silver layer then, the electrolytic silver that obtains reclaiming.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101116396A CN101544435B (en) | 2009-04-30 | 2009-04-30 | Method for treating electroplating wastewater containing cyanogen and silver and and device thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101116396A CN101544435B (en) | 2009-04-30 | 2009-04-30 | Method for treating electroplating wastewater containing cyanogen and silver and and device thereof |
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| Publication Number | Publication Date |
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| CN101544435A CN101544435A (en) | 2009-09-30 |
| CN101544435B true CN101544435B (en) | 2011-07-20 |
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| ITRM20120394A1 (en) * | 2012-08-06 | 2014-02-07 | Antonino Abrami | METHOD AND SYSTEM OF REDUCING THE CONCENTRATION OF SUSPENDED POLLUTANTS IN WATER FOR SITE ECOLOGY AND FOR BUYING |
| CN103787524A (en) * | 2012-10-30 | 2014-05-14 | 苏州市环境保护有限公司 | KMnO4 oxidation reaction based silver-containing wastewater treatment method |
| CN111377566A (en) * | 2018-12-27 | 2020-07-07 | 山东新海表面技术科技有限公司 | Method for surface treatment of cyanide in wastewater |
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Granted publication date: 20110720 Termination date: 20140430 |