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Basic Study of Electrochemical Treatment of Ammonium Nitrogen-Containing Wastewater Using Boron-Doped Diamond Anode
Katsuhito YOSHIDA, Shigeru YOSHIDA, Yuichiro SEKI, Toshiya TAKAHASHI, Ikko IHARA and Kiyohiko TOYODA
The authors electrochemically decomposed ammonium nitrogen (NH 4-N) using a boron-doped diamond anode and investigated its NH 4-N-decomposing properties. Boron-doped diamond anode, because of its high overpotential for oxygen evolution and high chemical stability, is an effective means to electrochemically reduce chemical oxygen demand (COD) in wastewater. Intensive studies have been done on the electrochemical decomposition of organic compounds using a diamond anode. In actual treatment of wastewater, however, removal of NH 4-N from wastewater is also essential because environmental regulations are becoming tighter. In this paper, the NH 4-N-decomposing properties of a boron-doped diamond anode were compared with those of conventional anodes, a PbO 2/Ti anode and a dimensionally stable anode (DSA).
Environmental issues have become serious social concerns of a global scale. Among these issues, the impact of water pollution is getting more serious because it is closely related to the health and lives of human beings. Eutrophying substances in water, like organic matters, nitrogen and phosphorous, are the most common pollutants caused by human activities. These substances are emitted not only by everyday life activities but also by agriculture, livestock raising and other industrial activities. Today, wastewater containing eutrophying substances is treated by the biotreatment process, in which microbes decompose these substances. Biotreatment is an economical wastewater treatment method, but it has some disadvantages, such as it takes a long treatment time, it requires large-scale treatment facilities, and the problem of how to get rid of sludge produced by treatment. As a new wastewater treatment method, electrochemical water treatment has been studied. In the electrochemical treatment process, organic pollutants in wastewater are electrochemically oxidized or reduced to non-hazardous inorganic substances. In this wastewater treatment method, electrode material is one of the important factors that affect treatment efficiency. In recent years, the application of boron-doped diamond (BDD) anode to wastewater treatment has been studied. BDD anode has some attractive properties such as high chemical stability and strong oxidization capability due to its high oxygen-overpotential in water electrolysis. In studying the electrochemical wastewater treatment process using BDD anode, the attention is focused mainly on the reduction of organic pollutants and chemical oxygen demand (COD). Previous studies show that a BDD anode is effective in reducing COD (1), (2), (3). In the practical wastewater treatment processes, however, reducing only COD is
not sufficient for most cases and it is necessary to reduce ammonium nitrogen (NH4-N) as well. A previous study reported that COD and ammonium in landfill leachate were both reduced by electrochemical treatment using the anodes made of different materials: a graphite anode, a PbO2/Ti anode, a dimensionally stable anode (DSA), and an Sn-Pd-Ru oxidecoated titanium (SPR) anode that uses the indirect oxidation effect of chlorine/hypochlorite (4). In a study described in this paper, the authors investigated the electrochemical decomposition characteristics of NH4-N with and without chloride ions using a BDD anode and compared the investigation results with those for the cases using a PbO2/Ti anode and a DSA.
2. Electrochemical decomposition mechanism of NH4-N
Without chloride ions (Cl–), NH4-N is oxidized to N2 or to various nitrogen oxides such as NO and N2O, following the steps described in Equation (1). Among the various reactions, Equation (2) is assumed to be the reaction of the decomposition of NH4-N to N2. NH3 → NH2OH → NOH → NO → NO2– → NO3– ↓↑ ↓→ N2O → N2 (1) NH4+ (<pH7) N2 NH3 + OH– → 1/2N2 + 3H2O + 3e– (2)
With Cl–, on the other hand, NH4-N is expected to be decomposed to N2 gas following the reactions called “breakpoint reactions” (5). Reaction on anode:2Cl– → Cl2 + 2e– Bulk reactions between the electrodes: (3)
SEI TECHNICAL REVIEW · NUMBER 65 · OCTOBER 2007 · 71
●: BDD. As shown in Fig. 3. some increase in the concentration of NO3-N. 2. The anodes were either a BDD anode (BDD grown on a Si substrate). DSA) conc (mg/L) Water Bath 200 150 100 50 NH4-N Magnetic Stirrer Fig. A Ti plate was used as a cathode. which is a form of toxic nitrogen. This test result indicates that NH4-N can be dissolved by the electrochemical oxidation when without the existence of Cl–. In both cases of the PbO2/Ti and BDD anodes. dation of NH4-N in Test Wastewater A (without Cl– and with SO42–). When Cl– exists. while in the case of the DSA. In this study. It is assumed that this difference was caused by the different oxidizing capabilities of the three electrodes. any of the three anodes reduces NH4-N more efficiently compared to the case without Cl–. Influence of anode materials on electrochemical oxidation of NH4-N when electrolyte contains chloride ions (◆ : PbO2/Ti. All of the PbO2/Ti. 3. BDD. Figure 3 shows the result of the electrochemical oxidation of NH4-N in Test Wastewater B (with Cl–). with a gap of 10 mm between them. Test Wastewater A was prepared to make the concentrations of NH4-N and SO42– to be 150 mg/L and 700 mg/L. 1. Test Wastewater B was prepared to make the concentrations of NH4-N and Cl– to be 150 mg/L and 700 mg/L. one with and one without Cl–. electrochemical treatments were conducted in a glass beaker equipped with an anode and a cathode.Cl2 + H2O → HOCl + H+ + Cl– HOCl + NH4+ → NH2Cl + H2O + H+ HOCl + NH2Cl → NHCl2 + H2O NHCl2 + H2O → NOH + 2H+ + 2Cl– NHCl2 + NOH → N2 + HOCl + H+ +Cl– (4) (5) (6) (7) (8) It can be expected from the above reaction equations that the decomposition characteristics of NH4-N differ by whether or not Cl– is contained. 1.5 A using a DC power supply. The sizes of the electrodes were both 100 x 50 mm. The experiments were carried out at a constant current of 1. Experimental results and discussion Figure 2 shows the result of the electrochemical oxi- Fig. △: DSA) 120 conc (mg/L) 80 40 0 NO3-N Pb02/Ti BDD DSA Cathode (Ti) Anode (BDD. a PbO2/Ti anode (PbO2 coated on a Ti substrate). In a beaker the anode and the cathode were placed vertically in parallel with each other. The concentration of NH4-N was determined using salicylate reaction and the concentration of nitrate nitrogen (NO3-N) was measured in accordance with the Japanese Industrial Standard JIS K0102. △: DSA) 72 · Basic Study of Electrochemical Treatment of Ammonium Nitrogen-Containing Wastewater Using Boron-Doped Diamond Anode . respectively. was observed. Influence of anode materials on electrochemical oxidation of NH4-N when electrolyte contains sulfate ions (◆: PbO2/Ti. When the BDD anode was used. ●: BDD. the increase of the NO3-N conc (mg/L) 40 Pb02/Ti BDD DSA NO3-N 20 0 200 conc (mg/L) 150 100 50 0 NH4-N 0 1 2 time (h) 3 4 Fig. meaning that Cl– works effectively in decomposing NH4-N. Schematic figure of experimental equipment 0 0 1 2 time (h) 3 4 4. and used NaCl and Na2SO4 as electrolytes to examine the decomposition characteristics of NH4-N. PbO2/Ti. or a DSA (IrO2 + RuO2). respectively. the increase in the NO3-N concentration was very small. Experiments Test wastewater solutions were prepared by mixing NH4HCO3 and Na2SO4 (Test Wastewater A) and by mixing NH4HCO3 and NaCl (Test Wastewater B). the authors prepared two types of reaction systems. The test wastewater solutions were stirred with a magnetic stirrer during electrolysis. and DSA could reduce NH4-N in the test wastewater solution.
148 (5) p.2.1431 G. Sumitomo Electric Hardmetal Corp I. Gao. on the condition that it is ensured that a sufficient time is spent on the reaction.W. Comninellis. Yue. Faculty of Agriculture. Lee. it is necessary to analyze substances other than NH4-N and NO3-N. Chang. C. Environmental Science and Technology (2003). but the NO3-N concentration decreased with time. it is necessary to verify the treatment abilities of BDD anode and DSA using actual wastewater. The Handbook of Chlorination. Laser Optics & Diamond-Electronics Department. Chiang. Kraft. This study also demonstrated that a BDD anode can reduce NH4-N to the same level as that by a DSA. although the decomposition rate differs considerably. P. and this indicates that Cl– is involved not only in decomposing NH4-N but also in forming NO3-N. I. the authors studied the electrochemical decomposition characteristics of NH4-N in wastewater with and without Cl– using a DSA anode. Anodic oxidation with doped diamond electrodes: a new advanced oxidation process. TOYODA • Ph. Sumitomo Electric Hardmetal Corp S. Kim. p. Vol. Assistant Professor. Michaud. p. SEKI • Assistant Manager. A. K. a BDD anode. In direct Oxidation Effect in Electrochemical Oxidation Treatment of Landfill Leachate. Faculty of Agriculture. Rodrigo. YOSHIDA • Diamond-Electronics Group. Kobe University K. Professor. G.Y. and P. To find out the cause of this phenomenon. Kobe University SEI TECHNICAL REVIEW · NUMBER 65 · OCTOBER 2007 · 73 . T. Since past studies reported that a BDD anode is superior to a DSA in removing organic pollutants. Van Nostrand Reinhold. H. F. IHARA • Ph. N. Sumitomo Electric Hardmetal Corp Y. 2nd edition. When the PbO2/Ti anode was used. Conclusions (4) In the experiment described above. D. Journal of Hazardous Materials (2003). Diamond-Electronics Group. TAKAHASHI • Manager.671 K. White. p. and the reducing rate was faster than the case without Cl–. Water Research (2006) Vol. Kim.concentration was observed at the beginning of the test. YOSHIDA* • Ph. C. Diamond-Electronics Group. and T. and E. I. Laser Optics & Diamond-Electronics Department.C. Duo. p. M. as the common types of wastewater contain some amount of chlorides in many cases. Park. J. J. Water Research (1995) Vol.29.172. (1986) pp. Stadelmann and M.21. Diamond-Electronics Group. it can be expected that a BDD anode is more applicable to practical wastewater treatment.247 L. Cerisola. Kim. G. USA Contributors (The lead author is indicated by an asterisk (*)). (5) (6) References X. This increase is considerably large compared with that in the case without Cl–. D. NH4-N was reduced with a little increase in the NO3-N concentration as was in the case without Cl–. 40. No. D. This experimental study demonstrated that NH4-N can be effectively decomposed by electrochemical treatment. Wen. Blaschke. When the DSA was used. A. Wastewater in general contains not only NH4-N but also various kinds of pollutants. L. To promote the practical use of BDD anode in wastewater treatment. the NO3-N concentration increased remarkably and 27% of the input nitrogen was oxidized to NO3-N and was accumulated.5021 M. 37. Sumitomo Electric Hardmetal Corp T. B103. Panizza. Laser Optics & Diamond-Electronics Department. G. M. and a PbO2/Ti anode. and every pollutant must be removed by wastewater treatment. D60 A. Y. I. (1) (2) (3) 5. Chen. Electrochemical conversion characteristics of ammonia to nitrogen. and Ch. E. Assistant General Manager. It was demonstrated that NH4-N could be decomposed by the electrochemical treatment process in both cases of with and without Cl–. Laser Optics & Diamond-Electronics Department. High ?Performance Ti/BDD Electrodes for Pollutant Oxidation. Chen. Journal of the Electrochemical Society (2001). Oxidation of 4-Chlorophenol at BoronDoped Diamond Electrode for Wastewater Treatment. No.
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