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Frontiers of Environmental Science & Engineering

ISSN 2095-2201

ISSN 2095-221X(Online)

CN 10-1013/X

Postal Subscription Code 80-973

2018 Impact Factor: 3.883

Front. Environ. Sci. Eng.    2019, Vol. 13 Issue (4) : 49    https://doi.org/10.1007/s11783-019-1130-7
RESEARCH ARTICLE
Combined Fenton process and sulfide precipitation for removal of heavy metals from industrial wastewater: Bench and pilot scale studies focusing on in-depth thallium removal
Huosheng Li1, Hongguo Zhang2, Jianyou Long3(), Ping Zhang4, Yongheng Chen1()
1. Institute of Environmental Studies at Greater Bay, Key Laboratory for Water Quality and Conservation of Pearl River Delta (Ministry of Education), Guangzhou University, Guangzhou 510006, China
2. Guangzhou University–Linköping University Research Center on Urban Sustainable Development, Guangzhou University, Guangzhou 510006, China
3. School of Environmental Science and Engineering, Guangzhou University, Guangzhou 510006, China
4. School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006, China
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Abstract

Addition of alkali to pH 10 is effective for precipitation of precipitable metals.

Fenton treatment is effective for substantial removal of Tl, Cd, Cu, Pb, and Zn.

Sulfide precipitation is a final step for removal of trace Tl, Cd, Cu, Pb, and Zn.

Bench and pilot studies demonstrated the effectiveness of this combined technique.

Thallium (Tl) in industrial wastewater is a public health concern due to its extremely high toxicity. However, there has been limited research regarding Tl removal techniques and engineering practices to date. In this investigation, bench and pilot studies on advanced treatment of industrial wastewater to remove Tl to a trace level were conducted. The treatment process involved a combination of hydroxide precipitation, Fenton oxidation, and sulfide precipitation. While hydroxide precipitation was ineffective for Tl+ removal, it enabled the recovery of approximately 70%–80% of Zn as Zn hydroxide in alkaline conditions. The Fenton process provided good Tl removal (>95%) through oxidation and precipitation. Tl was then removed to trace levels (<1.0 µg/L) via sulfide precipitation. Effective removal of other heavy metals was also achieved, with Cd<13.4 µg/L, Cu<39.6 µg/L, Pb<5.32 µg/L, and Zn<357 µg/L detected in the effluent. X-ray photoelectron spectroscopy indicated that Tl2S precipitate formed due to sulfide precipitation. Other heavy metals were removed via the formation of metal hydroxides during hydroxide precipitation and Fenton treatment, as well as via the formation of metal sulfides during sulfide precipitation. This combined process provides a scalable approach for the in-depth removal of Tl and other heavy metals from industrial wastewater.

Keywords Thallium      Pilot      Fenton      Sulfide precipitation      Heavy metal      Industrial wastewater     
Corresponding Author(s): Jianyou Long,Yongheng Chen   
Issue Date: 26 April 2019
 Cite this article:   
Huosheng Li,Hongguo Zhang,Jianyou Long, et al. Combined Fenton process and sulfide precipitation for removal of heavy metals from industrial wastewater: Bench and pilot scale studies focusing on in-depth thallium removal[J]. Front. Environ. Sci. Eng., 2019, 13(4): 49.
 URL:  
https://academic.hep.com.cn/fese/EN/10.1007/s11783-019-1130-7
https://academic.hep.com.cn/fese/EN/Y2019/V13/I4/49
Metal ion Metal concentration (mg/L, Mean±SDa))
Low High
Na 360±14.3 4245±381
K 798±8.82 13390±277
Cd 24.8±3.60 680.5±32.2
Cu 1.59±0.281 2.69±0.0813
Pb 1.35±0.122 8.57±0.431
Zn 346±25.3 1446±16.7
Tl 0.272±0.0235 5.46±0.383
Tab.1  Compositions of industrial wastewater samples from a Zn oxide production plant
Fig.1  Schematic diagram of the pilot plant for Tl removal from industrial wastewater.
Fig.2  Effects of sedimentation pH on (a, b) Zn and (c, d) Tl removal from industrial wastewater in the first treatment: (a, c) low strength wastewater and (b, d) high strength wastewater.
Fig.3  Effects of (a, b) H2O2 dosage and (c,(d) coagulation pH on Tl removal from industrial wastewater in the second treatment: (a, c) low strength wastewater and (b, d) high strength wastewater.
Fig.4  Effects of ((a), (b)) H2O2 dosage and ((c), (d)) precipitation pH on Tl removal from industrial wastewater in the third treatment: ((a), (c)) low strength wastewater and ((b), (d)) high strength wastewater.
Fig.5  Tl removal in each operational unit (1st means hydroxide precipitation, 2nd means Fenton treatment, and 3rd means sulfide precipitation) operating with (a) low and (b) high strength influent. The inlet sub-figure in Fig. 5(a) represents the Tl removal for the third and final effluent on a smaller scale. The different runs correspond to the water samples collected on different days.
Wastewater Process Cd (mg/L) Cu (mg/L) Pb (mg/L) Zn (mg/L)
Low strength Raw 24.5±3.51 1.85±1.34 1.16±0.265 340±10.5
1st 2.39±1.13 303±9.31 a) 630±20.3 69.8±2.63
2nd 540±21.2 a) 60.3±2.46 a) 50.1±3.54 a) 450±10.6 a)
3rd 10.5±1.21a) 20.4±1.98 a) 2.18±0.134 a) 150±6.18 a)
Effluent 13.4±1.03 a) 15.1±1.25 a) 5.32±0.367 a) 135±5.37 a)
High strength Raw 713±30.8 2.70±1.07 8.57±0.387 1459±102
1st 49.0±2.96 1.90±0.351 2.39±0.187 314±21.6
2nd 80.4±2.37 a) 105±2.64 a) 21.6±1.47 a) 40.4±2.56
3rd 10.3±1.16 a) 20.3±2.73 a) 1.38±0.173 a) 451±30.7 a)
Effluent 10.4±0.597 a) 39.6±4.89 a) 1.45±0.357 a) 357±24.8 a)
Tab.2  Concentrations of other major toxic heavy metals in the effluent from each operational unit
Fig.6  Mass balances of metals (Tl, Cd, Cu, Pb, and Zn) during treatment of high strength industrial wastewater.
Fig.7  XPS spectra of the precipitates from multiple treatment process: (a) Tl4f core level, (b) Cd3d core level, (c) Zn2p core level, and (d) S2p core level (third unit).
Reagents Price ($/t) Dosage (kt/m3) Cost ($/m3)
H2O2 384.62 0.0022 0.85
FeSO4 76.92 0.002 0.15
PAM 2461.54 0.000004 0.01
NaOH 615.38 0.002 1.23
Na2S 792.31 0.001 0.79
H2SO4 138.46 0.002 0.28
3.31 a)
Tab.3  Costs of the reagents used in the in-depth Tl removal process
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