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Article history: Electrolysis of aqueous sodium chloride has been widely used in the chloro-alkali process, and its
Received 17 May 2012 operating parameters are well-known. This electrochemical mechanism can be applied to both on-site
Accepted 4 August 2012 chlorine production for disinfecting water in small-scale drinking water treatment plants and as a
Available online 10 August 2012
portable chlorine generator for emergency use or for campers. However, the design information and
operating parameters affecting the current efficiency and power consumption of small-scale
Keywords: electrochlorination systems are limited even though these systems have become popular. We investigate
Drinking water
the significant design and operating parameters affecting current efficiency and power consumption in
Disinfection
an electrochlorination system. IrO2 electrodes, NaCl concentration, current density, a separator, and
Electrochlorination
IrO2 temperature control were selected as the design and operating parameters in the two-electrode batch
Current efficiency system. The results show that the most important parameter affecting current efficiency and power
Power consumption consumption of chlorine generation was NaCl concentration. At low NaCl concentrations (1000 mg/L),
the type of anode, current density, and the separator considerably affected current efficiency and power
consumption to generate chlorine, whereas at high NaCl concentrations (>35,000 mg/L), anode type
became insignificant, with current efficiency >90% and power consumption of 4–6 Wh/g.
ß 2012 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.
1. Introduction IrO2 electrode has better efficiency than the others to produce
chlorine in the presence of NaCl [7]. Furthermore, the chlorine
Chlorine is one of the most important chemicals in drinking solution generated in an electrochemical system is slightly more
water treatment plants to supply pathogen-free drinking water. efficient for inactivating microorganisms than free chlorine under
Safety problems are considerable, as chlorine required for certain pH conditions [8].
disinfection is transported in the gas phase by truck and stored In an electrochlorination system, chloride ions are oxidized to
in a tank [1,2]. To resolve these chlorine gas safety issues, on-site form chlorine on the anode surface by two-electron transfer
chlorine generation systems are necessary and can be achieved (Eq. (1)), and then the chlorine exists as hypochlorous acid and/or
using an electrochemical system that has many advantages, hypochlorite according to pH (Eqs. (2) and (3)) [9,10].
including process versatility, energy effectiveness, and environ-
2Cl ! Cl2 þ 2e (1)
mental compatibility [3]. Hence, an electrochemical chlorine
generation system, electrochlorination system, would be consid-
Cl2 þ H2 O ! HOCl þ Hþ þ Cl (2)
ered as an alternative process.
An electrochlorination system consists of electrodes, an
electrolyte, and a circuit, and anodes are a significant factor for HOCl $ Hþ þ OCl (3)
chlorine generation. According to the property of anodic materials, Electrolysis of aqueous sodium chloride to produce several
anodes are divided into active and nonactive electrodes; IrO2 and chemicals such as chlorine, sodium hydroxide, and hydrogen in
RuO2 are the former and boron-doped diamond (BDD) is the latter chloro-alkali process has been widely employed by applying these
[4–6]. Among various electrodes such as IrO2, RuO2, and BDD, the electrochemical reactions, and the design and operating param-
eters are well known [11]. However, concerns about electrolysis of
aqueous sodium chloride have been raised. First, the electrolysis of
* Corresponding author at: 599 Gwanak-ro, Gwanak-gu, Seoul 151-742, Republic
aqueous sodium chloride can be applied to treat wastewater and
of Korea. Tel.: +82 2 880 8927; fax: +82 2 876 8911. landfill leachate [12,13]. Furthermore, this has been increasingly
E-mail address: jeyong@snu.ac.kr (J. Yoon). applied due to the safety issues of handling chlorine gas and
1226-086X/$ – see front matter ß 2012 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jiec.2012.08.004
216 J. Choi et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 215–219
Vol DC n F
Current efficiency ð%Þ ¼ 100% (4)
iapp t
E iapp t 1
Power consumption ðWh=gÞ ¼ (5)
Vol DC 71 3600
where iapp is the applied current (A), t is the elapsed time (s), Vol is
the solution volume (L), DC is the concentration difference in
Fig. 1. Schematic of the electrochemical cell employed in this study ((a) the chlorine (M), n is the number of electrons required, F is the Faraday
undivided cell and (b) the divided cell). constant (96,485 C mol1), and E is the average voltage (V) during
J. Choi et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 215–219 217
Table 2
Details of the experimental conditions.
Type of electrode NaCl concentration (mg/L) Current density (mA/cm2) Separator Temperature control
electrochlorination. The current efficiency (Eq. (4)) is the ratio of power consumption is about 4.4 Wh/g [2] at NaCl concentration of
the electrical charge consumed to the total electrical charge passed >35,000 mg/L. One explanation is that current densities for
during the electrochemical reaction. Power consumption (Wh/g) is chlorine on IrO2-coated electrodes are very high as compared to
the total energy required for producing a unit of chlorine by exchange current densities for oxygen although oxygen evolution
electrochlorination (Eq. (5)). is thermodynamically preferred [21]. Excess NaCl concentration
higher than 35,000 mg/L is not recommended in field operation to
3. Results and discussion
4. Conclusions
Fig. 4. Current efficiency and power consumption as a function of current density
(electrode: IrO2-A, i = 33, 67, 100, 133, and 167 mA/cm2, [NaCl]0 = 1000 mg/L, no We report important design and operating parameters (type of
separator and temperature control, reaction time = 10 min). electrodes, NaCl concentration, current density, separator, and
temperature control) affecting current efficiency and power
enhance current efficiency. Fig. 4 shows the changes in current consumption in an electrochlorination system. The most critical
efficiency and power consumption with respect to current density. parameter affecting current efficiency and power consumption
Note that this experiment was performed under the low NaCl was NaCl concentration. Current efficiency increased by 62% and
concentration condition (1000 mg/L). As shown in Fig. 4, current power consumption decreased by 127 Wh/g as NaCl concentration
efficiency decreased slightly from 40% to 32%, whereas power increased from 1000 to 350,000 mg/L. The type of anode, current
consumption increased significantly from 28 Wh/g to 131 Wh/g as density, and the presence of a separator considerably affected
current density increased from 33 mA/cm2 to 167 mA/cm2. The current efficiency and power consumption for chlorine generation
diminished current efficiency with the increase in current density at a low NaCl concentration (1000 mg/L). In contrast, the type of
can be explained by the highly competitive reaction such as oxygen anode became insignificant at a high NaCl concentration
evolution under high current density conditions [22,23]. (>35,000 mg/L), revealing a current efficiency > 90% and power
consumption of 4–6 Wh/g.
3.3. Effect of temperature control and the separator
Acknowledgment
Fig. 5 shows the changes in current efficiency and power
consumption in the presence or absence of the separator and This research was supported by WCU (World Class University)
whether temperature control was used during electrolysis as program through the National Research Foundation of Korea
compared with the control condition. As shown in Fig. 5, the funded by the Ministry of Education, Science and Technology (R31-
presence of temperature control had no significant effect on 10013).
current efficiency (30–32%), which was consistent with previous
studies [15,16]. In contrast, the presence of the separator had a References
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