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Article history: A zinc-dominant ferrite catalyst for efcient degradation of organic dye was prepared by the calcination
Received 7 August 2016 of electroplating sludge (ES). Characterizations indicated that zinc ferrite (ZnFe2O4) coexisted with Fe2O3
Received in revised form structure was the predominant phase in the calcined electroplating sludge (CES). CES displayed a high
14 November 2016
decolorization ratio (88.3%) of methylene blue (MB) in the presence of H2O2 combined with UV irradi-
Accepted 17 November 2016
ation. The high efciency could be ascribed to the photocatalytic process induced by ZnFe2O4 and the
photo-Fenton dye degradation by ferrous content, and a small amount of Al and Mg in the sludge might
also contribute to the catalysis. Moreover, the degradation capability of dye by CES was supported by the
Keywords:
Electroplating sludge
synthetic ZnFe2O4 with different Zn to Fe molar ratio (n(Zn): n(Fe)), as 84.81%e86.83% of dye was
Zinc ferrite removed with n(Zn): n(Fe) ranged from 1:0.5 to 1:3. All synthetic ferrite samples in the simulation
Photocatalysis achieved adjacent equilibrium decolorization ratio, the exible proportioning of divalent metal ions
Fenton (M2) to trivalent metal ions (M3) applied in the synthesis indicated that the catalyst has a high
availability. Therefore, an efcacious catalyst for the degradation of dye can potentially be derived from
heavy metal-containing ES, it's a novel approach for the reutilization of ES.
2016 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jenvman.2016.11.039
0301-4797/ 2016 Elsevier Ltd. All rights reserved.
Z. Cao et al. / Journal of Environmental Management 193 (2017) 146e153 147
applications is ZnFe2O4 (Dom et al., 2015), it has been widely 1 h before transferring the contents to 1000 mL stainless steel
studied in the decomposition of organic contaminants such as autoclave. The temperature of the autoclave was maintained at
Rhodamine B (Guo et al., 2014; Liu et al., 2012; Nan et al., 2013), 230 C for half an hour and then the reaction mixture was allowed
methyl orange (Bhukal et al., 2014b; Fan et al., 2009; Kulkarni et al., to cool to room temperature. The product formed was washed
2016), and methylene blue (Fei et al., 2013; Feng et al., 2015; several times, ltered and dried at 100 C for 8 h. The synthesized
Sharma and Singhal, 2013; Shen et al., 2008; Soltani and Entezari, ferrites were employed as control to in the MB degradation.
2013). More importantly, the Fenton-like process can be induced
by the ferrous content (Casbeer et al., 2012; Jauhar et al., 2014;
Martirosyan and Luss, 2007; Reddy and Lee, 2013). 2.4. Adsorption and degradation experiments
Therefore, the aim of the current study is to 1) prepare Zn-
dominant ferrite catalyst from selected ES; 2) conduct the photo- The degradation was conducted in the apparatus as Fig. 2. In
Fenton degradation of MB by calcined electroplating sludge (CES); general, 0.5 g CES samples were added into 500 mL of MB solution
3) Synthesize ferrites with variable Zn/Fe molar ratio, and to vali- (initial concentration of MB is 10 mg/L). The initial pH was
date the feasibility of the reutilization of ES; and 4) Verify the controlled at 3 and the initial H2O2 concentration was 2.5 mmol/L,
environmental security of sludge-derived catalyst application. To according to the optimal reaction conditions study (data not
the best of our knowledge, it is the rst time to report on a novel shown). A 75 W Hg lamp (Toshiba SHL-100 UVQ-2) was employed
approach to reuse heavy metal-containing ES to form Zn-dominant as the UV source. For the kinetics, a proper amount of liquid sam-
ferrite-based catalytic system. ples were extracted from the system at 0, 10, 30, 60, 90 and 120 min
and separated by centrifuge for 10 min before spectrophotometric
2. Materials and methods measurements. The concentration of dye was determined at
664 nm for MB using an ultravioletevisible (UVeVis) spectropho-
2.1. Materials tometer (U-3010, Hitachi Co., Japan), The decolorization capacity of
MB was calculated by the following equation:
Raw ES was directly collected from Shanghai Hazardous Waste
C0 C
Management Centre. The water was freshly distilled and deionized W 100% (1)
C0
before used. All the reagents are analytical grade and procured from
Sino-pharm Group Chemical Reagent Co. Ltd., China.
where W stands for the decolorization rate (%), C0 and Ce are the
initial and equilibrium concentrations of MB (mg/L), respectively.
2.2. Preparation of calcined electroplating sludge
CES samples were prepared as Fig. 1. Dry ES was grinned and 2.5. Leaching test
sieved through a 0.15 mm mesh, samples were calcined in mufe
furnace (SX-G12123 Ruipu Co., China). The temperature was In this study, the US Environmental Protection Agency (US EPA)
increased to 300 C, 500 C and 700 C with 5 C/min, and then kept Toxicity Characteristic Leaching Procedure (TCLP) (1311) was fol-
constant for 6 h. The electroplating sludge calcined at different lowed to determine the chemical stability of the prepared catalyst.
temperatures was marked as CES300, CES500 and CES700, According to the standard procedure and the reaction condition,
respectively. distilled water with pH adjusted to 4.93 0.05 was chosen as the
extraction uid, and the volume ratio of solid to liquid was 1:20.
2.3. Synthesis of ZnFe2O4 The mixed samples were shaken at the rate of 302 rpm for 18 h,
and then were ltered to collect the ltrate. Finally, the leached
Pure ferrite was prepared by zinc nitrate(Guin et al., 2005). metal concentrations in the ltrate were determined with induc-
Stoichiometric amounts of Zn(NO3)2 and Fe(NO3)3$9H2O are dis- tively coupled plasma optical emission spectrometer (ICP-OES,
solved in water. The pH of the solution was adjusted to 8 by slow Leeman Co., USA).
addition of ammonia solution. The reaction mixture was stirred for
Fig. 3. XRD patterns of (a) CES700, (b) CES500, (c) CES300, and (d) raw ES.
3. Results and discussion
Table 3
FT-IR absorption band frequencies of CES samples.
Fig. 7. The decolorization rate of MB by (a) CES H2O2 without UV irradiation and (b) with UV irradiation; The initial MB concentration is 10 mg/L, and the dosage of solid 0.5 g, the
initial pH is 3, the initial H2O2 concentration is 2.5 mmol/L and A 75 W Hg lamp (Toshiba SHL-100 UVQ-2) was employed as the UV source.
degradation procedures of MB. Fig. 8 showed the changes in the sludge-derived catalyst. The photocatalytic process of ZnFe2O4 and
absorbance proles of MB solution in the CES700/H2O2/UV system. preponderances over pure ferrite Fe3O4 can be understood as
The reaction started with the MB concentration of 50 mg/L. Four follow.
characteristic peaks (246, 291, 615, 664 nm) were observed, which When irradiated with UV, photo-generated electrons (e CB) and
was in accordance with the reported. Absorption bands of MB at holes (h
VB) were excited in ZnFe2O4, and the photo-reactions were
648e655 nm, 620e634 nm, and 608e612 nm were for Azure A, B proceeded as Eqs. (2)e(6) (Daneshvar et al., 2007; Su et al., 2012).
and C, respectively (Zhang et al., 2001). As bands at 291 and 246 nm
were referred to phenothiazine species. All peaks reduced rapidly ZnFe2O4 (CES) hy/ ZnFe2O4 (CES) (e
CB hVB) (2)
along with the time increasing, it also could be observed from Fig. 7
that approximately 60% of the MB was removed during the rst h
VB dye / oxidation of dye (3)
20 min. The eventual disappearance of the original absorptions
suggested the almost complete degradation of MB (Zhang et al., h
VB H2O / H OH
(4)
2006).
h
VB OH / OH H
(5)
3.3. Preponderances of CES-derived ferrite in catalytic application
OH dye / degradation of dye (6)
ZnFe2O4 coexistent with Fe2O3 were predominant phases of
As Fe presented different oxidation states in all samples, a
photo-Fenton process could be initiated in the H2O2/UV system as
Eqs. (7)e(11)(Garrido-Ramrez et al., 2010; Kim and Kan, 2015; Li
et al., 2015a; Navalon et al., 2010).
H2O2 e
CB/ OH OH
(10)
Fe3 e
CB / Fe
2
(11)
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