Anal. Bioanal. Electrochem., Vol. 3, No.

6, 2011, 625 - 634

Analytical &
Bioanalytical
Electrochemistry
2011 by CEE www.abechem.com

Full Paper

Removal of Cyanide by Electrocoagulation Process

Ghassem Hassani1, Simin Nasseri1,2*and Hamed Gharibi1
1

Department of Environmental Health Engineering, School of Public Health, Tehran University of Medical Sciences, Tehran, Iran 2 Center of Water Quality Research, Tehran University of Medical Sciences, Tehran, Iran
*Corresponding Author, Tel: +9821 889 549 14; Fax: +9821 889 501 88 E-Mail: naserise@tums.ac.ir

Received: 29 November 2011 / Accepted: 19 December 2011 / Published online: 30 December 2011

Abstract- Free cyanide and its related compounds are the most known contaminants which are released from industrial effluents to the environment; the objective of this study was to evaluate the efficiency electrocoagulation reactor with iron plate in order to find optimum operational conditions for cyanide removal from cyanide-containing effluents. The reactor was tested under different operational conditions of voltage (20, 30, and 40 V), detention time (20, 30, 40, 60, and 90 min), and influent concentration (20, 30 40, and 50 mg/l). Since ferrous ion capability to react with free cyanide and its related compounds are (97%) well established, iron plate was used as electrode in the present study. Additionally, to prevent creating ferric ion and ferric hydroxide precipitates in the reactor which decrease the removal efficiency, bisulfite was applied to hold ferrous ion in the reactor. The optimum operational conditions were obtained after running the reactor for several times. Based on the results, the optimum removal efficiency was obtained at voltage of 40 V, detention time of 90 min, and influent concentration of 50 mg/l. Therefore, this process may be considered as an alternative method for the removal of cyanide from cyanide- containing wastewaters. Keywords- Cyanide Removal, Industrial Wastewater, Electrocoagulation, Ferrous Ion

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1. INTRODUCTION Cyanide, due to its strong affinity for almost any metal, has been utilized broadly in various industries which, in turn, can be detected in different forms and concentrations in the produced industrial wastewaters which are released into the environment [1]. It is proven that free cyanide and its related compounds (thiocyanates, simple inorganic salts, metal- cyanide complexes and organic cyanides) are toxic to living organisms, although the degree of toxicity varies from one form of cyanide to another [2]. Additionally, owing to the various natures of industrial wastewaters, the forms of cyanide in the industrial effluents differ from one another based on their origin. [3]. Although free cyanide (cyanide anion and molecular hydrogen cyanide) is known as the most toxic form of cyanide compounds, metal-cyanide complexes could be toxic if these complexes dissociate to free cyanide and metal cation; in fact, metal cyanide complexes toxicity is attributed to their dissociation to free cyanide in aquatic systems contributing to increasing the concentrations of HCN and CN- [1,4]. Needless to say, complete description of the abysmal effects of cyanides on human and aquatic organisms can be found in depth in [5-7]. In order to remove cyanide and its related compounds from industrial wastewater effluents, different methods have been proposed and applied, including oxidation processes, physical methods and biological processes [1,8,9]. Conceded that wide range of the proposed methods effectively remove free cyanide and some simple forms of cyanide- metal complexes, these methods have their own disadvantages making them hard to be acceptable. Oxidation processes are costly [10], and also physical methods just transform the cyanide compounds to another phase which makes secondary problems in terms of economy [11]. Furthermore, applying the biological treatment is limited due to highly toxic effects of free cyanide on the microorganisms in biological tank [12]. Additionally, alkaline chlorination which has been widely applied for cyanide compounds oxidization produces secondary by products (i. e. Trihalomethans(THMs); and cyanogens chloride) which are proven to be toxic and carcinogenic [1,13]. Furthermore, although aerobic and anaerobic biological treatments, under certain circumstances, have the feasibility to be applied in order to remove cyanide compounds, these methods are suffered by the presence of free cyanide due to its inhibitory effects on the microorganisms. Ferricyanide, the strongest form of metal cyanide complex, does not simply undergo any breakdown which can be resulted in accruing to where it is released, so it can be dissociated to HCN or CN- [14]. Hence, cyanide and its related compounds have to be considered prior to be discharged into the environment. It is argued that chemical treatment due to its capability to remove free cyanide and ferricyanide can be applied either as complementary treatment or as pretreatment [12]. However, this method is costly, needs large amounts of chemical substances, and produces large amounts of precipitants [15]. Hence, other methods should be taken into consideration

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so as to defray the costs and increase the efficiency and reliability. Electrocoagulation (EC), a proven process in which there is no need to use chemical substances during the operation which, in turn, produces by far less amount of precipitants compared to chemical treatment, can be taken into account due to its advantages over the chemical treatments [15,16]. The objective of this study was to evaluate the performance of the Electrocoagulation reactor with iron plates as electrode to remove free cyanide and ferricyanide from industrial effluents. Iron plates were used as electrode since ferrous iron released from the anode surface removes ferricyanide more efficiently than other chemical substances. In addition, owing to the easier maintenance of bipolar mode compared to monopolar, the plates were operated as the former one in the present study [17]. Ferricyanide removal by electrocoagulation with iron plates was evaluated under different operational conditions of pH, voltage and detention time.

2. MATERIALS AND METHODS 2.1. Experimental set up As shown in Fig. 1, a batch reactor containing 10 pieces of iron plate was applied; the plates were connected as bipolar mode to power supply with 040 V of electrical potential. Each plate had an effective surface area of 60 cm2 (12 cm5 cm), and the space between the plates was 1 cm. The reactor efficiency was firstly tested at initial free cyanide concentrations of 20, 30, 40, and 50 mg/l and also different operational conditions of voltage (20,30 and 40 V), and detention time (20,40,60,and 90 min). 2.2. Electrocoagulation reactor The EC process starts when electric current passes through monopolar plates, which relative to adjacent charged side of the iron plates, it makes either side of the plate as negative or positive region (Fig. 1) [17]. In order to know the concentration of ferrous ion which is released in the EC tank, a pretest was conducted; to be more precise, having high removal efficiency is directly related to the concentration of ferrous ions in the EC tank. Based on the other studies, the optimum cyanide removal occurs at pH=4.5- 6 [18]. This was provided by sodium bisulfite in this study. Sodium bisulfite was added to the solution up to concentration 300 mg/l. In addition, sodium bisulfite blocks the oxidization of ferrous to ferric ions contributing to the prevention of ferrous hydroxide precipitation in the tank [19]. Considering the stabilized solution by bisulfite, the released ferrous ions from the anode surface reacts directly with free cyanide and metal complex cyanides [12,14,19]. The following equations show the reactions which occur at the anode and cathode surfaces of the iron plates: [20] At the anode surface :

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4Fe(s) 4Fe2+ (aq) + 8e (1) At the cathode surface: 3H2O + 3e 3/2 H2 (g) + 3OH (2) As can be seen from the above equations, ferrous ions are released from the reaction 1 occurred at the anode surface. Depending upon the pH of the bulk solution, ferrous ions react with free cyanide in accordance with the reaction presented below [18]: Fe2+ + 6CN- Fe(CN)63(3) 3The produced hexacyanoferrate (III) [Fe(CN)6 ], thereafter, reacts with ferrous ions in accordance with the following reaction[18]: 4Fe+2 + 3Fe (CN)63- Fe4[Fe(CN)6]3 (4) The end product is called "Prussian Blue", the insoluble form, which turns the bulk solution to blue color. Furthermore, partial amount of free cyanide would be concurrently hydrolyzed by bisulfite ion which, in turn, produces ammonium formate (HCOONH4); it breaks down to water, carbon dioxide and ammonia [18,19]. Finally, having a better removal efficiency needs to raise the pH value to 88.5 so as to precipitate ferrous hydroxide which can be resulted in encapsulating the Prussian blue particles through the bulk solution [18]. Hence, it is needed to use an alkaline substance such as sodium hydroxide to make that happen in order to increase the removal efficiency.

Fig. 1. Schematic of the EC reactor 2.3. Chemicals In this study, all chemical compounds utilized were of analytical grade. Free cyanide and bisulfite were prepared by dissolving KCN and sodium bisulfite in the solution; respectively, the NaCl compound was used as electrolyte in the EC process. In order to increase the pH

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value to 88.5 after the EC process, sodium hydroxide (NaOH, 1 M) was added and the solution was stirred for 510 min. Finally, the concentration of the free cyanide was measured by titration method according to the standard methods [21].

3. RESULTS AND DISCUSSION 3.1. The effects of operational conditions on the cyanide removal The efficiency of the EC reactor was tested in order to determine the optimum conditions (voltage, influent concentration, and detention time) for cyanide removal. As it mentioned before, a proven pH value in which ferrous ion is used to remove free cyanide and its related compounds is between 4.5- 6; in this regard, it was prepared as an initial pH value whenever the reactor was tested. In Fig. 2-5, the impact of optimum operational conditions is illustrated. The reactor was firstly tested with the influent concentration of 20 mg/l free cyanide and different voltages; results shown in the Fig. 2.

100 80
voltage 20 voltage 30 voltage 40

cyanide removal %

60 40 20 0 20

Reaction time (min)

40

60

90

Fig. 2. Cyanide removal efficiencies of the reactor with different detention times and voltages at influent cyanide concentrations 20 mg/l

As shown in the Fig. 2, when the voltage increased, the removal efficiency raised as well; for example, when the voltage increased from 20 to 40 V, the removal efficiency increased from 39% to 68%, respectively. Thereafter, the influent concentration of free cyanide was

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increased to 30, 40, and 50 mg/l free cyanide. As can be seen from the (Fig. 2-5), the above behavior of removal efficiency which was affected by voltages was repeated in each concentration; in other word, by increasing the voltage in each influent concentration of free cyanide, removal efficiency increased as well. Considering the effect of voltage on cyanide removal, it was observed that application of 40 V, with the detention time of 90 min, resulted in the maximum removal efficiency as 97 % with the influent concentration of 50 mg/l. Interestingly, the bulk solution in the reactor turned to blue color after 90 min which is due to the existence of Prussian blue in the reactor; to be more precise, in view of turning the bulk solution in to the blue color, it can be implied that free cyanide changed to the insoluble form which can be precipitated by adding an alkaline solution. By taking detention time into consideration, it was observed that the maximum removal efficiencies for each concentration of free cyanide came up at 90 min of the operation. For example, with influent concentration of 50 mg/l and 40 V, the maximum removal efficiency of 97% was observed at 90 min of operation, which decreased to 71% when the detention time decreased to 60 min. Furthermore, when the influence concentration was increased from 20 to 50 mg/l free cyanide, the removal efficiency also increased which can be seen from Fig. 2-5. By considering the results, it can be postulated that the reactor works acceptably when the influent concentration increases from 20 to 50 mg/l free cyanide.

100 80
voltage 20 voltage 30 voltage 40

cyanide removal %

60 40 20 0 20

Reaction time (min)

40

60

90

Fig. 3. Cyanide removal efficiencies of the reactor with different detention times and voltages at influent cyanide concentrations 30 mg/l

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100 80 cyanide removal % 60 40 20 0 20 40 60 Reaction time (min) 90

voltage 20 voltage 30 voltage 40

Fig. 4. Cyanide removal efficiencies of the reactor with different detention times and voltages at influent cyanide concentrations 40 mg/l

100 voltage 20 voltage 30 voltage 40

80

cyanide removal %

60

40

20

0 20

Reaction time (min)

40

60

90

Fig. 5. Cyanide removal efficiencies of the reactor with different detention times and voltages at influent cyanide concentrations 50 mg/l In this study, the performance of the EC reactor was evaluated under different operational conditions of influent concentration of free cyanide, voltage, and detention times. Based on

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the results, it can be implied that the EC reactor may be capable to efficiently remove free cyanide from the industrial effluents. According to the results, the optimum conditions for free cyanide removal were obtained at the influent concentration of 50 mg/l free cyanide, voltage of 40 V, and detention time of 90 min . Considering the effect of voltage on the cyanide removal, a positive linear relationship was observed between these two factors. By comparing the results of the other studies, it was realized that having higher voltage directly contributes to the higher release of ferrous ion into the bulk solution wherein ferrous ion reacts with free cyanide [22,23]; in order words, in view of having high level of the ferrous ion in the EC tank, which came through the ferrous ion releases from anode surface, there is more probability to have reaction between ferrous ions and free cyanide. As it is mentioned earlier, the highest free cyanide removal, for all of the operations, was obtained at 90 min of operational time. It can be implied that when the detention time increase, concurrent release of ferrous ions also happens which, in turn; there is more chance to remove higher concentrations of free cyanide in the bulk solution. Furthermore, it should be mentioned that stirring the solution also plays an important role to have thorough mixing in the reactor. Although, running the operation time would have better removal efficiencies, temperature control becomes more difficult; in other words, passing electrical current through the bulk solution contributes to rising temperature which must be taken into the consideration. Hence, as shown in Fig. 1, this problem was controlled by passing water around the reactor . Finally, removal efficiency was influenced by influent concentration of free cyanide. It was observed that increasing the influent concentration ended up with better removal efficiencies. Interestingly, increasing both influent concentration and voltage showed better results. By taking this point into the consideration, it can be postulated that higher ferrous ion concentrations due to the application of high level of voltage (40), besides the high level of free cyanide in the reactor make the operational conditions more suitable in term of removal efficiency.

4. CONCLUSION In this study, EC reactor with iron plate was evaluated in order to remove free cyanide efficiently. Considering the operational conditions, it was observed that the best removal efficiencies occurred at the voltage of 40 V, detention time of 90 min, and influent concentration of 50 mg/l. By comparing EC technology with other methods for cyanide removal in terms of economy, this technology has several advantages over the other methods. Although it needs electrical power which is costly, having no need to purchase chemical compounds and also making safe place to store them rekindle the interest towards this proven

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method in terms of efficiency and reliability. Finally, due to the capability of this process to remove free cyanide and its related compounds, it can be considerate as an alternative method for cyanide removal from the cyanide- containing wastewater effluents.

Acknowledgment This research has been supported by Tehran University of Medical Sciences & Health Services grant (No. 11581-61-04-89).

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