Journal of Metallurgical Engineering (ME) Volume 2 Issue 4, October 2013 www.me‐journal.

org

Electrochemical Reduction/Oxidation in the

Abstract even death. Nickel higher than its critical level might
The electrochemical method is a promising technology for a bring about serious lung and kidney problems aside
clean environmental and is widely applied in the control of from gastrointestinal distress, pulmonary fibrosis and
wastewater pollution, especially in the removal of metal and skin dermatitis. Lead not only can cause central
oxidation of refractory organics. The heavy metal wastewater nervous system damage, but also damage the kidney,
treated by the electrochemical method is reviewed in this liver and reproductive system, basic cellular processes
literature. The key and challenges of the application of the and brain functions.
electrochemical method in the control of heavy metal
wastewater are pointed out. Heavy metals pollutants are mainly discharged by
electroplating wastewater, metallurgical industries,
Keywords
metallurgical industries and mining industries.
Electrochemical Oxidation; Heavy Metal; Cyanide; Complex Metal; Electroplating wastewater and metallurgical
Organic Pollutants; Wastewater wastewater are two types of typical heavy metals
water. In general, the electroplating wastewater
I nt roduc t ion contains a high level of heavy metals, such as copper,
During the last two decades, with the rapid nickel, cadmium, chromium, zinc, silver, gold, lead
development of industries and technologies, such as and tin, acid/alkali, cyanide and organic compounds. It
electroplating industries, metallurgical industries, is nonbiodegradable, highly toxic and has a probable
mining operations, fertilizer industries, power carcinogenic impact. The metallurgical wastewater,
generation facilities, electronic device manufacturing which is similar to the electroplating wastewater, also
units, wastewater containing heavy metals and organic includes arsenic and a high concentration of
pollutions compounds has been discharged into the suspended solid. Thus what we concern mostly is
environment increasingly, especially in developing heavy metals and some nonbiodegradable organic
countries. Heavy metals couldn t easy be removed contaminations. Heavy metal ions, which is not the
from the wastewater without advanced treatment unique form in the solution, could be react with NH3
solutions. Due to their high solubility in the aquatic or EDTA (ethylenediaminetetraacetic acid), CN‐
environments, heavy metals can be absorbed and generate metal complex, metal cyanide, respectively.
accumulate in living organisms. If the concentration of Although a lot of solutions have been investigated to
metals in human body beyond the allowable amount, treat the heavy metals such as chemical precipitation,
serious health disorders even the cancer could be absorption solution and ion exchange solution, metal
induced. Hexavalent chromium, of particular concern complex and metal cyanide, it also is a challenge as
because it is carcinogenic and mutagenic, diffuses these compounds couldn t be precipitated directly and
quickly in soil and aquatic environment, is a strong transformed into metal ions easily. However,
oxidizing agent, and irritates plant and animal tissues electrochemical method is a perfect solution to solve
in small quantities. this problem and mineralize the organic compounds as
well.
Most of heavy metals belong to persistent toxic
substance (PTS). Excessive zinc could cause eminent Electrochemical technology, one of advanced oxidation
health problems, such as stomach cramps, skin processes (AOPs), is the most promising technology
irritations, vomiting, nausea and anemia. Copper does for treatment of organic pollutants and heavy metals,
essential work in animal metabolism, but the excessive including electrodialysis, electro‐coagulation,
ingestion of copper brings about serious toxicological electro‐flotation, anodic oxidation and electrochemical
concerns, such as vomiting, cramps, convulsions, or reduction. The condition of the electrochemical

161
www.me‐journal.org Journal of Metallurgical Engineering (ME) Volume 2 Issue 4, October 2013

processes is moderate, without other chemical reagents obtained PAA on the surface of carbon felt to remove
added and is high energy efficiency, and is easily metal ions at low concentration from wastewater,
combined with other technologies. In this paper, four which can take place of the classical way of
aspects will be investigated briefly: a) heavy metals precipitation. Their work provided a novel strategy to
recover from the liquid, b) decomposition of metal meet the new criterion of “zero waste rejection” for
complex and metal cyanide by electrolysis, c) valence sustainable development of environmental issues.
transformation of heavy metal ions by electrochemical
oxidation/reduction, d) organic compounds mineralization Decomposition of Metal Complex and Metal Cyanide
through electrochemical technology. by Electrolysis
The metals and complexing agents such as EDTA, NH3,
H e a vy M e t a l Wa st e w a t e r T re a t m e nt by CN‐ and tartarate were encountered in manufacturing
Ele c t roc he m ic a l T e c hnology printed circuit boards for electroless copper plating,
metal finishing and washing effluents for remediation
Metals Recover from the Liquid by Electrochemical
of metal contaminated soils. Although a lot of methods
Recovery of heavy metals from waster is important not have been developed to treat the metals from
only in economical aspects, but also for environmental wastewater, chemical precipitation is the most wildly
protection. Different physico‐chemical treatment and economically used for the treatment of metals
techniques have emerged in the last decade for the effluents. However, the presence of strong complexing
treatment of electroplating wastewater, and their agents may make the precipitation process ineffective
advantages and limitations are also evaluated. Several at even high metal levels. In addition, the high buffer
electrochemical treatment techniques such as capacity of complex agents requires excessive amounts
electro‐coagulation, flotation, dialysis, deionization of reagents to neutralize alkalinity. The electrolysis
and deposition, have been investigated to remove the process is a meaningful, economic and feasible
metals from wastewater. solution to this problem. Electrodes not only support a
heterogeneous catalysis reaction place, but also aid to
D. Panias and coworkers recovered copper and nickel
transporting the electronic during the process. Power
precipitation from acidic polymetallic aqueous
solutions by the electrorecovery and neutralization. supports the voltage to control the condition of process
Acidic polymetallic wastewaters are generated during and the rate of reaction.
the pyrometallurgical treatment of chalcopyrite for the Juang et al used the apparatus (Fig. 1) to recover
production of primary copper. Most of wastewater metals Cu(II) and strong chelating agents EDTA (H4L)
streams originate from the copper refining and the from their molar ration of 1:1 complexed solutions. The
electrolyte regeneration stages, as well as the sulphuric iridium oxide coated on titanium (IrO2/Ti) was used as
acid and the precious metals plants. The feasibility of the anode which obtained an economically feasible
this electrorecovery was proved theoretically with the proposal that current efficiency and recovery of Cu are
thermodynamic analysis and experimentally under 60% and 95% after electrolysis only for 50 min,
various conditions. The Ni, Pb, Zn, Fe metals remain, respectively.
as expected, in the solution from which nickel can be
recovered with neutralization.
Le et al developed an efficient and low cost
preparation method (Diazonium‐Induced Anchoring
Process) to graft polyacrylic acid (PAA) on the gold
substrate and obtain a new PAA polymer film. As a
broad‐range chelating material, PAA was able to
capture several heavy metal ions at low concentration.
The release of those metal ions from the grafted PAA
film was obtained under electro‐induced‐acidification
by applying an anodic potential at the electrode. The FIG. 1 SCHEMATIC OF THE ELECTROLYSIS CELL
electrodes coated PAA film can be used as a secondary
When a current is applied to the electrolysis cell, the
step‐treatment after conventional ion exchange process
following oxidation reactions likely occur at the anode:
or precipitation to remove heavy metal ions from
wastewater. Her later works presented the use of 2H2O O2 +4H++4e Eθ=‐1.229V (1)

162
Journal of Metallurgical Engineering (ME) Volume 2 Issue 4, October 2013 www.me‐journal.org

4OH‐ O2 +2H2O+4e Eθ=‐0.401V (2) spectroscopic method. (eq 11). The removal efficiency
2OH‐ H2O2 +2e Eθ=‐0.547V (3) of the electrolysis process depended on a variety of
H2O2 O2 +2H++2e Eθ=‐0.682V (4) factors such as the hydrodynamic and mass transport
At the same time, the possible reduction reactions at characteristics, features of electrodes, and power
the cathode are: supply.
CuL2‐+2e Cu(s)+L4‐ (5) Y Gao and their coworkers used pulse current and
O2+2H2O+4e 4OH ‐ θ
E =0.401V (6) cylinder electrodes to remove cyanide and recover
2H++2e H2O Eθ=0V (7) high purity silver from the wastewater at the same
2H2O+2e 2H2+2OH‐ Eθ=0.828V (8) time. Under appropriate conditions, 95.0% of cyanide
Where is: E ‐‐‐‐standard reduction or oxidation
θ removal and 99.8% of silver recover had been achieved
potential. simultaneously within 3 h, with the remaining silver
less than 0.5 mg/L and cyanide less than 10.0 mg/L.
It is obvious that the current efficiency is reduced by
the main side reactions of the evolution of H2 and O2. Mineralization of Organic Compounds by
Motheo et al reported research on the removal of Electrochemical Technology
Cu(Ⅱ) complexed by humic acid at the concentration The organic compounds could be degraded directly on
of 10 mg/L and 100 mg/L, respectively. A filter‐press the electrode and indirectly with electro‐generated
cell with Ti/Ru0.3Ti0.7O2 anode and stainless steel reactive radicals such as ·O2, H2O2, ·OH, Cl2, HClO,
cathode was used and the differences of the ClO‐. The most wildly accepted mechanism on
performance with or without separating membrane pollutant mineralization was the combustion that
were compared. The experimental result indicated that occurred at the surface of electrodes where · OH
the main path of the removal was the electrostatic
radicals are accumulated.
interaction with the anode followed by diffusion
through the membrane and deposition at the cathode. Electrochemical degradation of bisphenol A (BPA) on
Additionally, the degradation of humic acid four types of anodes, Ti/BDD, Ti/Sb‐SnO2, Ti/RuO2 and
contributes to the rate of Cu (II) removal. Coupled Pt was carried out by Yu‐hong Cui et al. BPA was
with oxidation and reduction, Cu (II) removal rate of readily destructed at the Ti/Sb‐SnO2, Ti/BDD, Pt
100 percent was achieved at current efficiencies of 75%, anodes, and ineffectively oxidized at the Ti/RuO2
which showed an indication of the application to the anode. In comparison, with its high durability and
real treatment system. good reactivity for organic oxidation, the Ti/BDD
anode appeared to be the more promising one for the
Mental wastewater containing cyanide is produced
effective treatment of BPA and similar endocrine
mainly due to cyanide reagent applied in gold mining,
disrupting chemical (EDC) pollutants.
electroplating and metal finishing industries. The
conventional chemical method is to oxidize the The degradation of aspirin performed by a novel
cyanide to the less harmful cyanate by using NaClO, modified PbO2 electrode assisted by H2O2, indicated
Na2SO3 and H2O2 as oxidizing agent. Recently, the that H2O2 was effective to accelerate the organic
most promising strategy has been presented that CN‐ pollutants degradation. The removal of aspirin, COD
could be changed into nontoxic cyanate (CNO‐) at the and TOC reached 94%, 81%, 61% within 150 minutes
carbon electrode. According to the following formula, treatment, respectively.
CN‐ was directly (eq 9) and indirectly (eq 10) destroyed
by the electrochemistry process. Conc lusions

CN‐+2OH‐ CNO‐+2e+2H2O (9) Compared with other methods, the advantages of the
‐ ‐
CN +HO2 CNO +OH ‐ ‐ (10) electrochemical methods included lower operating
O2+H2O‐+2e HO2‐+OH‐ (11) costs and less usage of extra chemical reagents and
Keith et al presented a solution that indirect simultaneous achievements of fairly pure metals and
electrocatalytic degradation of CN‐ by exploiting the removal of organic pollutants. Perhaps, the biggest
reactive oxygen intermediated formed at N‐doped advantage is that the electrochemical method could be
carbon nanotube electrodes. The removal mechanism easily controlled to treat the metal wastewater, and
that CN‐ was reduced by HO2‐ (eq 11) was supported organic compounds are removed at the same time.
by cyclic voltammetry and bulk electrolysis and However, more economical and activity electrodes for
formation of CNO‐ was confirmed via the the treatment of special pollutions, advanced process

163
www.me‐journal.org Journal of Metallurgical Engineering (ME) Volume 2 Issue 4, October 2013

condition and more effectively current should be Environmental Science and Technology 45 (2011):
investigated. 3650‐3656.
N. Oyaro, O. Juddy et al., The Contents of Pb, Cu, Zn and
A CK N OWLEDGM EN T
Cd in Meat in Nairobi. . International Journal Food
This work was financially supported by the National
Agriculture Environment 5 (2007): 119–12.
Key Project of Scientific and Technical Supporting
Programs Funded by Ministry of Science & Q. Z. Dai, J.D. Wang et al., “Enhanced Degradation of
Technology of China (NO. 2011BAE07B09). Aspirin by Electrochemical Oxidation with Modified
PbO2 Electrode and Hydrogen Peroxide.” International
R EFEREN CES Journal of Electrochemical Science 7 (2012): 12895‐12906.
A. T. Paulino, F.A.S. Minasse et al., “Novel Adsorbent Based R. S. Juang, L.C. Lin. “Treatment of Complexed Copper (II)
on Silkworm Chrysalides for Removal of Heavy Metals Solutions with Electrochemical Membrane Process.”
from Wastewaters.” Journal of Colloid Interface Science Water Research 34 (2000): 43‐50.
301 (2006): 479–487. R. S. Juang, L.C. Lin. “Efficiencies of Electrolytic Treatment of
C. Comninellis. “Electrocatalysis in the Electrochemical Complexed Metal Solutions in a Stirred Cell Having a
Coversion/Combustion of Organic Pollutions for Waste Membrane Separator.” Journal of Membrane Science 171
Water Treatment.” Electrochemica Acta 11 (1994): (2000): 19–29.
1857‐1862. V. Coman, B. Robotin, P. Ilea. “Nickel Recovery/Removal
C. A. P Arellano, and S. S Martinez. “Indirect from Industrial Wastes: A Review.” Resources,
Electrochemical Oxidation of Cyanide by Hydrogen Conservation and Recycling 73 (2013): 229‐238.
Peroxide Generated at a Carbon Cathode. International X. T. Le, P. Viel, S. A. Sorin, P. Jegou, S. Palacin.
Journal of Hydrogen Energy 15 (2007) 3163–3169. “Electrochemical Behaviour of Polyacrylic Acid Coated
C. E. Borba, R. Guirardello, E. A. Silva, M. T. Veit, C. R. G. Gold Electrodes: An Application to Remove Heavy Metal
Tavares. “Removal of Nickel (II) Ions from Aqueous Ions from Wastewater.” Electrochimica Acta 54 (2009):
Solution by Biosorption in a Fixed Bed Column: 6089–6093.
Experimental and Theoretical Breakthrough Curves.” X. T. Le, P. Viel, P. Jégou, A. Sorin, S. Palacin.
Biochemical Engineering Journal 30 (2006): 184‐91. “Electrochemical‐switchable Polymer Film: An Emerging
C. P. Barbosa, G. R. P. Malpass et al., “Electrochemical Technique for Treatment of Metallic Ion Aqueous Waste.”
Removal of CuII in the Presence of Humic Acid.” Journal Separation and Purification Technology 69 (2009):
of the Brazilian Chemical Society 4 (2010): 651‐658. 135–140.
D. Simonsson. “Electrochemistry for a cleaner environment.” Y. H. Cui, X. Y. Li, G. H. Chen. ”Electrochemical Degradation
Chemical Society Reviews 26 (2007): 181‐189. of Bisphenol A (BPA) on Different Anodes.” Water
I. Giannopoulou, D. Panias. “Copper and Nickel Recovery Research 43 (2009): 1968‐1976.
from Acidic Polymetallic Aqueous Solutions.” Minerals Y. X. Gao, Y. Zhou et al., “Simultaneous Silver Recovery and
Engineering 20 (2007): 753–760. Cyanide Removal from Electroplating Wastewater by
J. D. Wiggins‐Camacho, and K. J. Stevenson. “Indirect Pulse Current Electrolysis Using Static Cylinder
Electrocatalytic Degradation of Cyanide at Electrodes.” Industrial and Engineering Chemistry
Nitrogen‐Doped Carbon Nanotube Electrodes.” Research 52 (2013): 5871‐5879.

164