CN101717136B - Method for purifying waste water and recovering waste materials on line in electroplating and chemical plating processes - Google Patents
Method for purifying waste water and recovering waste materials on line in electroplating and chemical plating processes Download PDFInfo
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Abstract
The invention provides a method for purifying waste water and recovering waste materials on line in electroplating and chemical plating processes. The method comprises the following steps of: directly arranging a capacitance deionizer in a water washing device on a production line to adsorb various negative ions and positive ions in waste water during charging a battery so as to purify the waste water; and then releasing and recovering waste materials through electrode discharge so as to realize zero release of pollutants. The invention ensures that the capacitance deionization method is suitable for the manufacturing processes of various electroplating or chemical plating products through the optimization of process parameters. Through on-line purification and recycle of washing water, the burden of the traditional waste water treatment system is obviously reduced, meanwhile, the quality of plating pieces is guaranteed because the water quality of the washing water is obviously improved, and the classified recovery of waste materials can be achieved. The method can also obviously reduce the COD in the waste water and has wide application prospect in the fields of electroplating and chemical plating.
Description
Technical field
The invention belongs to water-treatment technology field, be specifically related to a kind of capacitive deionization method of utilizing, in-line purification electroplate or chemical plating technology in the waste water that produced, and reclaim the method for useful matter in the waste water.
Background technology
Have than the historical process for treating surface of long hair exhibition as a kind of; Plating and electroless plating technology are not only played an important role in traditional industry; And many in modern times high-tech industries, also be absolutely necessary like fields such as electronics, microelectronics, communication, infotech, aerospace.But on the other hand; Electroplate and electroless plating is again a kind of high pollution industry of generally acknowledging, though with regard to the waste water total amount of its generation, they are than many other industries; All to lack like papermaking, printing and dyeing, chemical industry etc.; But often contain a large amount of heavy metal ion in the waste water that they produce, like chromium (Cr), cadmium (Cd), plumbous (Pb), nickel (Ni), tin (Sn), copper (Cu), zinc (Zn), silver (Ag), gold (Au) etc., and the various synthetic type organic that is difficult to natural degradation.These are unprocessed; Perhaps handle the below standard waste water in back and enter river course, pond; Permeate the ground, will cause soil, water source and atmospheric severe contamination, the toxicity of its height, carcinogenic and teratogenesis are difficult to reverse to the broken ring of the various ecosystems of nature often.
Owing to complicated component, toxicity height, the blowdown flow rate of plating and chemical plating waste water are big, its wastewater processing technology receives much concern always, and development is the history of existing decades so far.More common electroplating waste water treatment technology comprises chemical precipitation method, oxidation reduction process, electrolytic process, active carbon adsorption, ion exchange method, membrane filtration technique, reverse osmosis technology etc.Common handling procedure is following:
Electroplating wastewater → equalizing tank → charcoal absorption system → settling tank → flocculation basin → press filteration system → pH regulator pond → biochemical treatment system → filtering basin → ion exchange system → film processing system → few part reuse, most of discharging.
But these technology are still failed far away to solve and are electroplated and waste water pollution problem that electroless plating is produced at present.How further to reduce the pollution of plating and electroless plating, become the significant problem that solution is badly in need of in this field, and restricted the development in this field to a certain extent environment.
Electroplate and electroless plating seriously polluted, intractability is high, and is relevant with its process characteristic.In plating and electroless plating process, need clean to guarantee the quality of plating piece plating piece constantly, produced a large amount of waste water thus, strengthened the difficulty of wastewater treatment and the burden of Waste Water Treatment.To the wastewater problem of plating and electroless plating, present existing solution thinking is divided into two types: one type is to adopt the hypotoxic technology of low pollution to electroplate or electroless plating; Another kind of is constantly to make improvement to the wastewater processing technology of electroplating or electroless plating produced.
For first kind thinking, promptly original high pollution, highly toxic technology are improved, as with trivalent chromium (Cr
3+) replacement sexavalent chrome (Cr
6+) carry out chromium plating, cyanogenless electroplating technology and replace having cyanogen electroplating technology etc.But because there is the defective of technical aspect in this type technology, the difficult quality guarantee of product, so its application receives very big restriction.
Solve thinking, existing at present a large amount of research, report and technological development for second type.
A kind of method of removing heavy metal in the electroplating wastewater has been introduced in patented claim 200710071462.2.It is through containing chromium (Cr) waste water, nickeliferous (Ni) waste water, containing cadmium (Cd) waste water, cupric (Cu) waste water, containing zinc (Zn) waste water, contain gold (Au) waste water and argentiferous (Ag) waste water etc.; Or contain in the electroplating wastewater of mixture-metal of various heavy and add the wet mud of process hides; Stir then, leave standstill, mud granule thing post precipitation to be suspended carries out solid-liquid separation; Supernatant can discharge, harmless treatment separately after the sludge dewatering compression.
The Li Fude of Chengdu Inst. of Biology, Chinese Academy of Sciences, people such as An Muhui have introduced the method that a kind of microbial technique is handled electroplating wastewater in the patent No. is 93106616.6 patent.It adopts composite bacterias such as Fusobacterium nucleatum, Paracoccus denitrificans, blunt tarda and peptococcus anaerobius and sanitary wastewater and chromium plating wastewater mixing; Can effectively the hexavalent chrome reduction in the electroplating wastewater be become trivalent chromium; And be precipitated out from the aqueous solution with the chromium hydroxide compound form, reach the purpose of purification of water quality.
Publication number is that the Chinese patent of CN101234828 has been introduced a kind of integrated electroplating treatment method for waste water; Its combination based on chemical precipitation method and membrane technique is used; Chromate waste water and cyanide wastewater imported to carry out air supporting, chemical precipitation, coagulation and precipitate and separate in the Waste Water Treatment, reclaim cupric, nickeliferous, zinc-containing sludge respectively; Supernatant is then through apparatus processes such as sand filter, strainer, ultrafiltration, r-o-s, and water outlet can be returned plating shop and reuse.
But, more than these improve one's methods all be earlier with pending discharge of wastewater in Waste Water Treatment, and then handles or handles the back and reclaim, this does not solve, and Waste Water Treatment is born greatly, the not good problem of treatment effect; And undressed waste water gets into Waste Water Treatment through sewer line, causes the obstruction of sewer line easily, hinders carrying out continuously of complete processing.
And at present, also do not have relevant technology in plating/chemical plating technology process, to handle to waste water.The patent No. is that 01131022.7 Chinese patent discloses a kind of cyanogen system and contained two round-robin methods that reclaim of heavy metal-containing electroplating effluent; Through the retrieving arrangement that adopts ion exchange resin to process, tentatively realized the purification of waste water and circulated using again as washing the water recovery.It is to adsorb deleterious prussiate and heavy metal through ion exchange resin, and the water after fractionation by adsorption is delivered to a last processing procedure again as the required washing water of electroplating process; After resin is saturated; Recycle with the anion regeneration agent again; The toxic cyanide heavy metal substance is broken away from from resin, and the prussiate heavy metal substance that breaks away from makes prussiate be broken to nitrogen, carbonic acid gas and water again with the electrolysis of positive and negative electricity; The heavy metal substance that wherein belongs to cationic is adsorbed in negative electrode, gives recycling again.Yet; Defective below the processing recovery technology that this patent adopted exists: what (1) this technology adopted is that ion exchange resin adsorbs the prussiate heavy metal; Its principle is to utilize ion exchange resin that fixedly charged group is arranged; Realize adsorbing anti-charge ion through self-built power plant, therefore, its to can the adsorbed contaminants type and system in the composite type of pollutent mixture very big restriction is arranged; As only limit to handle the waste water that contains cyanogen system and heavy metal, electroplate or chemical plating waste water and can not be widely used in process various types; (2) loading capacity of the ion exchange resin that adopts of this technology is less, need regenerate more continually, and regenerative process need add regenerator, can't in same system, accomplish regenerative process, and inconvenient operation is unfavorable for the application of in-line purification process; (3) adopting ion exchange resin to adsorb often needs consumption acids or alkali, and the regenerative process after its absorption need apply electric current, and resource consumption is many, and other material easy generation of secondary pollution that add.Therefore, this technology also is difficult to realize online wastewater treatment in the plating/chemical plating technology, guarantees the quality of plating piece simultaneously.
(Capacitive Deionization CDI) is a kind of water treatment method that development in recent years is got up to the capacitive deionization technology.The ultimate principle of capacitive deionization technology is through applying electrostatic field to pending liquid, forcing the ion in the liquid is moved to the electrode that has opposite charges.Electrode with excellent conductive performance and bigger serface places electrostatic field to produce very strong electrostatic double layer at the interface at itself and electrolyte solution.The thickness of electrostatic double layer has only 1 ~ 10nm, but can attract a large amount of electrolyte ion of enrichment, and stores certain energy.In a single day and remove electric field, the ion of enrichment can be released to again in the bulk solution on the electrode, is convenient to centralized collection (this process is also referred to as " charging enrichment ").Compare with traditional wastewater processing technology; The CDI technology has following advantage: (1) only needs extra electric field; Can accomplish ionic absorption and discharge through electrode absorption (charging)/regeneration (discharge) process, and just can obtain to regenerate when discharging, reuse.And common ion exchange method, its regeneration needs a large amount of acidity and basic soln, produces the secondary wastewater of macro-corrosion property thus; (2) very high capacity usage ratio.Compare with the thermal process of tradition evaporation, capacitive deionization has higher energy efficiency; (3) simple to operate.Compare with high pressure pulse discharge plasma method, ultrafiltration and reverse osmosis technology, have more the scale operability.
But it is current; The CDI The Application of Technology is comparatively limited to, and is mainly used in sea water desaltination and purified water field, and existing indivedual patents relate to CDI Design of device and manufacturing thereof; Such as the patent No. (application number) is 01129623.2; 200810040737.0,200810178157.8 Chinese patent, USP 6309532 etc.But all these patents all are to how improving CDI device itself, analyzing, set forth and these are not installed waste water how to handle different sources.Though say from the principles of science; The CDI technology can be adsorbed any type of negatively charged ion and positively charged ion; But the kind of the contained zwitterion of different waste water is all very inequality with other pollutent, so a kind of " universal " CDI device that is directed against all waste water in fact is to be difficult to realize.And at present, the CDI technology is used for the desalination aspect more, for can being applied to electroplate or the wastewater treatment of electroless plating, and electroplate or the wastewater treatment of electroless plating in how to use should technology, any report is not arranged as yet.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art; Provide a kind of can be in plating/electroless plating process the method for in-line purification waste water; Thereby significantly reduce the generation and the pollution of waste water, and prevent the obstruction of sewer line, solve the wastewater treatment and a recovery difficult problem of plating and electroless plating.
Another object of the present invention is to simplify the washing process in plating/electroless plating, has guaranteed the quality product of plating/electroless plating in the time of the conserve water resource.
A further object of the present invention is to provide the method for the waste material in a kind of efficient recovery plating/chemical plating waste water.
The present invention realizes above-mentioned purpose through following technical scheme:
A kind of electroplate or chemical plating technology in the method for in-line purification waste water, through the capacitive deionization method purify electroplate or chemical plating technology in waste water.
Described capacitive deionization method be applied to electroplate or chemical plating technology in the washing stage.
Described capacitive deionization method is capacitor deionizing instrument to be set come the waste water in the treating water washing trough in washing bath.
Described capacitor deionizing instrument comprises with lower component: ion-conductance adsorption electrode, collector electrode, insulation layer.Ion-conductance adsorption electrode wherein is a NACF, and collector electrode is an expanded graphite plate.These parts connect in the following manner: collector electrode (graphite cake), ion-conductance adsorption electrode (active carbon fiber fabrics), insulation layer (fluid course), ion-conductance adsorption electrode (active carbon fiber fabrics), collector electrode (graphite cake), ion-conductance adsorption electrode (active carbon fiber fabrics), insulation layer (fluid course) ... stack successively/expand and form.
Capacitor deionizing instrument adsorbs the various zwitterions in the waste water through process of charging, thereby purifies liquid waste.
Its charging voltage is 1 ~ 30 volt; Usually the concentration of metal ions in waste water is under the situation of 1ppm ~ 3000ppm, and in the adsorption process of at every turn charging, the quantity that every square metre of electrode pair can be purified liquid waste is 30 ~ 100 liters.
The invention property ground is applied to capacitor deionizing instrument to electroplate/washing stage in the chemical plating technology, electroplate reducing, the pollution of chemical plating waste water, and guarantee to electroplate, the quality of product of electroless plating has great importance.Simultaneously, the present invention has practiced thrift the energy substantially when effectively reaching the purification purpose.
At first, the present invention adds capacitor deionizing instrument waste water is purified in plating/chemical plating technology, is creative meaning.
In existing plating or electroless plating process, the span of washing this step is big, length consuming time, and the wastewater flow rate of generation is very big.With the gold-plated tin continuous electroplating of selectivity is example, and its typical processes is following:
Terminal to be plated (workpiece) → hot degreasing tank → washing bath → electrolytic degreasing bath →
Washing bath 1 → washing bath 2 → washing bath 3 → acid-wash activation groove → washing bath 1 →
Washing bath 2 → washing bath 3 → nickel bath 1 → washing bath → nickel bath 2 → washing bath
→ ... → nickel bath 5 → washing bath 1 → washing bath 2 → ... → washing bath 5 →
Plating bath 1 → washing bath → ... → plating bath 3 → washing bath 1 → washing bath 2
→ ... → washing bath 5 → pot 1 → ... → pot 4 → washing bath 1
→ ... → washing bath 6 → rear treating groove → washing bath → drying unit → packing.
Can find out all having washing to handle this procedure on the production line between any two processing procedures from above-mentioned processing procedure, and the multiple tracks washing need be set usually.This be because the washing process effect to the quality product important influence: 1) if washing is not thorough, the liquid medicine in preceding one processing procedure can be brought in one processing procedure in back, clump and the one employed liquid medicine of processing procedure in back is polluted; 2) if wash insufficiently, the various components of liquid medicine can remain in the micropore and defective of galvanization coating, thereby cause plating piece to produce various quality problems.
In order to guarantee the quality of plating piece, traditional process method has to adopt lengthy and tedious washing treating processes, will wash the waste water that is produced again and finally be discharged in the Waste Water Treatment and focus on.Generally, in the production line, the quantity of its washing bath is about 3 ~ 5 times of work nest, and the wastewater flow rate that washing bath produced accounts for more than 80% of total wastewater flow rate that whole production line produces.This operational characteristic has caused plating/electroless plating will produce a large amount of waste water, has greatly increased the weight of the burden of Waste Water Treatment; In addition; Since water washing process must be continually with the clean water source (like deionized water; Ultrapure waters etc.) come used washing water in the place of water washing trough, the replacing frequency of washing water does not once wait by every several hours from continuous overflow, and this has caused the significant wastage of water resources.
The present invention directly is provided with capacitor deionizing instrument in washing bath, utilize the capacitive adsorption deionizing technology, through process of charging the pollutants in waste water ion constantly is adsorbed onto in the capacitor deionizing instrument.Since electroplate or waste water that electroless plating produced in contain a large amount of charged ions, therefore, the capacitive deionization technology can be well be complementary with the character of plating/chemical plating waste water.Simultaneously,, it is arranged in plating/electroless plating washing bath because capacitor deionizing instrument is big to the ionic adsorptive capacity, the pollutent that can the active adsorption plating piece in water washing process, cleans out, thus reach the purpose of purifying liquid waste.This has not only reduced the generation of waste water in the production process, has reduced the burden of wastewater treatment; Simultaneously, through a plurality of capacitor deionizing instruments are set continuously, can effectively ensure the quality of plating piece product in each washing bath.
Secondly, the present invention is fused to the capacitive deionization method in plating/chemical plating technology process pointedly, finds out the optimum combination that is applicable to wastewater characteristics in plating/chemical plating technology.Having differently significantly with other waste water in nature, be applicable to that the treatment process of handling such waste water also will have significant difference, especially in the waste water in-line treatment process, receive the influence of complicated factors such as coating bath liquid medicine based on plating/chemical plating waste water.Therefore, existing C DI is in sea water desaltination and pure water Application for Field in contrast, and CDI is used to electroplate or the wastewater treatment of electroless plating makes it bring into play effective function, need further grope and verify.The method that the present invention adopted is carrying out repeatedly drawing evidence after the reasonable optimizing test; Through applying 1 ~ 30 volt voltage, when concentration of metal ions is 1ppm ~ 3000ppm in the waste water, when 30 ~ 100 liters of every square metre of each charging processes of electrode pair; Can be when saving electric energy; Realize online purifying liquid waste, the replacing frequency of washing water is reduced to changed once in every tens of hours, even can reach more than several days and change once.
Remove this; This on-line processing method makes the waste water sewer line of just flowing through after treatment; No longer stop up sewer line, thereby solved in the prior art because all contaminations in the waste water is deposited on the sewer line wall when flowing through sewer line, and the technical barrier that causes sewer line to stop up.
The contaminated wastewater that this technology not only greatly reduces plating/electroless plating and produced has been realized online wastewater treatment, has simplified the washing process process of plating/electroless plating simultaneously, when guaranteeing the plating piece quality product, has practiced thrift water resources and electric energy.
Capacitor deionizing instrument of the present invention also can be after absorption be saturated or saturated nearly; Pass through discharge process; The ion that process of charging is adsorbed discharges again; Satisfy needs, realize the regeneration of electrode in the capacitor deionizing instrument simultaneously, in the washing water treatment procedure that gets into next round for waste recovery.
Compared with prior art, the present invention has following beneficial effect:
The CDI device to plating/chemical plating waste water that will design voluntarily to (1) the invention property is directly installed in the washing bath on the production line; Through directly the waste water in the washing bath being handled; With the metals ion of the inside and corresponding negatively charged ion is adsorbed onto the negative electrode of this device respectively and above the anode; Absorption when can realize metals ion and most of organism such as organic acid group, additive, tensio-active agent etc. is applicable in the manufacture craft of multiple plating/product of electroless plating.
(2) method provided by the present invention has realized the in-line treatment of real plating/chemical plating waste water first; It can be directly in washing bath with pollutants in waste water, like metals ion and most of organism (comprising organic acid, 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 basically 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.
(3) on-line processing method provided by the present invention is applicable to plating/electroless plating especially; Because the quality of washing water has material impact to the quality of plated item; This method wash water of effectively purifying waste water; Simplified the step of washing water in plating/chemical plating technology, guaranteed the quality of plating piece simultaneously, and effectively practiced thrift water resources.
(5) method provided by the present invention can realize the purifying treatment of plating/chemical plating waste water and the recovery of waste material in same device, and is easy to operate, effectively utilized resource.
(6) method provided by the present invention has not only effectively purified waste water, can significantly reduce the COD in the waste water simultaneously, greatly reduces the pollution of drainage water to environment.
The present invention is the watershed management that in procedure for producing, directly carries out pollutent, rather than after whole processing procedure finishes, just comes to concentrate and carry out so-called end treatment.Simultaneously; The technology of utilizing the present invention to plant is not only significantly saved water resources and cost for wastewater treatment, enhances productivity; And can also be with carrying out reuse after noble metal and the enrichment of various medicament component in washing bath; Significantly reduce the discharging of refuse and pollutent, this is the typical cleaner production process of a kind of ten minutes (Cleaner Production Process), has broad application prospects in plating/electroless plating field.
Embodiment
Below further specify technical scheme of the present invention through concrete 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.
Embodiment 1
The electrode area of the electrode pair of capacitor deionizing instrument is 5000 square centimeters; Be used to handle the nickel plating washing waste water that water produced; Metal ion content in the nickel plating washing waste water that water produced is 100ppm, COD value 930, and control water inlet (the water inlet volume is 120 liters) flow velocity is 4 liters/minute.Divide three test group, WV is respectively 2 volts, 10 volts and 20 volts.
Test-results is following:
| WV (volt) | 0 | 2 | 10 | 20 |
| Water outlet concentration of metal ions (ppm) | 100 | 36 | 9.5 | 3 |
| COD (mg/litre) | 930 | 432 | 98 | 72 |
Electrode to electro-adsorption is saturated under 20 volts of voltages among this embodiment carries out electric pole short circuit, makes in the water sample of ionic discharge desorb in electrode channel.Water inlet is 120 liters, and after absorption and desorb, wherein about 100 emersion water satisfy the reuse requirement fully, and about 20 liters are carried out enriching and recovering in addition.Utilize atomic absorption spectrometry and potassium dichromate oxidation to measure metallic nickel ions concentration and chemical oxygen demand COD in the enriching and recovering water sample respectively, the result is respectively 412ppm and 3260 mg/litre.
Embodiment 2
The electrode area that the capacitor deionizing instrument Activated Carbon Fiber Electrodes is right is 20000 square centimeters; Be used to handle the waste water that zinc-plated washing water is produced; Metal ion content in the waste water that zinc-plated washing water is produced is 790ppm; COD value 1340, control water inlet (300 liters of water inlet volumes) flow velocity is 4 liters/minute, 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.Divide three test group, WV is respectively 2 volts, 10 volts and 20 volts.
Test-results is following:
| WV (volt) | 0 | 2 | 10 | 20 |
| Water outlet concentration of metal ions (ppm) | 790 | 200 | 98 | 25 |
| COD (mg/litre) | 1340 | 525 | 98 | 56 |
The electrode saturated to electro-adsorption in the present embodiment carries out electric pole short circuit, makes the ionic discharge desorb, shows with the Atomic Absorption Spectroscopy AAS quantitative analysis, and ionic discharge resolution reaches more than 90%.
Embodiment 3
Electro-adsorption capacity to embodiment 1 and embodiment 2 used CDI devices is demarcated with the sodium chloride solution of 2000 mg/litre.The stop of control water inlet is 30 minutes time, and when 20 volts of WVs, the electro-adsorption capacity in 1 valency positively charged ion (sodium ion) that records is respectively 0.8 mmole/gram charcoal and 0.7 mmole/gram charcoal.
Claims (5)
1. the method for an in-line purification waste water in plating and chemical plating technology is characterized in that: purify the waste water in plating or the chemical plating technology through the capacitive deionization method; Described capacitive deionization method is capacitor deionizing instrument to be set handle waste water in washing bath; Described capacitor deionizing instrument comprises with lower component: ion-conductance adsorption electrode, collector electrode, insulation layer; The charging voltage of described capacitor deionizing instrument is 10～30 volts; The ion-conductance adsorption electrode is a NACF.
2. the method for in-line purification waste water in plating as claimed in claim 1 and the chemical plating technology is characterized in that: described capacitive deionization method be applied to electroplate or chemical plating technology in the washing stage.
3. the method for in-line purification waste water in plating as claimed in claim 1 and the chemical plating technology is characterized in that: it is to adsorb the various zwitterions in the waste water through process of charging that described capacitor deionizing instrument is handled waste water.
4. the method for in-line purification waste water in plating as claimed in claim 1 and the chemical plating technology; It is characterized in that: the concentration of metal ions in the described waste water is 1ppm～3000ppm, and the quantity that every square metre of electrode pair can be purified waste water in the adsorption process of at every turn charging is 30～100 liters.
One kind as claimed in claim 1 electroplate with chemical plating technology in the method for recovery waste material; It is characterized in that: purify in the waste water process in plating or the chemical plating technology through the capacitive deionization method; Capacitor deionizing instrument reclaims waste material through discharge process after adsorption process finishes.
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| CN2009101941069A CN101717136B (en) | 2009-11-24 | 2009-11-24 | Method for purifying waste water and recovering waste materials on line in electroplating and chemical plating processes |
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| CN101717136B true CN101717136B (en) | 2012-06-27 |
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| CN102701497A (en) * | 2012-07-06 | 2012-10-03 | 厦门溢盛环保科技有限公司 | Method for recycling cyanide from electroplating cyanide-containing wastewater |
| CN103043814B (en) * | 2012-08-02 | 2014-08-06 | 华夏新资源有限公司 | Method for recycling phosphorous electroless nickel plating solution element in wet process of surface treatment |
| CN106245059B (en) * | 2016-08-08 | 2018-03-09 | 侯梦斌 | It is a kind of based on the noble metal reclaimer and technique that flow through formula capacitive deionization method |
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