CN101891286A - System for purifying and recycling electroplating/chemical plating wastewater on line - Google Patents
System for purifying and recycling electroplating/chemical plating wastewater on line Download PDFInfo
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Abstract
The invention belongs to the technical field of water treatment, and relates to a system for purifying and recycling electroplating/chemical plating wastewater on line. The system comprises a washing device positioned on an electroplating/chemical plating production line, wherein a purifying device is arranged in the washing device and is a capacitive deionization device; the capacitive deionization device comprises at least one electrode pair consisting of ion electroadsorption electrodes, collector electrodes and an insulating layer; two ion electroadsorption electrode layers covers the outer layer of the insulating layer in the electrode pair, and then two collector electrode layers covers the outer layer of the ion electroadsorption electrode layers; and one side of the insulating layer is an anode, and the other side of the insulating layer is a cathode. By combining the characteristics of the electroplating/chemical plating wastewater and the specific conditions of the process flow, a wastewater treatment and recovery system which is suitable to be practically applied to the field is arranged, so that various application parameters are optimized, and the wastewater amount is obviously reduced; meanwhile, the quality of plated parts is ensured and water resources are effectively saved; and in addition, the on-line recovery of waste materials is realized and resources are effectively utilized.
Description
Technical field
The invention belongs to water-treatment technology field, relate to electrochemistry and water technology, be specifically related to the system of a kind of in-line purification and recycling electroplating and chemical plating waste water.
Background technology
Along with the sharp increase of global population and the fast development of industrial and agricultural production, the Freshwater resources worsening shortages, simultaneously the water that causes because of industrial or agricultural and sanitary wastewater discharging pollutes and also is on the rise.Not only reduced its functions of use after the water pollution, the contradiction of further having aggravated shortage of water resources, but also serious threat is to human safe drinking water and health.Therefore, various is that the technology and the technology of target constantly released to solve shortage of water resources, and wherein waste water recycling is an effective way that solves shortage of water resources.Because the overwhelming majority in mankind itself and the industrial or agricultural water after use all the mode with waste water be discharged into occurring in nature, so waste water recycling has not only been opened up new water source, and reduce pollution to environment, be to kill two birds with one stone.
In view of the diversity and the complicacy of kind of waste water, the related waste water of this patent refers in particular to be electroplated and waste water that the electroless plating industry produces in process of production.Current have many technology can be applied to electroplate processing with chemical plating waste water, as flocculation sediment, activated carbon adsorption, membrane separation technique, ion exchange method, reverse osmosis technology etc.Publication number is the treatment process that the Chinese patent of CN101157509 has been introduced a kind of electroplating wastewater low emission, it adopts complex arts such as membrane concentration, membrane sepn, ion-exchange and ultraviolet catalytic oxidation, at first to the electroplating wastewater pre-treatment, then pickling waste waters, cyanide containing wastewater and passivation and electroplate rinsing composite waste three class waste water are handled respectively, can realize the part Wastewater Recovery, remain unrenewable waste water and reach the GB first discharge standard and discharge.
The patent No. is that the Chinese patent of 200410023427.X discloses a kind of processing method that reclaims nickel (Ni) from waste water, do negative electrode by adopting gac, enhancing generates the absorption property of nickel hydroxide during to electrolysis, thereby make the nickel hydroxide of recovery purer, and the rate of recovery of nickel can reach more than 99%.
More than these technological methods all be basically earlier with pending discharge of wastewater in Waste Water Treatment, and then is handled or is handled recovery afterwards.
In recent years, (Capacitive Deionization CDI) has characteristics such as less energy-consumption, capacity usage ratio height and non-secondary pollution and has received concern more and more widely in fields such as sea water desaltination, wastewater treatments the capacitive deionization technology because of it.Compare with traditional wastewater processing technology, the CDI technology only needs extra electric field, can finish absorption and the release to the waste water intermediate ion by electrode absorption (charging)/regeneration (discharge) process, and just can obtain to regenerate when discharging, and reuses.Device absorption, regenerated synoptic diagram are as shown in Figure 1.
The patent No. is that 01129623.2 Chinese patent has been introduced a kind of multi-stage electric capacitance deionizer, to overcome big, the more defective of material therefor of being taken up space that related single-pole device exists in two patents of United States Patent (USP) 5192432 and Japanese Patent JP94-325983.Deionizer in this patent is simple and compact for structure, and liquid flow path both can have been connected also can be in parallel, thereby improve the ion remaval rate.
Publication number is that the Chinese patent of CN 101518748A has been introduced a kind of deionizer and manufacture method thereof, it mainly improves the efficient of device by the spacing between the even maintenance electrode, improve electroconductibility by the contact resistance that reduces between carbon material and the collector simultaneously.
Above-mentioned patent and United States Patent (USP) 6,761,809,6,824,662,7,083,733,7,279,083 etc. in recent years all relate to the CDI device.But these patents have all only carried out describing qualitatively to the structure of their related CDI devices, and to the CDI device to give full play to its function many important parameters that should have, as correlation technique parameter of electrode pair area, interelectrode distance, the voltage range that applies, employed activated carbon fiber etc., all there is not quantitatively characterizing, obviously, the design of such device is to be difficult to the actual wastewater treatment of satisfying particular type.And electroplating and the electroless plating field, owing to contain a large amount of heavy metal ion in the waste water that it produced, as chromium (Cr), cadmium (Cd), plumbous (Pb), nickel (Ni), tin (Sn), copper (Cu), zinc (Zn), silver (Ag), gold (Au) etc., and the various synthetic class organic compound that are difficult to natural degradation, the intractability of plating and chemical plating waste water will be higher than common waste water far away.How the CDI technology is applied to electroplate/processing of chemical plating waste water, how the equipment of use adapts to the processing of plating/chemical plating waste water, and these all are open questions still in the prior art.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of can be applied to electroplate/system that chemical plating waste water is handled, can in-line purification and reclaim and electroplate and chemical plating waste water.
Invention provides a kind of in-line purification and has reclaimed the system of plating or chemical plating waste water, comprises the water washing device that is positioned on plating/electroless plating production line, and is positioned over the capacitor deionizing instrument in the water washing device.This device also can reclaim the useful matter in the waste water simultaneously to electroplating and chemical plating waste water in-line purification and reuse.Capacitor deionizing instrument is at process of charging enrichment ion; Discharge waste material at discharge process.
This capacitor deionizing instrument comprises the electrode pair that at least one is made of ion-conductance adsorption electrode, collector electrode and insulation layer; The skin of insulation layer is coated with two ion-conductance adsorption electrode layers in the electrode pair, and the skin of electro-adsorption electrode layer is coated with two collector layers then respectively; One side of described insulation layer is anodal, and opposite side is a negative pole.The size and location of ion-conductance adsorption electrode layer, collector layer and insulation layer are corresponding mutually and superimposed.
Ion-conductance adsorption electrode layer wherein is an activated carbon fiber, and collector layer is an expanded graphite plate, and insulation layer is the insulation porous barrier.The specific surface area of activated carbon fiber is 800～2000 meters squared per gram, and thickness is 1～3 millimeter; The thickness of described expanded graphite plate is 0.2～2 millimeter.
Insulation layer is divided into anodal and negative pole two portions with electrode pair, and the spacing between positive pole and the negative pole is 0.1～10 centimetre.Preferred spacing is 0.5～3.0 centimetre.The vesicular structure of insulating barrier can pass through fluid between positive pole and negative pole.
Capacitor deionizing instrument can be board-like, also can be rolling.
Board-like capacitor deionizing instrument is the electrode group that a plurality of electrode pairs constitute.Each electrode pair intermediate ion adsorption electrode layer is that area is 200～5000 square centimeters.Between each electrode pair, can separate by back up pad, back up pad also is an insulating.Pressure strip can be installed in the two ends of electrode group, makes that the structure of whole device is more compact.
10000～50000 square centimeters of the electrode pair areas of rolling capacitor deionizing instrument.
As the part in the water washing device in the plating/electroless plating production line, the needs that the parameter of capacitor deionizing instrument should realistic application, in order to reach the reasonable resources configuration, the present invention has done optimization to its volume with washing water simultaneously.Wherein, the ionic adsorption electrode total area ratio of water washing device volume and electrode group is 30～500 liters/square metre.
Remove this, in order to realize the abundant purification of washing water in energy-conservation, water washing device and capacitor deionizing instrument wherein are the multistage gradient settings in the system of the present invention;
The ratio of the volume of first step water washing device and described electrode pair/electrode group intermediate ion adsorption electrode total area is 30～200 liters/square metre; The ratio of the volume of second stage water washing device and electrode pair/electrode group intermediate ion adsorption electrode total area is 100～500 liters/square metre.The charging voltage of capacitor deionizing instrument is 1～30 volt.
Capacitor deionizing instrument among the present invention is arranged in the washing water device on plating/electroless plating production line, constitute a purification of waste water and recovery system, behind capacitive deionization discharge process adsorption cleaning waste water, discharge waste material by desorption, realize the regeneration of electrode simultaneously.
Each processing parameter of in-line purification of the present invention system is the optimum combination that draws in optimization Test repeatedly.Evidence, under technical parameter provided by the present invention, the waste water that plating and electroless plating are produced can be adsorbed in washing bath effectively, is purified to a great extent when making it enter next washing bath; And the processing parameter of next washing bath also is provided with according to the characteristic of the water outlet after purifying through upper level, saves power supply to reach in the wash water of effectively purifying waste water.
Compared with prior art, the present invention has following beneficial effect:
(1) system of in-line purification provided by the invention and recovery plating or chemical plating waste water, particular case in conjunction with plating/chemical plating waste water characteristics and technical process, be provided with the wastewater treatment and the recovery system that are suitable for being applied to this field, various application parameters have been optimized, realized the online treatment of real plating/chemical plating waste water, it can be directly in washing bath with pollutants in waste water, (comprise organic acid as metal ion and most of organism, additive, tensio-active agent etc.), online (original position) removal/purification, so not only can make the long-term reuse of washing water, significantly reduce the wastewater flow rate that is produced on the whole production line, and because the washing waste water that water produced substantially no longer contains pollutent after treatment, even after long-term reuse, discharge, also greatly reduce the burden of existing Waste Water Treatment, thereby the expense of wastewater treatment is obviously descended.
(2) system of in-line purification provided by the present invention and recovery plating or chemical plating waste water, by capacitor deionizing instrument being becomed privileged setting at plating/chemical plating technology, and with it reasonably as the organic formation in the plating/chemical plating technology, simplified the step of washing water in plating/chemical plating technology greatly, guarantee the quality of plating piece simultaneously, and effectively saved water resources.
(3) system provided by the present invention can realize the purifying treatment of plating/chemical plating waste water and the online recovery of waste material in same device, and is easy to operate, effectively utilized resource.
Description of drawings
Fig. 1 is absorption, the regeneration synoptic diagram of capacitive deionization technology.
Fig. 2 is a capacitor deionizing instrument synoptic diagram of the present invention (board-like), wherein 1 expression electrode supporting plate (pressure strip up and down); 2 expression graphite cakes (collector electrode); 3 expression activated carbon fiber materials (ion-conductance adsorption electrode); 4 expression insulation porous barriers (fluid channel).
Fig. 3 is wherein 1 an expression electrode supporting plate (pressure strip up and down) of capacitor deionizing instrument synoptic diagram of the present invention (rolling); 2 expression graphite cakes (collector electrode); 3 expression activated carbon fiber materials (ion-conductance adsorption electrode); 4 expression polyethylene films.
Embodiment
Below further specify technical scheme of the present invention by specific embodiment.
In order to verify method provided by the present invention in the effect aspect purifying waste water, the present invention also adopts atomic absorption spectrometry and potassium dichromate oxidation to detect the concentration of metal ions and the chemical oxygen demand COD of water outlet respectively.
Board-like capacitor deionizing instrument:
Selecting activated carbon fiber for use is ion-conductance adsorption electrode material, and thickness is 3 millimeters, specific surface area 1100 meters squared per gram; Expanded graphite plate with 1 mm thick is made collector electrode.
Cut 10 of the activated carbon fiber of 50 centimetres of 50 cm x, cut 10 of the graphite cakes of 50 centimetres of 50 cm x, the area of every plate electrode layer is 2500 square centimeters, and the electrode pair spacing is 0.5 centimetre.
The CDI device electrode group that assembling is made up of 5 electrode pairs, the assembling sequence of parts is: following pressure strip, the centre is arranged in order 5 groups of graphite cake-activated carbon fiber-insulation porous barrier-activated carbon fiber-graphite cake combination, separates with back up pad between every group, loads onto pressure strip at last.
The rolling capacitor deionizing instrument:
Selecting activated carbon fiber for use is ion-conductance adsorption electrode material, and thickness is 3 millimeters, specific surface area 1100 meters squared per gram.Expanded graphite plate with 1 mm thick is made collector electrode.
Cut 2 of the activated carbon fiber of 100 centimetres of 50 cm x, cut 2 of the graphite cakes of 100 centimetres of 50 cm x.
Graphite cake, activated carbon fiber, insulation porous barrier, activated carbon fiber, graphite cake, the sealed polyethylene plastic of long strip shape are stacked successively, and graphite cake is wherein reserved an end and is higher than activated carbon fiber as the conduction ear.Rolling-in then forms the suitable right cylinder of diameter, is loaded on the cylindrical vessel sealing, reserves the conduction ear of graphite cake, and liquid one end advances, and another brings out.
With the board-like CDI device of embodiment 1, place the water washing device of 100 liters of capacity, nickel plating washing water is carried out electro-adsorption test in parallel.
Metal ion content in the nickel plating washing water is 300ppm, COD value 1100,4 liters/minute of water inlet flow velocitys.Reach 100ppm note with the water outlet nickel ion concentration, the plating water treatment amount under 2,10,20 volts of operating voltage on every square metre of electrode pair the results are shown in table 1.The concentration of metal ions of water outlet and chemical oxygen demand COD adopt atomic absorption spectrometry and potassium dichromate oxidation to detect respectively.
Table 1: the CDI device is to the influence of the wash water of purifying waste water under the different operating voltage
| Operating voltage (volt) | 2? | 10? | 20? |
| The electrode pair total area (cm 2)? | 25000? | 25000? | 25000? |
| Water treatment amount (L) when the water outlet concentration of metal ions reaches 100ppm | 60? | 220? | 490? |
| Electrode pair water treatment capacity (the L/m of unit 2)? | 24? | 88? | 196? |
| COD(mg/l)? | 645? | 433? | 390? |
Data from table 1 as can be seen, under the situation that other technical parameter remains unchanged, operating voltage is high more, the CDI device is good more to washing water purification effect.But, from the angle of related work safety of persons and saving energy consumption is considered that the design of the operating voltage of this CDI device will be no more than 12 volts.
Except for the following differences, all the other are all with embodiment 3.
Regulate the electrode pair spacing and be respectively 0.1,3 and 10 centimetre, place the water washing device of 100 liters of capacity.Plating water treatment amount when setting operating voltage and being 10 volts on every square metre of electrode pair the results are shown in table 2.
The electrode pair spacing of table 2:CDI device is to the influence of the wash water of purifying waste water
| Electrode pair spacing (cm) | 0.1? | 3? | 10? |
| The electrode pair total area (cm 2)? | 25000? | 25000? | 25000? |
| Water treatment amount (L) when the water outlet concentration of metal ions reaches 100 ppm | 492? | 450? | 260? |
| Electrode pair water treatment capacity (the L/m of unit 2)? | 192.8? | 180? | 104? |
| COD(mg/l)? | 390? | 497? | 630? |
Data from table 2 as can be seen, under the situation that other technical parameter remains unchanged, the electrode pair spacing of CDI device is more little, it is good more to washing water purification effect.But, when interelectrode distance is too small, (when being 0.1 centimetre) such as the interelectrode distance in the table 2, because fluid course is too narrow, resistance to flow is excessive, unusual difficulty during actually operating.Therefore, our preferred electrode pair spacing is 0.5～3.0 centimetre.
Embodiment 5
Rolling CDI device with embodiment 2 carries out the electro-adsorption test to zinc-plated washing water.
The size of CDI device electrode centering ion-conductance adsorption electrode layer, collector layer and insulation layer and position are corresponding mutually and superimposed, the electrode pair of three different area is set, the area of single electrode layer is respectively 5000,10000 and 15000 square centimeters, and the electrode pair spacing is 0.5 centimetre.Place the water washing device of 100 liters of capacity.
The metal ion content of zinc-plated washing water is 790ppm, COD value 1340, and 4 liters/minute of control water inlet flow velocitys reach the 200ppm note with water outlet tin ion concentration liter, are 10 times in operating voltage, and the plating water treatment amount on every square metre of electrode pair the results are shown in table 4.The concentration of metal ions of water outlet and chemical oxygen demand COD adopt atomic absorption spectrometry and potassium dichromate oxidation to detect respectively.
The electrode pair area of table 3:CDI device is to the influence of the wash water of purifying waste water
| The electrode pair total area (cm 2)? | 10000? | 20000? | 50000? |
| Water treatment amount (L) when the water outlet concentration of metal ions reaches 200ppm | 30? | 180? | 610? |
| Electrode pair water treatment capacity (the L/m of unit 2)? | 30? | 90? | 122? |
| COD(mg/l)? | 1090? | 915? | 873? |
Data from table 3 as can be seen, under the situation that other technical parameter remains unchanged, the electrode pair area of CDI device is big more, it is good more to washing water purification effect.Because the space of the washing bath of plating and electroless plating is limited, thereby has determined that the CDI device size can not be excessive, this has also determined the right electrode area of necessary control CDI device electrode.
Claims (10)
1. the system of an in-line purification and recycling electroplating or chemical plating waste water, comprise the water washing device that is positioned on plating/electroless plating production line, it is characterized in that: refining plant is set in water washing device, described refining plant is a capacitor deionizing instrument, and this capacitor deionizing instrument comprises the electrode pair that at least one is made of ion-conductance adsorption electrode, collector electrode and insulation layer; The skin of insulation layer is coated with two ion-conductance adsorption electrode layers in the electrode pair, and the skin of ion-conductance adsorption electrode layer is coated with two collector layers then; One side of described insulation layer is anodal, and opposite side is a negative pole.
2. the system of in-line purification as claimed in claim 1 and recycling electroplating or chemical plating waste water is characterized in that: described ion-conductance adsorption electrode layer is an activated carbon fiber, and collector layer is an expanded graphite plate.
3. the system of in-line purification as claimed in claim 2 and recycling electroplating or chemical plating waste water is characterized in that: the specific surface area of described activated carbon fiber is 800～2000 meters squared per gram, and thickness is 1～3 millimeter; The thickness of described expanded graphite plate is 0.2～2 millimeter.
4. the system of in-line purification as claimed in claim 1 and recycling electroplating or chemical plating waste water is characterized in that: described insulation layer is the insulation porous barrier.
5. as the system of claim 1 or 4 described in-line purifications and recycling electroplating or chemical plating waste water, it is characterized in that: the spacing between described positive pole and the negative pole is 0.1～10 centimetre.
6. the system of in-line purification as claimed in claim 5 and recycling electroplating or chemical plating waste water is characterized in that: the spacing between described positive pole and the negative pole is 0.5～3.0 centimetre.
7. as the system of claim 3 or 6 described in-line purifications and recycling electroplating or chemical plating waste water, it is characterized in that: the electrode group that has an electrode pair or a plurality of electrode pair to constitute in the capacitor deionizing instrument, each electrode pair intermediate ion adsorption electrode layer are that area is the rolling of 200～5000 square centimeters board-like or 10000～50000 square centimeters.
8. the system of in-line purification as claimed in claim 7 and recycling electroplating or chemical plating waste water is characterized in that: the ionic adsorption electrode total area ratio of described water washing device volume and described electrode group is 30～500 liters/square metre.
9. the system of in-line purification as claimed in claim 8 and recycling electroplating or chemical plating waste water is characterized in that: described water washing device and capacitor deionizing instrument wherein are the multistage gradient settings; The ratio of the volume of first step water washing device and described electrode pair/electrode group intermediate ion adsorption electrode total area is 30～200 liters/square metre; The ratio of the volume of second stage water washing device and electrode pair/electrode group intermediate ion adsorption electrode total area is 100～500 liters/square metre.
10. as the system of claim 1 or 9 described in-line purifications and recycling electroplating or chemical plating waste water, it is characterized in that: the charging voltage of described capacitor deionizing instrument is 1～30 volt.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017124798A1 (en) * | 2016-01-22 | 2017-07-27 | 同济大学 | Composite membrane separation method applicable to desalting and recycling of sewage |
| CN109987779A (en) * | 2017-12-29 | 2019-07-09 | 宁波方太厨具有限公司 | A kind of water filtering system |
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| CN1330043A (en) * | 2001-06-25 | 2002-01-09 | 清华大学 | Multi-stage electric capacitance deionizer |
| CN101337717A (en) * | 2008-09-28 | 2009-01-07 | 上海纳晶科技有限公司 | High efficiency energy-conserving barrier diaphragm capacitance deionization device |
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- 2010-04-02 CN CN2010101441925A patent/CN101891286B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1330043A (en) * | 2001-06-25 | 2002-01-09 | 清华大学 | Multi-stage electric capacitance deionizer |
| CN101337717A (en) * | 2008-09-28 | 2009-01-07 | 上海纳晶科技有限公司 | High efficiency energy-conserving barrier diaphragm capacitance deionization device |
Non-Patent Citations (1)
| Title |
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| 《工业水处理》 20020831 孙晓慰等 电吸附水处理技术及设备 第1-3、40页 1-10 第22卷, 第8期 2 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017124798A1 (en) * | 2016-01-22 | 2017-07-27 | 同济大学 | Composite membrane separation method applicable to desalting and recycling of sewage |
| CN109987779A (en) * | 2017-12-29 | 2019-07-09 | 宁波方太厨具有限公司 | A kind of water filtering system |
| CN109987779B (en) * | 2017-12-29 | 2024-01-19 | 宁波方太厨具有限公司 | Water filtration system |
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