CN105016431A - Method and apparatus for removal and recovering of heavy metal ions from wastewater - Google Patents
Method and apparatus for removal and recovering of heavy metal ions from wastewater Download PDFInfo
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- CN105016431A CN105016431A CN201510436419.6A CN201510436419A CN105016431A CN 105016431 A CN105016431 A CN 105016431A CN 201510436419 A CN201510436419 A CN 201510436419A CN 105016431 A CN105016431 A CN 105016431A
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 87
- 150000002500 ions Chemical class 0.000 title claims abstract description 79
- 239000002351 wastewater Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 69
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010949 copper Substances 0.000 claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 239000011733 molybdenum Substances 0.000 claims abstract description 9
- 238000003487 electrochemical reaction Methods 0.000 claims description 25
- 230000000694 effects Effects 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000008187 granular material Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 239000003610 charcoal Substances 0.000 claims description 10
- 238000006056 electrooxidation reaction Methods 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 238000009713 electroplating Methods 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 238000004065 wastewater treatment Methods 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 238000007747 plating Methods 0.000 claims description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 20
- 238000012545 processing Methods 0.000 abstract description 10
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052793 cadmium Inorganic materials 0.000 abstract description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 239000011133 lead Substances 0.000 abstract description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052753 mercury Inorganic materials 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 abstract description 3
- 239000010937 tungsten Substances 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
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- 230000035484 reaction time Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
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- 238000006479 redox reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
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Abstract
The present invention relates to a method and an apparatus for electrochemical processing of heavy metal ion-containing wastewater by use of an activated carbon basket as an electrode. According to the method, by combination of physical adsorption concentration, electrochemical reduction adsorption and electrochemical catalytic oxidation, heavy metal ion-containing wastewater is processed, and copper, lead, zinc, iron, cobalt, nickel, manganese, cadmium, mercury, tungsten, molybdenum, and all other heavy metal pollutants in the wastewater can be effectively and thoroughly removed. The method not only can process wastewater containing a high concentration of heavy metal ions, is also suitable for processing wastewater containing extremely dilute concentrations of heavy metal ions (the concentration range is from 0 to hundreds of thousands of ppm), meanwhile compared with the traditional method, the method greatly reduces the processing cost, is inexpensive and simple in operation and equipment, can be recycled to run, and has great practical value.
Description
Technical field
The invention belongs to technical field of waste water processing, be specially the removal technique of heavy metal ions in wastewater, relate to a kind for the treatment of process containing wide cut concentration range effluent containing heavy metal ions and device, be specifically related to a kind of gac basket and do electrode, electrochemistry assists the method and apparatus removing heavy metal ions in wastewater.
Background technology
Heavy metal ion-containing waste water is mainly from trade effluents such as mining, non-ferrous metal, plating, electrolysis, agricultural chemicals, medicine, tobacco, paint, pigment.Heavy metal ion mainly comprises all heavy metal ion such as copper, lead, zinc, iron, cobalt, nickel, manganese, cadmium, mercury, tungsten, molybdenum.Because heavy metal ion can not disintegrate, easily accumulate in vivo, destroy the normal metabolic activity of organism, to the mankind and environmental hazard very big.
Along with people's environmental pollution attention degree improves constantly, more and more higher to the requirement of wastewater treatment.In current heavy metal ion-containing waste water treatment process, used equipment and process or processing speed are slow, primary treatment amount is little, otherwise invest high, floor space large, or easily produce secondary pollution, cost is high.As: although active carbon adsorption less investment, take up an area little, charcoal absorption speed is slow, loading capacity is little, is not suitable for processing the higher waste water of Pollutant levels; Although the precipitator method are removed, scope is wide, efficiency is high, easily in treating processes, produces secondary pollution, consumes a large amount of precipitation agent, completely removal of heavy metal ions, cannot cannot process pole dilute concentration effluent containing heavy metal ions simultaneously; Ion exchange method can realize non-wastewater discharge in treating processes, but its investment is high, and floor space is large, and Pollutants in Wastewater concentration should not be too high, and can not be effective to all ion-exchange; Biosorption process cheaper starting materials is easy to get, can efficient recovery heavy metal ion, advantages of good adsorption effect, but the culture propagation speed adopted physical strength that is slow, biological adsorption agent is weak, poor chemical stability and can not change the valency of metal ion in adsorption process, reduce the toxicity of heavy metal ion.Also the technique adopting electrochemical method to be separated heavy metal ions in wastewater is had in prior art, such as, Authorization Notice No. is the treatment process that patent discloses a kind of heavy metal containing sewage of CN101088938B, adopt electrochemical catalytic oxidation technology, pH value being adjusted to neutral sewage introduces in reaction tower, air is filled with in reaction tower, and pig scrap is added in reaction tower, the catalyzer such as gac and sponge iron deoxidizing agent, make sewage generation oxidation-reduction reaction, iron in sewage is oxidized, heavy metal ion is reduced into unbound state heavy metal, but usually exist with the form of complex compound due to the heavy metal ion in sewage and be difficult to crack in weak oxide environment, therefore this inventive method can not remove the heavy metal ion in sewage completely, and the iron-carbon micro-electrolysis treatment technology that the method does not break traditions, the electric current of high voltage is connected with in reaction tower, and due to the contact area of sewage and electrode pad itself very little, electrochemical reaction efficiency is still lower.In addition, application number be 201410325704.6 patent application also disclose a kind of anodizing technique for removing prussiate and heavy metal, adopt anodizing technology, catalytic carrier gac is added at anodizing trench bottom, to improve oxidation efficiency, but whole application documents all clearly do not describe activated carbon catalysis carrier, namely whether load has catalyzer not describe activated carbon catalysis carrier, and the kind of catalyzer and consumption etc., also not clearly demonstrating these at the gac of anodizing trench bottom is how to accelerate cracking of this metal complex, therefore, this technical scheme is unclear, in addition, the method adopts platinum alloy series as electrode, not only material expensive, and electrode pad and waste water area little, electrolytic efficiency is low.
In sum, make full use of and optimize the removing process of existing heavy metal ions in wastewater, develop a kind of heavy metal ion be applicable to containing wide cut concentration range, remove from waste water and reclaim method and the device of heavy metal ion simply efficiently, improve the clearance of heavy metal ion, reduce costs, realize energy-saving and emission-reduction, reduce the wasting of resources, there is very important realistic meaning.
Summary of the invention
The present invention is directed to the deficiency of problem and the current prior art proposed in background technology, there is provided a kind of remove from waste water and reclaim method and the device of heavy metal ion, the method creatively proposes to make electrode with gac basket, the new technology of electrochemistry auxiliary treatment heavy metal ion-containing waste water, adopt physical adsorption, electrochemical reduction adsorbs, electrochemical catalytic oxidation such as to be separated at the technology combined with flocculation sediment, eliminate the heavy metal ion in electroplating wastewater (or other heavy metal ion-containing waste water) to greatest extent, and described method removal effect is good, equipment is simple, processing efficiency is high and working cost is low, equipment is capable of circulation, continuous high-efficient operates.
First object of the present invention is achieved in that
Remove from waste water and reclaim the method for heavy metal ion, comprising waste water to introduce in electrochemical reaction apparatus and be removed, in described electrochemical reaction apparatus, being provided with anode and negative electrode; Anode and negative electrode are mesh basket or the frame of plastics or insoluble metal making, gac and the electrochemical oxidation catalyst of large grained is filled with inside anode basket or frame, fill method is that gac and granules of catalyst mix mutually or gac and catalyzer layering are arranged, and is drawn is connected to positive source in the middle of anode gac basket by carbon-point or insoluble metal wire; Be filled with the gac of large grained inside described negative electrode basket or frame, be connected to power cathode by wire; Described catalyzer is made up of the mixture of multiple transition-metals and their oxides, the effect of described catalyzer is: the anodic oxidation DeR for organic-complex thing provides catalysis and provides the metal ion being convenient to organic product precipitation, and the volume of anode and cathodic activity charcoal basket is respectively 10% ~ 50% of this electrochemical reaction apparatus useful volume.
Further, apply direct current between the anode and cathode of the apparatus of electrochemical reaction described in technique scheme, current density is 5mA/dm
2~ 10A/dm
2, current/voltage is 100mv ~ 30v.
Further, in order to accelerate catalyzed oxidation speed, in waste water described in technique scheme, add oxygenant, described oxygenant can be one or more in oxygen, hydrogen peroxide or potassium permanganate, sodium chlorate, clorox.
Further, agitator gentle agitation waste water is adopted during wastewater treatment described in technique scheme.
Further, transition metal described in technique scheme is iron, platinum plating is black iron, copper, manganese, nickel, titanium, vanadium, molybdenum, cobalt, platinum, silver; Described transition metal oxide is the oxide compound of iron, copper, manganese, nickel, titanium, vanadium, molybdenum, cobalt etc.
Further, catalyst content described in technique scheme is 1% ~ 20% of quality of activated carbon, and described activated carbon granule particle diameter is 5 ~ 60 orders.
Further, waste water described in technique scheme is electroplating wastewater or other waste water containing heavy metal ion.
Further, insoluble metal described in technique scheme is titanium, titanium alloy or other precious metal alloys.
Further, heavy metal ion described in technique scheme comprises copper, lead, zinc, iron, cobalt, nickel, manganese, cadmium, mercury, tungsten, molybdenum.
Second object of the present invention is achieved in that a kind ofly to be removed and reclaims the device of heavy metal ion from waste water, is provided with anode and negative electrode in described device; Described anode and negative electrode are mesh basket or the frame of plastics or insoluble metal making, gac and the electrochemical oxidation catalyst of large grained is filled with inside anode basket or frame, fill method is that gac and granules of catalyst mix mutually or gac and catalyzer layering are arranged, and is drawn is connected to positive source in the middle of anode gac basket by carbon-point or insoluble metal wire; Be filled with the gac of large grained inside described negative electrode basket or frame, be connected to power cathode by wire; Described catalyzer is made up of the mixture of multiple transition-metals and their oxides, and the volume of anode and cathodic activity charcoal basket is respectively 10% ~ 50% of this electrochemical reaction apparatus useful volume.
Further, in technique scheme catalyzer adopt transition metal and transition metal oxide and the present invention first object described in identical.
Of the present inventionly a kind ofly remove from waste water and reclaim method and the device of heavy metal ion, be removed by kinds of reaction synergy and reclaimed heavy metal ion in this electrochemical reactor, realizes the heavy metal ion in degree of depth removal waste water.Its wastewater treatment principle and technique effect as follows:
(1) anodizing reduction process:
Anode: complex thing (or other organic heavy metal ion) concentrates by gac, be adsorbed onto its surface (the very large anode surface of specific surface area), and these organic heavy metal ions are electrochemically oxidized degraded under catalyst.Its principle is on the anode surface, the organic complex ion in complex thing (or other organic heavy metal ion) at the electrode surface with in solution due to electrode reaction produce active oxygen ion (OH*, H
2o
2, O
3deng) or the oxygenant generation oxidizing reaction that adds, the oxidized degraded of organism, heavy metal ion the is broken away from constraint of complexing ion.Meanwhile, be oxidized to organic acid organism and can also react to generate with heavy metal ion and precipitate, play the effect of coagulating sedimentation.
The step more complicated of anodic oxidation reactions, such as copper ions complex compound (or other organism) waste water, contingent reaction is as follows:
1)、 [Cu(CN)
4]
2-+ 2O
3+ 4OH* - 4e →Cu
2 ++4CO
2↑+ 2N
2↑ +2H
2O
2)、 [CuR
4]
n-+ OH* -ne →ROOCu ↓+2nH
2O；
(2) negative electrode: in electrochemical reaction process, heavy metal ion (free or broken away from the heavy metal ion of complexing ion constraint after anode is electrochemically oxidized) concentrates, is adsorbed onto its surface (activated carbon surface by gac, the very large anode surface of specific surface area), under cathodic current effect, heavy metal ion obtains electronics and is reduced into metal simple-substance, is attracted to the surface of cathodic activity charcoal simultaneously or is deposited on cathode bottom.If in addition waste water solution pH lower than 7 time (acid waste water), along with the carrying out of electrolytic reaction, a large amount of H
+be reduced into H
2after effusion is gone, heavy metal ion just can be reduced; Negative electrode also can produce a large amount of OH simultaneously
-, also can react to metal ion and produce corresponding precipitation of hydroxide and removal of heavy metal ions.
The step more complicated of cathodic reduction reaction, such as copper ions waste water, contingent reaction is as follows:
1）、Cu
2 ++2e → Cu↓
2)、 Cu
2 ++2OH
-→ Cu(OH)
2↓。
Advantage of the present invention is:
(1) electrochemical reaction apparatus of the present invention, in anode gac basket (frame), gac can play the effect of Adsorption Concentration complex thing (or other organic heavy metal ion), degrades under catalyst action to its electrochemical oxidation simultaneously; Gac in cathodic activity charcoal basket or frame can by heavy metal ion adsorbed concentrated, and the minimum concentration requirement that make concentration of heavy metal ion reach electrochemical cathode reduction to separate out, even so extremely the heavy metal ion of dilute concentration also can compare H at cathode surface
+have more to obtain electronic edge and being restored, degraded, like this by the redox reaction of apparatus of the present invention, effectively can remove the heavy metal ion (concentration range can be 0 to hundreds of thousands of ppm) of wide cut concentration in waste water, and equipment is simple, easy to operate, floor space is little, and cost is low, effective;
(2) because gac is a material with huge specific surface area, to the basket of gac or frame be loaded with as electrode, just can reach the electrode area than the general electrode slice much bigger (hundred times even several more than thousand ten thousand times) in ordinary electrode reaction, its electrochemical efficiency improves greatly, electrochemical treatment cost is reduced greatly, and this is the most outstanding advantage of the present invention;
(3) catalyzer can effectively be adsorbed on the activated carbon in catalytic process, it is avoided to run off fast, the method is compared with Conventional electrochemical oxidation style, increase anode-catalyzed oxidation area and catalytic effect, improve current efficiency, substantially reduce the reaction times, improve treatment effect and processing cost;
(4) the precipitated metal simple-substance that gets off or compound solid in electrochemical reaction apparatus of the present invention, heavy metal can be refined after oven dry and serve as industrial raw material, be sold to other industrial trades, like this can be cost-saving, the recycling of metal solid can be accomplished again.
Embodiment
The method of electrode, electrochemistry auxiliary catalysis oxide treatment electroplating wastewater (or other heavy metal ion-containing waste water) made by the gac basket that the present invention proposes, electrochemistry removal is carried out, to reach the requirement of discharging standards to electroplating wastewater (or other heavy metal ion-containing waste water).The present invention utilizes this electrochemical treatment new technology effectively can remove the feature of heavy metal ions in wastewater, compare the unicity of the common electrochemical reaction technology reported, establish the new approaches that electrode made by gac basket, electrochemistry is assisted, redox is degraded, thus provide a kind of new technology of efficient removal heavy metal pollution in wastewater thing.
Technical scheme of the present invention is:
Remove from waste water and reclaim the method for heavy metal ion, comprising waste water to introduce in electrochemical reaction apparatus and be removed, in described electrochemical reaction apparatus, being provided with anode and negative electrode; Anode and negative electrode are mesh basket or the frame of plastics or insoluble metal making, gac and the electrochemical oxidation catalyst of large grained is filled with inside anode basket or frame, fill method is that gac and granules of catalyst mix mutually or gac and catalyzer layering are arranged, and is drawn is connected to positive source in the middle of anode gac basket by carbon-point or insoluble metal wire; Be filled with the gac of large grained inside described negative electrode basket or frame, be connected to power cathode by wire; Described catalyzer is made up of the mixture of multiple transition-metals and their oxides, the effect of described catalyzer is: the anodic oxidation DeR for organic-complex thing provides catalysis and provides the metal ion being convenient to organic product precipitation, and the volume of anode and cathodic activity charcoal basket is respectively 10% ~ 50% of this electrochemical reaction apparatus useful volume.When process contains electroplating wastewater (or other organic waste water) of heavy metal ion, first, the pending electroplating wastewater (or other organic waste water) containing heavy metal ion is placed in electrochemical reactor; Then between the anode basket, negative electrode basket of described electrochemical reactor, constant current is applied by power-supply system, control voltage is 100mv ~ 30v, and with waste water described in agitator gentle agitation, make described waste water generation electrochemical reaction, conduction time is 5min ~ 24h, then leaves standstill, precipitates, is separated, get supernatant liquor check weighing metal ion content, supernatant liquor directly can be discharged after up to standard, bottom be squeezed containing the precipitation of heavy metal residue thing, dries, refine rear recovery.
The multiple concerted reaction detailed process occurred in above-mentioned electrochemical reactor is as follows: 1, " gac " of the load of anode basket is by the complex thing in waste water or organic heavy metal ionic adsorption, concentrated; 2, these enriched materials are cracked into the heavy metal ion of unbound state under " catalyzer " effect by the active oxygen ion oxidation that electrode produces; 3, the gac of negative electrode basket load is by concentrated for the free heavy metal ion produced after heavy metal ion free near described negative electrode and anode electrochemical oxidation, absorption; 4, simultaneously, the cathodic reaction OH that makes heavy metal ion obtain electronics under cathodic current effect to be reduced into heavy metal simple substance or to produce with catholyte
-in conjunction with the corresponding precipitation of hydroxide of formation; 5, electrolysis complete after waste water can be introduced in next electrochemical reactor unit (each electrochemical reactor unit is the same with above-mentioned electrochemical reactor), be finally introduced in cleaning section (as coagulation, precipitation), be finally purified water; 6, in production process, also the above-mentioned waste water obtained after each electrochemical reactor process can be left standstill, precipitate, be separated, obtain supernatant liquor, measure residual gravity concentration of metal ions in described supernatant liquor, if the concentration of heavy metal ion recorded lower than national heavy metal wastewater thereby emission standard, then can directly discharge, if exceed standard, then again repeat process, till up to standard by above-mentioned steps; 7, finally by after above-mentioned electrochemical reactor process bottom containing heavy metal residue thing precipitation squeezing, dry, refine after reclaim.Below by specific embodiment, technical scheme of the present invention is described in detail.
Embodiment 1
Design an electrochemical reaction apparatus, in described device, be provided with anode and negative electrode; Described anode and negative electrode are titanium basket, and be filled with gac and the electrochemical oxidation catalyst of large grained inside anode titanium basket, described gac and granules of catalyst mix mutually, drawn be connected to positive source in the middle of anode gac basket by carbon-point or insoluble metal wire; Be filled with the gac of large grained inside described cathode titanium basket, be connected to power cathode by wire; Described catalyzer is made up of copper sheet and hopcalite thereof, described copper sheet and oxide content thereof are 10% of quality of activated carbon, described activated carbon granule particle diameter 60 order, the volume of described anode and cathodic activity charcoal basket is respectively 30% of this electrochemical reaction apparatus useful volume, be provided with magnetic stirring apparatus below described electrochemical reactor, can be used to stir waste water.
Introduced in above-mentioned electrochemical reaction apparatus by the electroplating wastewater of certain Electroplate Factory (be 3400mg/L containing copper, nickel, meta-alkalescence), the spacing between electrode is 3cm, and between electrode, applying constant current by electrochemical workstation, (current density is about 100mA/ dm
2, voltage is 2 ~ 3v about), and to be degraded solution by magnetic stirring apparatus gentle agitation, reaction times is 50min, staticly settles after processing, and then gets supernatant liquor check weighing metal ion content, after process, heavy metal ion total content is down to 300mg/L, and clearance reaches 91%.
Embodiment 2
Design an electrochemical reaction apparatus, in described device, be provided with anode and negative electrode; Described anode and negative electrode are nylon wire, gac and the electrochemical oxidation catalyst of large grained is filled with inside anode nylon wire, described gac and catalyzer layering are arranged, and drawn be connected to positive source in the middle of anode gac basket by carbon-point or insoluble metal wire; Be filled with the gac of large grained inside described negative electrode nylon wire, be connected to power cathode by wire; Described catalyzer is made up of iron nail and hopcalite thereof, described iron nail and oxide content thereof are 15% of quality of activated carbon, described activated carbon granule particle diameter 30 order, the volume of described anode and cathodic activity charcoal basket is respectively 40% of this electrochemical reaction apparatus useful volume, be provided with magnetic stirring apparatus below described electrochemical reactor, can be used to stir waste water.
Introduced in above-mentioned electrochemical reaction apparatus by the electroplating wastewater of certain Electroplate Factory (be 250mg/L containing copper, nickel, chromium, meta-alkalescence), the spacing between electrode is 3cm, and between electrode, applying constant current by electrochemical workstation, (current density is about 100mA/ dm
2, voltage is 2 ~ 3v about), and to be degraded solution by magnetic stirring apparatus gentle agitation, reaction times is 40min, staticly settles after processing, and then gets supernatant liquor check weighing metal ion content, after process, heavy metal ion total content is down to 0.5mg/L, and clearance reaches 99.8%.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. remove from waste water and reclaim the method for heavy metal ion, it is characterized in that: waste water is introduced in electrochemical reaction apparatus and be removed, in described electrochemical reaction apparatus, be provided with anode and negative electrode; Anode and negative electrode are mesh basket or the frame of plastics or insoluble metal making, gac and the electrochemical oxidation catalyst of large grained is filled with inside anode basket or frame, fill method is that gac and granules of catalyst mix mutually or gac and catalyzer layering are arranged, and is drawn is connected to positive source in the middle of anode gac basket by carbon-point or insoluble metal wire; Be filled with the gac of large grained inside described negative electrode basket or frame, be connected to power cathode by wire; Described catalyzer is made up of the mixture of multiple transition-metals and their oxides, the effect of described catalyzer is: the anodic oxidation DeR for organic-complex thing provides catalysis and provides the metal ion being convenient to organic product precipitation, and the volume of anode and cathodic activity charcoal basket is respectively 10% ~ 50% of this electrochemical reaction apparatus useful volume.
2. according to claim 1ly remove from waste water and reclaim the method for heavy metal ion, it is characterized in that: apply direct current between the anode and cathode of described electrochemical reaction apparatus, current density is 5mA/dm
2~ 10A/dm
2, current/voltage is 100mv ~ 30v.
3. according to claim 1ly remove from waste water and reclaim the method for heavy metal ion, it is characterized in that: in described waste water, add oxygenant, described oxygenant is one or more in oxygen, hydrogen peroxide or potassium permanganate, sodium chlorate, clorox.
4. according to claim 1ly remove from waste water and reclaim the method for heavy metal ion, it is characterized in that: during described wastewater treatment, adopt agitator gentle agitation waste water.
5. according to claim 1ly remove from waste water and reclaim the method for heavy metal ion, it is characterized in that: described transition metal is iron, platinum plating is black iron, copper, manganese, nickel, titanium, vanadium, molybdenum, cobalt, platinum, silver; Described transition metal oxide is the oxide compound of iron, copper, manganese, nickel, titanium, vanadium, molybdenum, cobalt etc.
6. according to claim 1ly remove from waste water and reclaim the method for heavy metal ion, it is characterized in that: described catalyst content is 1% ~ 20% of quality of activated carbon, described activated carbon granule particle diameter is 5 ~ 60 orders.
7. removing from waste water and reclaiming the method for heavy metal ion according to any one of claim 1-6, is characterized in that: described waste water is electroplating wastewater or other waste water containing heavy metal ion.
8. remove from waste water and reclaim the device of heavy metal ion, it is characterized in that: in described device, be provided with anode and negative electrode; Described anode and negative electrode are mesh basket or the frame of plastics or insoluble metal making, gac and the electrochemical oxidation catalyst of large grained is filled with inside anode basket or frame, fill method is that gac and granules of catalyst mix mutually or gac and catalyzer layering are arranged, and is drawn is connected to positive source in the middle of anode gac basket by carbon-point or insoluble metal wire; Be filled with the gac of large grained inside described negative electrode basket or frame, be connected to power cathode by wire; Described catalyzer is made up of the mixture of multiple transition-metals and their oxides, and the volume of anode and cathodic activity charcoal basket is respectively 10% ~ 50% of this electrochemical reaction apparatus useful volume.
9. according to claim 8ly remove from waste water and reclaim the method for heavy metal ion, it is characterized in that: described transition metal is iron, platinum plating is black iron, copper, manganese, nickel, titanium, vanadium, molybdenum, cobalt, platinum, silver; Described transition metal oxide is the oxide compound of iron, copper, manganese, nickel, titanium, vanadium, molybdenum, cobalt etc.
10. according to claim 8ly remove from waste water and reclaim the method for heavy metal ion, it is characterized in that: described catalyst content is 1% ~ 20% of quality of activated carbon, described activated carbon granule particle diameter is 5 ~ 60 orders.
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Application publication date: 20151104 |