CN102001729A - Electrolytic treatment method of heavy metal-containing wastewater - Google Patents

Electrolytic treatment method of heavy metal-containing wastewater Download PDF

Info

Publication number
CN102001729A
CN102001729A CN2009101022083A CN200910102208A CN102001729A CN 102001729 A CN102001729 A CN 102001729A CN 2009101022083 A CN2009101022083 A CN 2009101022083A CN 200910102208 A CN200910102208 A CN 200910102208A CN 102001729 A CN102001729 A CN 102001729A
Authority
CN
China
Prior art keywords
ion
heavy metal
particle
waste water
exchange
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2009101022083A
Other languages
Chinese (zh)
Inventor
莫一平
张晓忠
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HUZHOU SIFANG GREEN AUTOMATION TECHNOLOGY Co Ltd
Original Assignee
HUZHOU SIFANG GREEN AUTOMATION TECHNOLOGY Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by HUZHOU SIFANG GREEN AUTOMATION TECHNOLOGY Co Ltd filed Critical HUZHOU SIFANG GREEN AUTOMATION TECHNOLOGY Co Ltd
Priority to CN2009101022083A priority Critical patent/CN102001729A/en
Publication of CN102001729A publication Critical patent/CN102001729A/en
Pending legal-status Critical Current

Links

Abstract

The invention discloses an electrolytic treatment method of heavy metal-containing wastewater, by which the heavy metal can be effectively removed. The wastewater is subject to electrolytic treatment in an electrolysis device. The structure of the electrolysis device is as follows: an anode (2) electrically connected with the positive pole of a DC power supply (1) and a cathode (5) electrically connected with the negative pole of the DC power supply are arranged in an electrolytic tank (4); and filler (3) is arranged between the two electrodes and formed by mixing electronic conductive material (7) and particles (8) with ion exchange performance. The electrolytic treatment method of the invention is suitable for removing and recycling the heavy metal in the wastewater.

Description

The electrolytic processing method of heavy metal-containing waste water
Technical field
The present invention relates to a kind of electrolytic processing method of heavy metal-containing waste water, relate in particular to a kind of deep treatment method of heavy metal-containing waste water, be particularly useful for containing the processing of low concentration heavy metal water, belong to field of environment protection.
Background technology
Heavy metal is meant that in periodic table of elements metal grid nucleidic mass is greater than 40 metallic element, as copper, mercury, cadmium, zinc, lead, nickel, chromium, manganese, iron etc.Heavy metal, particularly mercury, cadmium, lead, chromium etc. have significant bio-toxicity.They can not be degraded by microorganisms in water body, and can only take place that various forms transform mutually and dispersion, enrichment process (i.e. migration).
Heavy metal contamination has now become one of maximum water pollution problems of harm.Because heavy metal element has characteristics such as difficult degradation, easily accumulation, toxicity are big, in addition can also be absorbed and enter food chain by waterplant and animal, be detrimental to health.Therefore, the heavy metal contamination in the water body especially should be subjected to people's attention.
Heavy metal contamination in the water body mainly comes from the waste water of mining, Metal smelting, metal processing, store battery, plating and Chemical Manufacture, the man-made pollution sources such as burning, applying pesticides chemical fertilizer and domestic refuse of fossil oil, and natural source such as geological erosion, weathering.
Fast development along with quickening of urbanization process and industrial or agricultural, the most cities of China all exist more serious quality problem, a large amount of undressed municipal wastess, contaminated soil, trade effluent and sanitary sewage and atmospheric fallout constantly enter in the water, heavy metal contaminants content in the water body is sharply raise, begun to have influence on the water body quality.The pollution level of the heavy metal section of ten large watersheds such as the Yellow River in 2003, Huaihe River, Song Hua River, the Liaohe River all reaches super V class.
After heavy metal enters aquatic ecosystem, be distributed in each integral part of aquatic ecosystem, to the each several part of the ecosystem all can produce serious influence (being ecologic effect).Heavy metal in the water body can be absorbed by hydrobiont and accumulate in its body, after the intravital heavy metal of biology runs up to a certain degree, the symptom of being injured will occur, physiology is obstructed, arrested development, in addition dead, and make impaired, the collapse of whole aquatic ecosystem 26S Proteasome Structure and Function.
Heavy metal in the water body can directly enter human body by tap water, hydrobiont that also can be by entering food chain and enter human body indirectly with the vegetables and the grain of the water pouring of heavy metal contamination.After heavy metal enters human body, being difficult for excreting, accumulating gradually, is many-sided, multi-level to the harm of HUMAN HEALTH, and its toxicological effect mainly shows influence the fetus normal development, causes dysgenesia, reduction human quality etc.Heavy metal is interior iron, vitamins C and other the essential nutritive substances of storing of depleted body seriously, cause the immunity system defence capability to descend, and intrauterine embryo growth is stagnated and some other deformity.In addition, heavy metal can also suppress the activity of anthropochemistry reaction enzymes, and tenuigenin is poisoned, thereby the injury nervous tissue also can cause directly tissue poisoning, the critical organ such as the tissues such as liver, kidney of infringement human body function of detoxification.Be listed in violent in toxicity as Hg, Pb, Cd, Cr etc. and carried out keypoint control.Studies show that danger such as that heavy metal elements such as Cr, Co, Ni, Cd, Se all have is carcinogenic, teratogenesis, mutagenesis.
Seriously influence just because of heavy metal causes environment and human beings'health, people have proposed more and more higher requirement to the control of heavy metal contaminants.On August 1st, 2008, the formal GB 21900-2008 " plating pollutant emission standard " that implements proposed more strict emission request to the heavy metal contaminants of electroplating enterprise.This has also promoted heavy metal contamination to administer processing and the advanced treatment technology that Study on Technology turns to low concentration heavy metal water greatly.
The treatment process of heavy metal wastewater thereby mainly is divided into three kinds of physico-chemical processes, biological treatment and electrolytic process.Physico-chemical processes is the most frequently used method of present heavy metal containing wastewater treatment, comprises chemical precipitation method, ion exchange method, resin absorption method, Activated Zeolite Adsorption, active carbon adsorption, membrane separation process etc.Wherein chemical precipitation method is most widely used general, and it is that heavy metal ion is changed into oxyhydroxide or the sulfide that is insoluble in water, removes through precipitation then.Recently the polymer trapping agent method that application increases gradually also can be summed up as chemical precipitation method.Chemical precipitation method has to be used simply, and easy to operate advantage, but can only handle the waste water of slight pollution particularly when contain complexing agent in the waste water, utilizes chemical precipitation method can't obtain the result of being satisfied with.
The application of ion exchange method in heavy metal containing wastewater treatment is also comparatively extensive, it be utilize the peculiar ion-exchange performance of ion exchange resin with the heavy metal ion of waste water and resin itself with Na +Or H +Exchange, with heavy metal ion enrichment to resin, and Na +Or H +Then be released in the waste water.It is fast that ion exchange method has processing speed, the characteristics that effluent quality is good, but regeneration of ion-exchange resin is pretty troublesome, and the heavy metal solution of being born again still needs further to handle the cost height.
Resin absorption method, Activated Zeolite Adsorption, active carbon adsorption are referred to as absorption method, they can adsorb the heavy metal ion in the waste water, its mesolite also has ion-exchange capacity, but still to be adsorbed as the master, by absorption the heavy metal ion in the waste water is removed.It is good that absorption method has a regulation effect, the advantage of instant effect, but processing power is low, and the regeneration trouble of sorbent material, the processing cost height is used and few.
Membrane separation technique is more a kind of heavy metal containing wastewater treatment technology of development in recent years, and it utilizes selection perviousness that polymeric membrane has to divide heavy metal ion in dried up, comprises electrodialysis, reverse osmosis, ultrafiltration etc.Membrane separation technique has processed waste water and can return-enclosure use, level of automation is high and can realize the advantage of closed cycle and receive increasing concern, but there is the problem of operational condition harshness, complicated operating process in membrane separation technique, and need strict pretreatment technology, especially the film blockage problem can not be well solved always, thereby limits its widespread use.
Biological process is a kind of heavy metal containing wastewater treatment technology that produces along with development of biology the eighties in 20th century, be referred to as the water ecology recovery technique again, the ecosystem that comprises microorganism, waterplant, hydrocoles and their formations shifts, transforms heavy metal contaminants, thereby water body is purified.Characteristics such as biological process has effective, and cost is low, but long processing period, it is slow to take effect, thereby does not obtain large-scale application, still is in conceptual phase at present.
Above-mentioned treatment process is just removed the heavy metal in the waste water mostly, and strictly speaking this is a kind of transfer of pollutent, is not recycled fully, has the possibility of secondary pollution.The effective means of heavy metal that reclaims in the waste water is an electrolytic process, and it is to utilize the principle of galvanic deposit that the heavy metal ion in the waste water is deposited on the cathode surface, has non-secondary pollution, the body refuse amount is few, deposition is come out advantages such as the recyclable utilization of heavy metal.
But existing electrolytic process adopts plate electrode mostly, processing efficiency is low, and limiting current sharply reduces along with the reduction of the heavy metal ion in the waste water, especially the heavy metal wastewater thereby of lower concentration, result can not be satisfactory, so it only is suitable for handling the heavy metal wastewater thereby of high density.In addition the specific conductivity of waste water is low, in order to improve the electroconductibility of waste water, need add conducting salt sometimes, so just has been unfavorable for the reuse of waste water.
In order to improve current efficiency, increase mass transfer velocity, make it can in dilute solution, reclaim metal effectively, the heavy metal electrolytic recovery technology of applying three-dimensional electrode is developed.Three-diemsnional electrode has great face body ratio, and very big active contact area promptly just can be provided in very little volume, has improved current efficiency and treatment effect greatly, makes the application of electrolytic process obtain further expansion.
Yet, it is still not satisfactory when the applying three-dimensional electrode is handled low concentration heavy metal water, as when the concentration of heavy metal ion in the waste water is lower than 1ppm, be difficult to further carry out advanced treatment, therefore can't reach the emission request of the GB 21900-2008 standard of national up-to-date promulgation.On the other hand, we know that metallic conductor all has shielding effect, in three-diemsnional electrode, really work just towards the skim of counter electrode, inner most of electrode all is not fully used.
We are also noted that the waste water of existing three-dimensional electrode electrolysis processing heavy metal can not be used for treatment of cyanide waste water, and cyanide wastewater still adopts broken cyanide, the method for neutralization precipitation step-by-step processing, and this has also limited the application of three-dimensional electrode electrolysis method.
Summary of the invention
It is not enough that the present invention will solve the existing concentration of treatment of existing three-dimensional electrode electrolysis processing heavy metal wastewater thereby technology, the problem that the electrode utilization ratio is low, the electrolytic processing method of heavy metal-containing waste water of the present invention is provided for this reason, present method can effectively be removed contained heavy metal in the waste water, can also realize broken cyanide, metal recovery single stage method processing heavy metal wastewater thereby.
For addressing the above problem; the technical solution used in the present invention is; its special character is that described waste water is charged into electrolyzer as described below makes electrolysis treatment; the structure of this electrolyzer is: anode that is electrically connected with dc power anode and the negative electrode that is electrically connected with dc power cathode are set in a cell body; between two electrodes stopping composition is set, this stopping composition is mixed by electronic conductive material and the particle with ion-exchange performance.
Described electronic conductive material is at least a in electronic conduction particle, wire cloth, foamed metal, the charcoal fiber.
Described electronic conduction particle is at least a in activated carbon granule, graphite granule, metallic particles, boron-doped diamond particle, conductive metal oxide particle, the electronic conduction high molecular polymerization composition granule.
Described charcoal fiber is at least a in activated carbon fiber, activated carbon felt, active carbon cloth, graphite felt, the Graphite cloth.
Described particle with ion-exchange performance is at least a in ion-exchange resin particles, zeolite granular, sieve particle, the bentonite clay particle.
The particle cumulative volume that has ion-exchange performance in the described stopping composition is 10%~90% of a stopping composition cumulative volume.
Described grain diameter is 0.1mm~10mm.
The present invention can be with the porous insulation barrier film with described anode and/or negative electrode and the isolation of described stopping composition.
Described barrier film is at least a in ion-exchange membrane, porous ceramics barrier film, microporous polypropylene membrane, polyethene microporous membrane, fibreglass diaphragm, synthon barrier film, asbestos diaphragm, nonmetallic filter cloth or the filter screen.
Described direct supply is constant voltage or constant voltage dc source, constant current or current stabilization direct supply, regular a kind of in communicating DC power supply or the pulse dc power.
Description of drawings
Fig. 1 is the heavy metal containing wastewater treatment schematic representation of apparatus;
Fig. 2 is with membranous heavy metal containing wastewater treatment device synoptic diagram;
Fig. 3 is the filler particles fundamental diagram of heavy metal containing wastewater treatment device inside;
Fig. 4 is another mode of operation principle schematic of the inner filler particles of heavy metal containing wastewater treatment device;
Fig. 5 is broken cyanide, recovery metal single stage method principle schematic;
Be labeled as among the figure: 1 direct supply, 2 anodes, 3 stopping composition, 4 cell body, 5 negative electrodes, 6 barrier films, 7 electronic conductive materials, 8 have the particle of ion-exchange capacity, the pending heavy metal wastewater thereby of I, the waste water after II handles, E direction of an electric field, M N+Heavy metal ion, M metal, M (CN) x Y-The cyanogen complex ion of heavy metal, CNO -The cyanic acid ion, CO 2Carbonic acid gas, N 2Nitrogen.
The invention will be further described below in conjunction with accompanying drawing.
Shown in Figure 1 is a kind of heavy-metal waste water treatment device provided by the invention. Be provided with at least one pair of electrode in a cell body 4, one of them electrode is the anode 2 that is electrically connected with the positive pole of dc source 1, and another electrode is the negative electrode 5 that is connected with the negative electricity of dc source 1. Between anode and negative electrode, fill out and be provided with inserts 3, inserts 3 by electronic conductive material 7 and around described positive and negative electrode and electronic conductive material 7 or the particle with ion-exchange capacity 8 of gap-fill form.
Electronic conductive material 7 is selected from has the big material with electron conduction of specific surface, such as electronic conduction particle, woven wire, foam metal and charcoal fiber etc. Preferred electronic conduction particle and charcoal fiber.
Described electronic conduction particle refers to the conductive particle of electronics as main carrier, comprise activated carbon granule, graphite particle, metallic particles, boron-doped diamond particle, conductive metal oxide particle, electron-conducting polymer polymer beads etc., preferred activated carbon granule, graphite particle and metallic particles.
Described charcoal fiber has hole to be enriched, and specific area is big, is a kind of desirable three-dimensional electrode conductive material, and utilizes the charcoal fiber also to have equipment as the electronic conductive material in the inserts and install and use the easy advantage of maintenance. The charcoal fiber comprises NACF, activated carbon felt, active carbon cloth, graphite felt, Graphite cloth etc., preferred active carbon fibre peacekeeping graphite felt.
Particle 8 with ion-exchange capacity refers to that particle itself has dissociable cation, is generally Na+Or H+, they can with solution such as water body in metal ion exchange, with metal ion complexes to the matrix of particle, simultaneously with original Na+Or H+Be discharged in the water body. Material with particle of ion-exchange capacity comprises ion exchange resin, zeolite, molecular sieve and bentonite etc., wherein preferred ion exchange resin and zeolite.
These particle shared volume ratios in whole inserts with ion-exchange capacity depend on the heavy metal kind in the pending waste water, the original concentration of heavy metal and the result that will reach etc., described volume ratio is generally 10%~90%, and preferred 30%~60%.
When the inserts that comprises electronic conductive material was particle, the grain diameter size had significant impact with water treatment effect. The little then specific surface of particle diameter is big, and treatment effect is good, but easily causes the packed layer obstruction of hardening. But particle diameter is too big, can significantly reduce specific area again, and treatment effect also reduces greatly. Therefore the particle diameter of particle is selected preferred 0.5~5mm, more preferably 1~3mm between 0.1~10mm.
In order to prevent being short-circuited between the positive and negative electrode, particularly proportion is hour in inserts 3 at the particle 8 with ion-exchange capacity, it is very big that electronic conductive material 7 is in contact with one another the possibility that forms short circuit, a kind of effective measures that prevent short circuit with the insulation diaphragm of porous with arbitrary electrode or two electrodes and inserts isolation, just anode is isolated with barrier film 6 generally speaking, as shown in Figure 2.
Barrier film 6 is not so long as have electron conduction, and have porous, can be all available through solution or ion, comprise amberplex, porous ceramics barrier film, microporous polypropylene membrane, polyethene microporous membrane, fibreglass diaphragm, synthetic fibers barrier film, asbestos diaphragm, nonmetal filter cloth or filter screen etc., optimization polypropylene microporous barrier, polyethene microporous membrane, synthetic fibers barrier film, nonmetal filter cloth or filter screen etc. In the not too high water treatment occasion of ask for something, adopting nonmetal filter cloth or filter screen is the low and effective selection of a kind of cost.
Heavy metal method of wastewater treatment provided by the invention belongs to electrochemical process for treating, external dc source must be arranged so that direct current to be provided. Can meet the demands with constant pressure and flow or voltage stabilizing current stabilization type dc source generally speaking, but in some special application scenario, in order to prevent electrode passivation, also can adopt the dc source of regular commutation. Along with the development of modern electronic technology, pulse power manufacturing cost is decrease, adopts the pulse power can effectively eliminate the electrode polarization phenomenon, greatly improves the treatment effect of heavy metal waste water.
The hybrid particles that following elder generation forms take electronic conductive material such as graphite particle and the particle with ion-exchange capacity such as ion-exchange resin particles is as the principle of inserts heavy metal method of wastewater treatment provided by the invention as example describes in detail.
In an electrolyzer 4, be provided with DSA anode 2 and stainless steel cathode 5, filling of filling out between anode and negative electrode expects that 3 is (to be generally Zeo-karb by graphite granule and ion-exchange resin particles, can only exchange with the positively charged ion in the waste water, can not exchange with negatively charged ion) composite grain formed.When graphite granule cumulative volume during less than ion exchange resin bead cumulative volume, surrounded by ion-exchange resin particles around the graphite granule morely, can not contact with each other between the graphite granule, and ion-exchange resin particles does not have electron conduction, so there is not the possibility of short circuit negative electrode and anode in this, so negative electrode and anode all needn't separate with barrier film, as shown in Figure 1.
Shown in Figure 3 is the partial enlarged drawing of stopping composition 3 under the above-mentioned situation, as can be seen from the figure surrounded by the particle 8 that ion-exchange resin particles promptly has ion-exchange capacity, cut apart by ion-exchange resin particles between the graphite granule and can not electrically contact as the graphite granule of electronic conductive material 7.When after applying direct current between negative electrode and the anode, just set up an electric field E from left to right.According to electricity knowledge, we know in this electric field, and isolated each other graphite granule goes out electric charge with sensed, and the cathodic side of graphite granule goes out negative charge with sensed, forms a negative potential; Graphite granule then induces positive charge towards anodic one side, forms a positive potential.So just form a multiple polar graphite granule packed bed, each graphite granule all is multiple polar, have an anode and a negative electrode, be equivalent to a miniature electrochemical reactor, whole electrolytic processing apparatus just is made up of numerous so miniature electrochemical reactor, has improved electrolysis treatment efficient greatly.
When containing heavy metal ion M N+Waste water I when being full of these stopping composition, because the speed of ion-exchange is much larger than the electrodeposition rate of these heavy metal ion, so the heavy metal ion in the waste water is at first carried out ion-exchange and is entered into ion exchange resin with ion-exchange resin particles, so just enrichment in ion exchange resin of the heavy metal ion in the waste water.Because ion-exchange resin particles and graphite granule and be in contact with one another, so will obtain electronics and move powering at graphite granule that to be deposited as heavy metal simple substance be metal M in the heavy metal ion of ion-exchange resin particles and graphite granule on-load side joint synapsis:
M n++ne -→M
The heavy metal ion migration back density loss of described ion-exchange resin particles and graphite granule contact position, the heavy metal ion in other places will be diffused into herein, thereby guarantees that electrodeposition process constantly carries out.
Because ion-exchange resin particles is also with the heavy metal ion enrichment in the waste water, and then migration galvanic deposit on graphite granule, because the concentration of heavy metal ion in the ion-exchange resin particles is far above the concentration of heavy metal ion in the waste water at this moment, so electrodeposition process is much easier, efficient is also much higher.Simultaneously numerous graphite granule is arranged in whole stopping composition, be equivalent to have numerous miniature electrochemical treater, improved the electrodeposition efficiency of heavy metal ion greatly, even the heavy metal wastewater thereby of lower concentration also can obtain good treatment.
We know, when the graphite granule cumulative volume in the stopping composition during greater than the ion-exchange resin particles cumulative volume, ion-exchange resin particles can't surround graphite granule fully, so just may have electrically contacting between the graphite granule, so just may between negative electrode and anode, have some electronic conduction passages.In order to prevent short circuit, one of them electrode must be carried out electronic isolation with stopping composition, generally speaking anode is separated with porous insulating material and stopping composition, can effectively avoid the short circuit of anode and negative electrode, but can realize the ionic conducting, electrochemical process can be carried out smoothly, as shown in Figure 2, make barrier film 6 among the figure anode 2 and packing material 3 are separated.
The packing layer partial enlarged drawing of this moment has been represented among the figure be mingled with ion-exchange resin particles in the middle of the graphite granule as electronic conductive material 7 as shown in Figure 4, always maintains electron channel between the graphite granule.When applying direct current between the cathode and anode, whole packing layer all is a negative pole, and all graphite granules are all electronegative, and promptly each graphite granule all is unipolarity.When pending heavy metal wastewater thereby I is full of these stopping composition, its principle of work and traditional three-diemsnional electrode are identical, but special character of the present invention is also to be filled with ion-exchange resin particles in the gap of three-diemsnional electrode, ion-exchange resin particles is as the trapping agent of heavy metal ion, earlier the heavy metal ion in the waste water is captured galvanic deposit on three-diemsnional electrode then.Because the speed of ion-exchange is more much bigger than the speed of galvanic deposit, so filled the three-diemsnional electrode of heavy metal capturing agent, processing speed is faster, and efficient is higher, and result is also far better.
The front has been addressed the present invention and has been also had a not available function of conventional three-dimensional electrode, can handle the heavy metal wastewater thereby that contains cyanogen exactly, and realization broken cyanide, galvanic deposit are removed the heavy metal single stage method and finished.Now the principle of handling is described in detail.
If handle the heavy metal wastewater thereby that contains cyanogen, as shown in Figure 3, stopping composition intermediate ion exchange resin particle cumulative volume must make each graphite granule can both induce corresponding positive charge and negative charge, as shown in Figure 5 greater than the graphite granule cumulative volume.
According to the ion complexation theory, we know that the cyanogen complex ion of heavy metal is generally electronegative, and we are temporarily with M (CN) x Y-Expression is if the valence state of heavy metal ion is n+, then
Y=x-n (x>n) generally speaking
So, M (CN) x Y-Can't be captured by ion exchange resin.By electricity knowledge as can be known, electronegative particle can be attracted by positive charge, like this M (CN) x Y-Just attracted to the positively charged side of graphite granule, and lose electronics, anodic oxidation reactions takes place at this:
M(CN) x y-+2xOH -→M n++xCNO -+2xe -
Ju Du cyanide ion is oxidized to the CNO of little poison like this -, discharge simultaneously by the heavy metal ion M of cyanogen complexing N+, heavy metal ion one is released, and is just captured by ion exchange resin, chat face to face before taking place then and electrodeposit reaction and heavy metal ion is removed.
And CNO -Can also further be oxidized to CO in the positively charged side of graphite granule 2And N 2:
2CNO -+4OH -→2CO 2↑+N 2↑+2H 2O+6e -
So just cyanide ion has been carried out not having the processing of poisoning completely, simultaneously the heavy metal ion galvanic deposit has been removed, thereby realized that broken cyanide and removing heavy metals single stage method finish.
When adopting wire cloth, charcoal fiber or foamed metal to fill as electronic conductive material, the situation of filling with above-mentioned conductive particle is the same, just on these material configurations continuity is arranged, and is different with the filling mode of conductive particle.Such as, realize the multipole filling, wire cloth, charcoal fiber or foamed metal can be cut into many lamellar materials with specified shape according to the shape and the filling mode of electrolyzer, the wire cloth that these are cut out, charcoal fiber or the parallel placement of foamed metal sheet material and assurance do not contact each other then, in the middle of these wire cloths, charcoal fiber or foamed metal sheet stock, fill particle again, so just formed an electrolytic processing apparatus multipole packing layer, that have the stereoscopic three-dimensional electrode with ion-exchange capacity.Its principle of work is with above-mentioned to mix the electrolyzer of filling with the particle with ion-exchange capacity with conductive particle identical.
For another example, realize the unipolarity filling, as long as will be electrically connected between above-mentioned populated wire cloth, charcoal fiber or the foamed metal sheet stock, simultaneously one of them electrode (being generally anode) is isolated getting final product with porous insulation diaphragm, its principle of work is also identical with the electrolyzer that above-mentioned unipolarity conductive particle is filled.
With method provided by the invention can be efficiently, apace the heavy metal contaminants in the water body is removed, the heavy metal that is deposited on the electro-conductive material can also be recycled it by certain suitable method, such as directly use with pending heavy metal wastewater thereby in identical metal as electro-conductive material, just can realize the recovery of heavy metal in the waste water.
Can handle the heavy metal wastewater thereby that all can galvanic deposit with method provided by the invention, as copper, zinc, lead, chromium, cadmium, nickel, cobalt etc.
Be particularly useful for containing the processing of low concentration heavy metal water with method provided by the invention, finish and to reach the emission request of stipulating in the GB21900-2008 standard.
Embodiment
Embodiment 1
In a square electrolyzer, be provided with ruthenium titanium anode, the netted negative electrode of stainless steel, the packing volume ratio is that the particle diameter of 1: 1 (be the volume of ion exchange resin account for whole packing layer 50%) is that activated carbon granule and the particle diameter of 0.84mm (20 order) is the Zeo-karb particle of 0.42mm (40 order) between anode and negative electrode.Ruthenium titanium anode connects the positive pole of constant pressure and constant flow pattern direct supply, and stainless steel cathode connects negative pole.The waste water of nickeliferous 943mg/L being charged in the electrolyzer, open direct supply, is 1A/dm with the current density 2The electric current constant-current electrolysis handled 10 minutes, the waste water after the electrolysis treatment detects through atomic absorption spectrophotometry, nickeliferous in the water is 1.25mg/L, the clearance of nickel reaches 99.87%.
Embodiment 2~11
Repeat embodiment 1, different treatment condition and results are listed in the table below.In the table, " electro-conductive material " i.e. be " electronic conductive material ", and " ion-exchange particles " i.e. be " particle with ion-exchange capacity ", and " ion-exchange particles volume accounting " is the ratio that ion-exchange particles accounts for the stopping composition cumulative volume.
Embodiment 12
Repeat embodiment 7, difference is that direct supply adopts regular communicating DC electric current, every commutation in 1 hour once, handles continuously 10 days in the electrolysis treatment process, and treatment effect remains unchanged.Begin to descend and handle 2 days aftertreatment effects continuously by the method for implementing 7.
Embodiment 13
Repeat embodiment 8, difference is to replace constant pressure and constant flow pattern direct supply with the pulse power, and dutycycle is 45%, and the nickel content of handling in the water of back is 0.05, and the clearance of nickel reaches 99.97%.

Claims (10)

1. the electrolytic processing method of heavy metal-containing waste water, it is characterized in that described waste water is charged into electrolyzer as described below makes electrolysis treatment, the structure of this electrolyzer is: be provided with in a cell body (4) and anodal anode (2) that is electrically connected of direct supply (1) and the negative electrode (5) that is electrically connected with dc power cathode, stopping composition (3) is set between two electrodes, and this stopping composition is mixed by electronic conductive material (7) and particle (8) with ion-exchange performance.
2. method according to claim 1 is characterized in that described electronic conductive material is at least a in electronic conduction particle, wire cloth, foamed metal, the charcoal fiber.
3. method according to claim 2 is characterized in that described electronic conduction particle is at least a in activated carbon granule, graphite granule, metallic particles, boron-doped diamond particle, conductive metal oxide particle, the electronic conduction high molecular polymerization composition granule.
4. method according to claim 2 is characterized in that described charcoal fiber is at least a in activated carbon fiber, activated carbon felt, active carbon cloth, graphite felt, the Graphite cloth.
5. method according to claim 1 is characterized in that described particle with ion-exchange performance is at least a in ion-exchange resin particles, zeolite granular, sieve particle, the bentonite clay particle.
6. method according to claim 1, the particle cumulative volume that it is characterized in that having in the described stopping composition ion-exchange performance is 10%~90% of a stopping composition cumulative volume.
7. according to claim 1,2,3,5 or 6 described methods, it is characterized in that described grain diameter is 0.1mm~10mm.
8. method according to claim 1 is characterized in that with the porous insulation barrier film described anode and/or negative electrode and the isolation of described stopping composition.
9. method according to claim 8 is characterized in that described barrier film is at least a in ion-exchange membrane, porous ceramics barrier film, microporous polypropylene membrane, polyethene microporous membrane, fibreglass diaphragm, synthon barrier film, asbestos diaphragm, nonmetallic filter cloth or the filter screen.
10. method according to claim 1 is characterized in that described direct supply is constant voltage or constant voltage dc source, constant current or current stabilization direct supply, regular a kind of in communicating DC power supply or the pulse dc power.
CN2009101022083A 2009-09-03 2009-09-03 Electrolytic treatment method of heavy metal-containing wastewater Pending CN102001729A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2009101022083A CN102001729A (en) 2009-09-03 2009-09-03 Electrolytic treatment method of heavy metal-containing wastewater

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2009101022083A CN102001729A (en) 2009-09-03 2009-09-03 Electrolytic treatment method of heavy metal-containing wastewater

Publications (1)

Publication Number Publication Date
CN102001729A true CN102001729A (en) 2011-04-06

Family

ID=43809479

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2009101022083A Pending CN102001729A (en) 2009-09-03 2009-09-03 Electrolytic treatment method of heavy metal-containing wastewater

Country Status (1)

Country Link
CN (1) CN102001729A (en)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102381753A (en) * 2011-09-26 2012-03-21 中国科学技术大学 Bioelectrochemical film reactor device
CN102557205A (en) * 2012-01-21 2012-07-11 杭州普普科技有限公司 Novel method and apparatus for enriching and separating metal ions in sewage
CN102583620A (en) * 2012-02-16 2012-07-18 浙江工业大学 Method for removing heavy metal ions from waste water and solidifying and recycling
CN102730800A (en) * 2011-04-12 2012-10-17 中国科学院长春应用化学研究所 Method and device for utilizing intermittent energy to electrolyze water
CN102861550A (en) * 2012-09-07 2013-01-09 常州大学 Method for synthesizing iron-modified bentonite
CN102895942A (en) * 2012-09-07 2013-01-30 常州大学 Method for synthesizing iron modified bentonite
CN102895941A (en) * 2012-09-07 2013-01-30 常州大学 Method for synthesizing iron-aluminum modified bentonite
CN102923889A (en) * 2011-08-12 2013-02-13 翁伟胜 An electrolysis device
CN103232095A (en) * 2013-04-26 2013-08-07 清华大学 Device and method for recovering activity of zero-valent iron passivated in Cr pollution removal process
CN103359809A (en) * 2013-07-11 2013-10-23 陈艺文 Ion removing device
CN103420456A (en) * 2013-05-15 2013-12-04 上海理工大学 Method for removing ammonia nitrogen by three-dimensional electrode
CN103785677A (en) * 2014-01-26 2014-05-14 河北欧美环境工程有限公司 Integrated device for heavy metal contaminated soil remediation and leacheate recycling and method thereof
CN104085964A (en) * 2014-07-07 2014-10-08 常州大学 Electrochemical treatment method for removing lead ions from water by adopting polyaniline/attapulgite paper electrode
CN104250035A (en) * 2014-09-18 2014-12-31 清华大学 Electrically driven deionizer and method for treating water by adopting deionizer
CN104370349A (en) * 2014-11-06 2015-02-25 杨新玉 Device for purifying wastewater and waste gas containing medium/low-concentration heavy metal ions
CN105143114A (en) * 2013-04-22 2015-12-09 松下知识产权经营株式会社 Liquid processing apparatus
CN105174490A (en) * 2015-09-15 2015-12-23 湖南农业大学 Device and method for removing cadmium in irrigation water by utilizing three-dimensional electrode of solar-assisted microorganisms
CN106115986A (en) * 2016-07-01 2016-11-16 武汉大学 The antifouling stifled hydrocone type strainer filtering device that a kind of electrochemistry strengthens
WO2017071564A1 (en) * 2015-10-27 2017-05-04 雅本化学股份有限公司 Three-dimensional electrode filler and manufacturing method thereof
CN107487908A (en) * 2017-08-15 2017-12-19 广东博地环境工程有限公司 One kind fluidisation pole plate electric flocculation reactor and its method of work
CN108570689A (en) * 2018-04-24 2018-09-25 大连交通大学 Electrolysis prepares the device and method of chlorine dioxide

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102730800B (en) * 2011-04-12 2014-05-21 中国科学院长春应用化学研究所 Method and device for utilizing intermittent energy to electrolyze water
CN102730800A (en) * 2011-04-12 2012-10-17 中国科学院长春应用化学研究所 Method and device for utilizing intermittent energy to electrolyze water
CN102923889A (en) * 2011-08-12 2013-02-13 翁伟胜 An electrolysis device
CN102381753B (en) * 2011-09-26 2013-03-20 中国科学技术大学 Bioelectrochemical film reactor device
CN102381753A (en) * 2011-09-26 2012-03-21 中国科学技术大学 Bioelectrochemical film reactor device
CN102557205A (en) * 2012-01-21 2012-07-11 杭州普普科技有限公司 Novel method and apparatus for enriching and separating metal ions in sewage
CN102583620B (en) * 2012-02-16 2013-11-13 浙江工业大学 Method for removing heavy metal ions from waste water and solidifying and recycling
CN102583620A (en) * 2012-02-16 2012-07-18 浙江工业大学 Method for removing heavy metal ions from waste water and solidifying and recycling
CN102895941A (en) * 2012-09-07 2013-01-30 常州大学 Method for synthesizing iron-aluminum modified bentonite
CN102861550A (en) * 2012-09-07 2013-01-09 常州大学 Method for synthesizing iron-modified bentonite
CN102895942B (en) * 2012-09-07 2014-10-29 常州大学 Method for synthesizing iron modified bentonite
CN102895942A (en) * 2012-09-07 2013-01-30 常州大学 Method for synthesizing iron modified bentonite
CN102895941B (en) * 2012-09-07 2015-01-14 常州大学 Method for synthesizing iron-aluminum modified bentonite
US9663391B2 (en) 2013-04-22 2017-05-30 Panasonic Intellectual Property Management Co., Ltd. Liquid processing apparatus
CN105143114B (en) * 2013-04-22 2017-11-24 松下知识产权经营株式会社 Liquid handling device
CN105143114A (en) * 2013-04-22 2015-12-09 松下知识产权经营株式会社 Liquid processing apparatus
EP2977356A4 (en) * 2013-04-22 2016-05-11 Panasonic Ip Man Co Ltd Liquid processing apparatus
CN103232095A (en) * 2013-04-26 2013-08-07 清华大学 Device and method for recovering activity of zero-valent iron passivated in Cr pollution removal process
CN103420456A (en) * 2013-05-15 2013-12-04 上海理工大学 Method for removing ammonia nitrogen by three-dimensional electrode
CN103359809A (en) * 2013-07-11 2013-10-23 陈艺文 Ion removing device
CN103359809B (en) * 2013-07-11 2015-06-10 赵然 Ion removing device
CN103785677A (en) * 2014-01-26 2014-05-14 河北欧美环境工程有限公司 Integrated device for heavy metal contaminated soil remediation and leacheate recycling and method thereof
CN103785677B (en) * 2014-01-26 2016-08-17 河北欧美环境工程有限公司 Heavy-metal contaminated soil reparation and leacheate recycle integrated apparatus and method thereof
CN104085964A (en) * 2014-07-07 2014-10-08 常州大学 Electrochemical treatment method for removing lead ions from water by adopting polyaniline/attapulgite paper electrode
CN104250035A (en) * 2014-09-18 2014-12-31 清华大学 Electrically driven deionizer and method for treating water by adopting deionizer
CN104370349A (en) * 2014-11-06 2015-02-25 杨新玉 Device for purifying wastewater and waste gas containing medium/low-concentration heavy metal ions
CN105174490A (en) * 2015-09-15 2015-12-23 湖南农业大学 Device and method for removing cadmium in irrigation water by utilizing three-dimensional electrode of solar-assisted microorganisms
WO2017071564A1 (en) * 2015-10-27 2017-05-04 雅本化学股份有限公司 Three-dimensional electrode filler and manufacturing method thereof
CN106115986A (en) * 2016-07-01 2016-11-16 武汉大学 The antifouling stifled hydrocone type strainer filtering device that a kind of electrochemistry strengthens
CN107487908A (en) * 2017-08-15 2017-12-19 广东博地环境工程有限公司 One kind fluidisation pole plate electric flocculation reactor and its method of work
CN108570689A (en) * 2018-04-24 2018-09-25 大连交通大学 Electrolysis prepares the device and method of chlorine dioxide

Similar Documents

Publication Publication Date Title
CN102001729A (en) Electrolytic treatment method of heavy metal-containing wastewater
CN103723868B (en) Water purifier
Dermentzis Removal of nickel from electroplating rinse waters using electrostatic shielding electrodialysis/electrodeionization
CN103304038B (en) Electrochemical-biological membrane synergistic reactor and application thereof in nitrogen-containing organic wastewater
CN105858779B (en) A method of by recycling metal in low-concentration heavy metal ions waste water
CN102329007A (en) Microbial desalting cell (MDC)
US3954594A (en) Electrochemical cell for decreasing the cyanide and heavy metal content of an aqueous solution
US3970531A (en) Decreasing the cyanide and heavy metal content of an aqueous solution
CN102070268B (en) Environmentally-friendly treatment method and device for organic sewage
CN106830449A (en) Effectively reduce the method and its processing system of chemical nickle-plating wastewater pollutant
CN105541020B (en) Composite type artificial wetland desalination system based on CDI
CN104163479A (en) Method and device for removing nitrate nitrogen in water by using three-dimensional electrodes
CN103951017B (en) A kind of electrolysis treatment contains cyanogen copper-contained electroplating waste water and reclaims the method for copper
Liu et al. Overview of recent developments of resource recovery from wastewater via electrochemistry-based technologies
CN103641207B (en) A kind of Zinc-containing electroplating waste water combined electrolysis groove treatment process
CN103641206B (en) A kind of method applied the process of combined electrolysis groove and contain cadmium electroplating wastewater
Ayub et al. Removal of heavy metals (Cr, Cu and Zn) from electroplating wastewater by electrocoagulation and adsorption processes
CN101618905A (en) Method for treating phosphoric wastewater through ozone-enhanced electrocoagulation
CN204022519U (en) A kind of for the water treatment device except the nitric nitrogen that anhydrates
CN108298744A (en) A kind of non-biochemical deep treatment method of breeding wastewater
CN104341029A (en) EDI (Electro-deionization) and electro-catalytic integrated reactor and method for removing nitrate
CN106986424A (en) A kind of electromagnetism cooperative reinforcing microelectrolysis processing high-concentration industrial waste liquid and the method for reclaiming high level heavy metal
El-Shazly et al. Investigations and kinetics study for the effet of solution flow rate on the performance of electrocoagulation unit used for nutrients removal
JP3536092B2 (en) Method for removing phosphorus from water to be treated using electric field
CN206486383U (en) Effectively reduce the processing system of chemical nickle-plating wastewater pollutant

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Open date: 20110406