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JECE-192; No. of Pages 7

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Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece

Feasibility test for waste-reclaimed material to remove Cu2+ and Zn2+: Kinetics and applications to treat a real plating wastewater
Young-Hoon Jo, Si-Hyun Do, Sung-Ho Kong *
Department of Chemical Engineering, Hanyang University, Seoul 133-791, Republic of Korea

A R T I C L E I N F O

A B S T R A C T

Article history: Received 29 April 2013 Received in revised form 30 October 2013 Accepted 31 October 2013 Keywords: Waste-reclaimed material (WR) Cu2+ Zn2+ Adsorption A plating wastewater

Applicability of waste-reclaimed material (WR) to remove heavy metals (Cu2+ and Zn2+) in a plating wastewater was investigated. The mass (mg) of both Cu2+ and Zn2+ removed from solution was linearly increased when the initial concentrations increased from 10 to 100 mg/L. Experimental data was well predicted by both Langmuir and Freundlich models. In the Langmuir model, the values of RL (a dimensionless constant separation factor) indicated that adsorption of both Cu2+ and Zn2+ on WR were favorable (i.e. RL for Cu2+ were 0.3370.048 and RL for Zn2+ were 0.7750.256). Kinetically, adsorption of both Cu2+ and Zn2+ was predicted by pseudo-second order model. The highest qe of Cu2+ and Zn2+ were 1.6 101 and 8.1 102 mg/g, respectively. Moreover, the initial adsorption rate, h k2 q2 e , was increased when initial concentrations of metal ions increased. The effect of pH on the removal of Cu2+ and Zn2+ revealed that some degrees of Cu2+ and Zn2+ were removed at the acidic condition. Moreover, all Cu2+ was removed at pH 7, while Zn2+ was completely removed at pH 9. Therefore, those results indicated that the surface characteristics, specically both the surface charge and chemical compositions, could make WR a potential adsorbent. The use of WR showed that removal of metal ions satisfy the regulatory requirements (i.e. under 3.0 mg/L of Cu2+ and 5.0 mg/L of Zn2+) in Korea when experiments using large-scale reactors were conducted 20 times in plating wastewater. 2013 Elsevier Ltd. All rights reserved.

Introduction Wastewaters containing heavy metals are often encountered in chemical process industries such as metal nishing, mining operations and electroplating [1]. Discharges of heavy metals (i.e. especially ionic forms of metals) easily bound with living tissues, sedimentary materials and detritus, causing noticeable adverse effects to the human health; therefore, it has become hazardous to discharge them into the environment [2]. Various processes (i.e. adsorption, chemical precipitation/ coagulation, ultraltration, electrodialysis, etc.) have been practiced to remove the dissolved metal ions from aqueous solution [3]. Among these processes, adsorption is known as one of the applicable treatment techniques, and it offers exibility in operation accompanied with a satisfaction of lower levels of metal ion concentration in efuent [4,5]. Mostly, surface characteristics that provide the higher adsorption capacity including ion exchange ability are important to select materials as adsorbents [611]. Zeolite, which is a large surface area with micro-porous character, has been used as sorbent, cation exchanger, and catalyst

* Corresponding author. Tel.: +82 2 2220 0489; fax: +82 2 2293 8551. E-mail address: shkong@hanyang.ac.kr (S.-H. Kong). 2213-3437/$ see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.jece.2013.10.017

[1215]. The general composition of zeolite can be represented by My/z[(SiO2)x(AlO2)y]nH2O where M is the exchangeable ion metal with a valency [9]. It has been observed that heavy metals were effectively removed through ion exchange when zeolite was used [1618]. Zamzow et al. [18] reported that zeolite removed metal ions as following selectivity, Pb2+ > Cd2+ > Cs+ > Cu2+ > Co2+ > Cr3+ > Zn2+ > Ni2+ > Hg2+. In addition, it has been reported that diffusion of exchangeable ions through the channel/void of zeolite was the rate determining step, and the rates of metal ion adsorption was predicted by second order kinetic model [9,17]. Recently, various materials including industrial waste-materials (i.e. ashes, diatomite, clay, etc.) as adsorbents have shown the ability to remove metal ions [19,20]. Generally, their adsorption has been interpreted by physical/chemical interactions followed by complex formations between metal ions and surface [21]. Moreover, the pH of solution has been noticed as the important factors to adsorption. Papandreou et al. [22] showed that Cu adsorption was intensied in the pH range of 67 when ashes were used as an adsorbent. Hui et al. [23] observed that the afnity order was Cu2+ > Cr3+ > Zn2+ > Co2+ > Ni2+ when coal y ashes were used as adsorbents at pH 3. Previously, our research group investigated the feasibility of waste-reclaimed materials (WR) for treatments of contaminants [24,25]. WR is a mixture of bottom ashes from a power plant and dredged soils. When WR was tested as lling materials in a

Please cite this article in press as: Y.-H. Jo, et al., Feasibility test for waste-reclaimed material to remove Cu2+ and Zn2+: Kinetics and applications to treat a real plating wastewater, J. Environ. Chem. Eng. (2013), http://dx.doi.org/10.1016/j.jece.2013.10.017

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2 Y.-H. Jo et al. / Journal of Environmental Chemical Engineering xxx (2013) xxxxxx Table 1 Physicochemical characteristics of the WR. Total pore volume (cm3 g1) Mesopore area (m2 g1) Pore diameter (nm) Porosity (%) Surface area (m2 g1) Cation exchange capacity (meq (100 g)1) Point of zero charge (PZC) Size (mm) Specic gravity 6.7 103 3.91 1.41 30 14.6 3.45 4.3 38 1.41

permeable reactive barrier (PRB), we observed that WR had adsorption ability for volatile organic compounds (i.e. benzene, toluene, ethyl benzene, and xylene (BTEX)) [24]. Moreover, we tested WR regeneration by using various oxidants for a long-term operation on PRB, and we also observed that WR had a catalytic ability to increase the reactivity of oxidants to degrade BTEX [24]. Furthermore, WR was applied for oxidation of cyanide (CN) when H2O2 was used as oxidant [25]. We observed not only the catalytic ability of WR for oxidation of cyanide to cyanate, but also the adsorption of cyanide on WR [25]. Especially, WR was modied by the attachment of irons for its effectiveness, and we noticed the possibility of WR as metal ion adsorbent. Therefore, those indicated that WR could be used for the removal of metal ions in wastewater. The objective of this study was the removal of Cu2+ and Zn2+ using WR material. First of all, adsorptions of Cu2+ and Zn2+ on WR were conducted to determine the adsorption behavior. Experimental data were also evaluated as aspects of adsorption isotherm and kinetics. Then, the inuences of pH on the metal ion (Cu2+ and Zn2+) adsorption were studied. Finally, the obtained optimum parameters were applied to treat real plating wastewater from an industrial zone in Ansan, Korea. Materials and methods Materials Copper sulfate (CuSO45H2O) was purchased from Kanto Chemical (Osaka, Japan) and zinc sulfate (ZnSO47H2O) was from Shinyo Pure Chemical (Tokyo, Japan). Nitric acid (HNO3) and sodium hydroxide (NaOH) were purchased from Kanto Chemical, and these were used for pH adjustment. WR is supported by the Center for Resource Processing of Solid Wastes (CRP-SW) at Kyonggi University, Korea. The raw materials of the WR were 70% bottom ash from a power plant and 30% dredged soil. Briey, raw materials were pulverized until they were below 150 mm, and then a pelletizer was employed in the molding process. These molded lumps were dried at 110120 8C for 48 h and calcination was done by rotary kiln at 11251150 8C for 15 min. The WR consisted of 53.1% SiO2, 17.3% Al2O3, 6.8% Fe2O3, 1.8% CaO, 0.6% MgO, 0.9% Na2O, 1.2% K2O, 1.2% TiO2, 0.2% P2O5, 0.2% ZrO2, 12.6% C (element carbon) and 4.1% ignition loss (the unit was wt%). Mostly, the results from X-ray diffraction (XRD) analysis indicated the complexity of WR, even though quartz (SiO2) mullite and (3Al2O32SiO3) were identied as the most common crystalline [25]. Moreover, WR was a mesoporous material (see in supplementary material, Fig. S1) and results of the physicochemical characteristics were presented in Table 1. Supplementary material related to this article can be found, in the online version, at doi:10.1016/j.jece.2013.10.017. The WR was washed ten times using de-ionized water with a resistivity of 18 MV cm (Millipore system, Young-Lin Co., Korea), dried at 105 8C for 1 day and stored in a desiccator before conducting experiments. For the pilot test, a real plating wastewater, which contained heavy metals, was taken from the industrial complex located at Ansan, Kyonggi-do, Korea. The representative characteristics of a plating wastewater were shown in Table 2.
Table 2 Representative characteristics of a plating wastewater. pH 6.97.1
a b

Effects of initial concentrations of metal ion (Cu2+ or Zn2+) Removals of metal ions (Cu2+ or Zn2+) were conducted with a 40 mL of glass vial, which contained 10 g of WR in 20 mL of solution. The initial pH of all solutions was xed at 5 by adding 0.1 N of HNO3. Initial concentrations of metal ion were ranged from 10 to 100 mg/L. Then, each sacriced batch reactor was mounted on a shaking incubator (LPN-0201F-S, Hanbaek St.) at 200 rpm and 25 8C. All reactions were performed for 24 h. When sample was retrieved, it was ltered through a 0.45 mm Teon lter, measured by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). Adsorption kinetics In kinetics, a following is the pseudo-rst order kinetic equation in the form [26]. dqt k1 qe qt dt logqe qt log qe k1 t 2:303 (1) (2)

where k1 (L/min) is the rate constant of the pseudo-rst order adsorption, qe (mg/g) the amount of divalent metal ions adsorbed at equilibrium, and qt (mg/g) is the amount of divalent metal ions on the surface of the WR at any time, t (h) in Eq. (1). If the plot of log (qe q) versus time (t) of Eq. (2) is a linear, k1 and qe could be determined from the slope and intercept of the plot. In addition, the pseudo-second order is expressed as following [27]. dqt k2 qe qt 2 dt t 1 1 qt k2 q2 q e t e (3) (4)

where k2 (g/mg min) is the rate constant of the pseudo-second order adsorption in Eq. (3). The term, k2 q2 e in Eq. (4), is also known as initial adsorption rate (h). In this case, if the plot of t/qt versus time (t) of Eq. (4) is a linear, k2 and qe could be determined from the slope and intercept. Adsorption isotherms The linear form of either Langmuir (Eq. (5)) or Freundlich (Eq. (6)) is followed [28]. Ce 1 Ce qe Q 0 b Q 0 (5)

TOCa (mg/L) 114118

SSb (mg/L) 106310

SO42 (mg/L) 7811400

Cl (mg/L) 9602020

Hardness (mg/L as CaCO3) 112836

Cu2+ (mg/L) 1938

Zn2+ (mg/L) 115

Cr6+ (mg/L) 16

Total organic carbon (TOC). Suspended solid (SS).

Please cite this article in press as: Y.-H. Jo, et al., Feasibility test for waste-reclaimed material to remove Cu2+ and Zn2+: Kinetics and applications to treat a real plating wastewater, J. Environ. Chem. Eng. (2013), http://dx.doi.org/10.1016/j.jece.2013.10.017

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log qe log K F

1 n log C e

1.6

(6)
1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 0

The equation of line is y = ax + b, where a = 0.60, b = 0.12, r 2 = 0.99 ( ), and a = 0.32, b = 0.11, r2 = 0.96 ( ).

Removal of metal ion (mg)

where qe (mg/g) is the equilibrium uptake, Ce (mg/L) is the equilibrium concentration, Q0 (mg/g) is the saturated monolayer sorption capacity, b (L/g) is the sorption equilibrium constant, KF is Freundlich coefcient, and n indicates the presence of a heterogeneous surface and binding sites with different energies. Effects of pH Adsorptions of metal ion (Cu2+ or Zn2+) with WR were investigated at various levels of pH (3, 5, 7, 9 and 12). At the same time, metal ion without WR was also prepared at various levels of pH. The pH of the solution was adjusted by adding 0.1 N HNO3 or 0.1 N NaOH. The initial concentration of metal ion was xed at 30 mg/L and the amounts of WR in 20 mL of solution were 10 g. Moreover, the reaction was carried out on a shaking incubator until 24 h. Treatment of real plating wastewater using a large-scale reactor Real plating wastewater was treated using a large-scale cylindrical reactor (a stainless steel (SUS 304) reactor) connected in series. The volume of each reactor was 2.7 m3 (1.2 m of diameter 2.4 m of height), and each reactor was lled with 2000 kg of WR (the size of WR was ranged from 1.3 to 1.8 cm). Two reactors (reactor I and reactor II) in series were used to treat 1 m3 of wastewater, which meant that wastewater stayed in reactor I and then it was moved to reactor II. Preliminarily, the level of regulation was satised with at least 2 h of retention time of each reactor. Samples from reactors I and II were pretreated by ltration (Teon lter of 0.45 mm), and ltrate was stored at 4 8C in a refrigerator before being analyzed. Analytical procedures Metal ion concentrations were determined by ICP-AES (PerkinElmer, optima 4300DV, USA). Specically, efuent from a series of large-scale reactor was pretreated with 2% HNO3 (i.e. to minimize the interference of organic matter) before metal ions were analyzed. The surface area of the WR was determined by the BrunauerEmmettTeller (BET) (BELSORP-mini II using N2) method. The pore distribution was analyzed by the Barrett JoyneHalenda (BJH) model. The point of zero charge (PZC) of the WR was determined by Zeta potential analyzer (Otsuka model ELS2, Japan) from the Korea institute of ceramic engineering and technology (KICET). It was a plot of zeta potential (mV) on the aqueous dispersions of a certain amount (0.1%, w/v) from the WR (i.e. WR sample was ground in a Pin mill and screened through a 100 mm sieve.) over a pH range from 2 to 9. The cation exchange capacity (CEC) of the WR was measured by the ammonium acetate method provided from the National Instrumentation Center for Environmental Management (NICEM, Korea). The pH was monitored with a pH-200L meter (ISTEK, Korea). Results and discussion Effects of initial concentrations of metal ion (Cu2+ or Zn2+) Removal of metal ions (Cu2+ and Zn2+) from solution using WR at the pH of 5 indicated that removals of both Cu2+ and Zn2+ gradually increased until 18 h of reaction time, and those were constant after 18 h of reaction time (See in supplementary material, Fig. S2). When the initial concentration of Cu2+ increased from 10 to 100 mg/L, the removal percentage (%) of Cu2+ decreased

Cu2+ Zn2+

20

40

60

80

100

Initial concentration of metal ion (mg/L)

Fig. 1. Removals of Cu2+ and Zn2+ as a function of the initial metal ion concentration in the system contained WR.

from 94 to 76% and removal percentage of Zn2+ decreased from 58 to 34% at the same concentration range of Zn2+. In addition, it was shown in Fig. 1 that the mass of the metal ions removed from the solution proportionally increased with the increasing of the initial metal ion concentrations in the solution. It was showed that Cu2+ was removed from 0.2 to 1.31 mg and Zn2+ was from 0.1 to 0.71 mg. The adsorption behavior was dependent on the initial concentrations of metal ions. Supplementary material related to this article can be found, in the online version, at doi:10.1016/j.jece.2013.10.017. Moreover, it was clearly observed that Cu2+ was removed more favorably than Zn2+ when the WR was used as the adsorbent. The adsorption isotherm indicated that the current experimental data were well predicted by both Langmuir and Freundlich model (See in supplementary material, Fig. S3). Based on parameters of Langmuir and Freundlich in Table 3, correlation coefcients (r2) for both models were higher than 0.98. Supplementary material related to this article can be found, in the online version, at doi:10.1016/j.jece.2013.10.017. It has been reported that the adsorption of Cu2+ and Zn2+ on zeolites and low-rank coal could be interpreted by Langmuir model [29,30]. In the present study, the calculated sorption capacity (Q0) of Cu2+ and Zn2+ were 0.153 and 0.106 mg/g, respectively. In addition, a dimensionless constant separation factor (RL) could be calculated by the Eq. (4) [31]. RL 1 1 bC 0 (7)

where C0 is the initial metal ion concentration (mg/L) and b is the Langmuir adsorption equilibrium constant (mL/mg). If adsorption is favorable, then RL is between 0 and 1, and if it is unfavorable, RL is larger than 1. Moreover, if adsorption is irreversible, RL is equal to 0 [31]. In the present study, the calculated value of RL for Cu2+ and Zn2+ were 0.3370.048 and 0.7750.256, respectively when initial concentrations of both increased from 10 to 100 mg/L. Therefore,
Table 3 Parameters of Langmuir and Freundlich model in the system contained WR. Langmuir Q0 (mg/g) Cu2+ Zn2+ 0.153 0.106 b (L/mg) 0.197 0.029 r2 0.977 0.995 Freundlich KF 0.028 0.006 1/n (L/g) 0.525 0.653 r2 0.988 0.987

Please cite this article in press as: Y.-H. Jo, et al., Feasibility test for waste-reclaimed material to remove Cu2+ and Zn2+: Kinetics and applications to treat a real plating wastewater, J. Environ. Chem. Eng. (2013), http://dx.doi.org/10.1016/j.jece.2013.10.017

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Table 4 Kinetic parameters of Cu2+ and Zn2+ adsorptions on WR. Conc. (mg/L) Pseudo-rst order qe (mg/g) Cu
2+

Pseudo-second order k1 (1 min

1

qe (mg/g) 2.0 10 5.9 102 8.5 102 1.2 101 1.6 101 1.4 102 4.0 102 5.9 102 7.1 102 8.1 102
2

k2 (g/mg min) 4.3 10 1.3 101 5.3 102 3.5 102 2.6 102 2.5 101 8.6 102 5.0 102 4.3 102 4.2 102
1

h (mg/g min) 1.7 10 3.4 104 3.8 104 4.7 104 6.4 104 4.7 105 1.3 104 1.8 104 2.2 104 2.7 104
4

r2 0.99 0.99 0.98 0.98 0.99 0.96 0.96 0.97 0.96 0.95

10 30 50 70 100 10 30 50 70 100

1.5 10 5.4 102 7.7 102 1.7 101 1.9 101 1.1 102 2.9 102 7.2 102 7.5 102 7.7 102

7.9 10 8.4 104 9.7 104 9.5 104 9.5 104 5.0 104 5.0 104 7.6 104 6.8 104 5.6 104

0.97 0.95 0.90 0.88 0.95 0.92 0.95 0.86 0.88 0.87

Zn2+

adsorption of Cu2+ and Zn2+ on WR were favorable, according to RL. Furthermore, it was observed that RL was decreased with the increasing initial concentration of both metal ions. Specically, adsorption of Cu2+ was close to irreversible when the initial concentration of Cu2+ was 100 mg/L. Adsorption kinetics The adsorptions of Cu2+ and Zn2+ on WR were evaluated kinetically. Parameters of the tested models (i.e. pseudo-rst order and pseudo-second order) were summarized in Table 4. It revealed that adsorptions of those metal ions on WR tted well with pseudo-second order model. As shown in Table 4, the correlation coefcients (r2) ranged from 0.86 to 0.97 for the pseudo-rst order model and those ranged from 0.95 to 0.99 for the pseudo-second order model. Moreover, it was shown in Fig. 2 that experimental data in the present study were closely predicted by using pseudo-second order model. In addition, it has been reported that pseudo-second order model was the appropriate model to describe the adsorption of heavy metals on adsorbents such as zeolite and bottom ashes [3234]. According to the kinetic parameters of the pseudo-second order model, the rate constant (k2) decreased but the value of qe increased when initial concentrations of Cu2+ and Zn2+ were increased from 10 to 100 mg/L. The highest qe for Cu2+ was 1.6 101 mg/g and that for Zn2+ was 8.1 102 mg/g. Moreover, it was noticed that k2 for Cu2+ were higher than that for Zn2+ in lower concentrations when the initial concentrations were below 50 mg/L. On the other hand, k2 for Cu2+ were lower than that for Zn2+ in higher concentrations when the initial concentrations were above 50 mg/L. The initial adsorption rate also indicated the preference of Cu2+ adsorption on the WR in the present study. Initial adsorption rate (h), which was a function of rate constant 2+ and q2 e , increased linearly when the initial concentrations of Cu and Zn2+ were increased from 10 to 100 mg/L (the relation of h and initial concentration was shown in Fig. S4, Supplementary Material). Based on this relation, Cu2+ was more preferably adsorbed on WR than Zn2+. It has been reported that adsorbents (i.e. zeolite, ash and coals) showed more afnity to Cu2+ than Zn2+ [23,35,36]. Mishra and Tiwari [35] reported that Cu2+ had more afnity on the adsorbent than Zn2+ because the hydrolysis constant (pKh) of Cu2+ (8.0) was lower than that of Zn2+ (9.0). Supplementary material related to this article can be found, in the online version, at doi:10.1016/j.jece.2013.10.017. Effect of pH The pH of the solution is known as an important parameter (i.e. affects the degree of ionization of metal ions and the surface charge of the adsorbents) in the adsorption process [37]. Moreover, metal ions in solution are converted to the insoluble metal hydroxide

depending on the pH condition. The effects of the pH on Cu2+ and Zn2+ removal were conducted when WR was used or not, and the results were shown in Fig. 3. Without WR, less than 0.1 mg of Cu2+ was removed from the solution below the pH 5. At low pH, the dominant species is Cu2+ [39]. Moreover, the removal of Cu2+ was dramatically increased between the pH 5 and the pH 7, and then Cu2+ was removed completely at the pH 9 and above. It has been reported that the precipitation of Cu2+ (i.e. Cu(OH)2) occurred when the initial pH of the solution was adjusted to 5.74 [23]. Therefore, the removal of Cu above pH 5 without WR could be due to precipitation. On the contrary, more than 0.4 mg of Cu2+ was adsorbed at the pH 3 when WR was used. Moreover, removal of Cu2+ was gradually increased until the pH of 7. All of Cu2+ was removed from the solution by both adsorption and precipitation at the pH of 7. It was showed that maximum removal of Cu2+ occurred at pH 7 when WR was used. Those results indicated that the surface characteristics of WR, which were particularly the chemical compositions and the surface charges, affected the adsorption of metal ions. In an acidic condition (below the pH 5), metal oxides (i.e. SiO2, Al2O3, and Fe2O3) on WR might be provided the bonding sites to Cu2+ [38]. Moreover, the PZC of WR was determined as 4.3, and this indicated that the surface of WR was negatively charged above the pH of 4.3. Therefore, as the pH of solution increased above PZC, Cu2+ (i.e. positive charge) in aqueous solution were more attracted to the surface of WR. However, above the pH 5 some portion of Cu might be also removed by precipitation. In Zn2+ removal, Zn2+ was negligibly removed from the solution until pH 5 when WR was not applied. The dominant species of Zn is Zn2+ when the solution is below the pH 7 [39]. The removal of Zn dramatically increased between pH 7 and pH 9. Moreover, at the pH 9, Zn was completely precipitated. When WR was used, more than 0.2 mg of Zn2+ was adsorbed at the pH 3. After that, removal of Zn by both adsorption and precipitation was proportionally increased until the pH 9, and all of Zn was removed at the pH of 9. Therefore, we found that all of Cu2+ was removed at pH 7 with the WR, while Zn2+ was completely removed at pH 9. Treatment of heavy metals in a real plating wastewater The concentrations of Cu2+ and Zn2+ in inuent and efuent were shown in Table 5 when two large-scale reactors lled with 2000 kg of WR were connected in series (reactors I and II). As shown in Table 5, Cu2+ in inuent was ranged from 18.6 to 38.0 mg/ L while Zn2+ was from 1.4 to 15.2 mg/L. Based on efuents from reactor II, removal percentages of Cu2+ and Zn2+ were approximately 7491 and 7898%, respectively. Moreover, adsorption process was quite sufcient to remove Zn2+ as only reactor I. It was reported that adsorbents including waste-materials were tested to remove heavy metal ions [40]. For example, zeolite removed 6879% of Zn2+ in wastewater [9] and a peanut hull

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a
100

80

t/qt (min.g/mg) of Cu 2+

60

10 mg/L 30 mg/L 50 mg/L 70 mg/L 100 mg/L

40

20

0 0 5 10 15 20 25

b
140 120 100 80 60 40 20 0 0 5 10 10 mg/L 30 mg/L 50 mg/L 70 mg/L 100 mg/L

Time (h)

2+ t/qt (min.g/mg) of Zn

15

20

25

Time (h)
Fig. 2. Pseudo-second order predictions of Cu2+ (a) and Zn2+ (b) removal on WR.

carbon removed 43% of Cu2+ in plating industry wastewater [10]. Therefore, the current tested adsorbent, WR, could be a potential one as aspect of both treatability of heavy metals (Cu2+ and Zn2+) and reuse of wastes (i.e. the source of WR was waste). The results in Table 5 also indicated that both Cu2+ and Zn2+ satised the regulatory requirements in Korea when concentrations of Cu2+ and Zn2+ in a real plating wastewater were less than 26.7 and 15.2 mg/L, respectively. Further, Zn2+ satised recommendation of concentration (under 2.0 mg/L) in the World Health Organization (WHO) when Zn2+ in inuent was less than 15.2 mg/L. Above all, the

use of WR showed that removal of metal ions was possible by recommendation of concentration (i.e. under 3.0 mg/L of Cu2+ and 5.0 mg/L of Zn2+) in Korea when experiments involving large-scale reactors were conducted 20 times in real plating wastewater. However, it was noticed that the regulation was not satised when the concentration of Cu2+ was above 26.7 mg/L, and it was overcome by the increasing retention time. When retention time was extended 23 h at each reactor (reactors I and II), the concentration of Cu2+ in efuent was satised for the regulation in Korea (See in supplementary material, Fig. S5). We also observed the removal

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Table 5 Treatment of Cu2+ and Zn2+ from plating wastewaters using reactors in series. Noa 1 2 3 4 5 6 7 8 9 2 5 8
a b c d

Inuent (mg/L) Cu2+ 23.2 38.0 31.7 30.8 26.7 26.5 26.4 19.1 20.3 15.2 1.4 2.5

Efuent from reactor I (mg/L) N.Ac 13.1 9.6 N.A. N.A. 4.5 N.A. N.A. 4.9 0.4 N.A. N.A.

Efuent form reactor II (mg/L) 2.1 8.1 6.8 8.0 2.0 2.7 2.8 1.8 2.0 0.3 0.3 0.4

Level of regulation in Koreab 3.0

Level of regulation in WHO 1.5

Zn2+d

5.0

2.0

Sample numbers. Efuent quality standard of wastewater in Korea. Not Available. It indicated that sample was not measured. Sample numbers of other than 2, 5, and 8 contained less than 0.4 mg/L of Zn2+ in inuent, so it was not shown.

of other ions like Cr6+ in plating wastewater. The removal percentages of Cr6+ ranged from 30 to 75% when concentrations of Cr6+ in inuent were 1.16.5 mg/L. Therefore, it could indicate that heavy metal ions other than Cu2+ and Zn2+ could also be removed with this process.

Supplementary material related to this article can be found, in the online version, at doi:10.1016/j.jece.2013.10.017.

Conclusions This study showed that WR prepared from bottom ash with soil could be used as an effective adsorbent for heavy metals (Cu2+ and Zn2+) removal in industrial plating wastewater. Equilibrium data of both Cu2+ and Zn2+ was well tted by both the Langmuir and Freundlich models, and the order of afnity was followed as Cu2+ > Zn2+. Kinetically, adsorption of both Cu2+ and Zn2+ was predicted by using the pseudo-second order model with higher correlation coefcients (r2 > 0.95). Moreover, initial adsorption rate, h (mg/g min), linearly increased. As a result obtained from large-scale reactor in series, the removal efciency of Cu2+ and Zn2+ was approximately 7491% and 7898%, respectively, and the proposed process containing WR was applicable to treat a real plating wastewater. Acknowledgments This work was supported by the Korea Environmental Industry & Technology Institute (KEITI, Project No.: 071-081-126) and BK 21 of Korea. Substrate was supported by CRP-SW at Kyonggi University, Korea.

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Fig. 3. Effect of pH on the removal of Cu2+ (a) and Zn2+ (b) with/without WR (Cu or Zn species by literature [39]).

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Please cite this article in press as: Y.-H. Jo, et al., Feasibility test for waste-reclaimed material to remove Cu2+ and Zn2+: Kinetics and applications to treat a real plating wastewater, J. Environ. Chem. Eng. (2013), http://dx.doi.org/10.1016/j.jece.2013.10.017