Simultaneous removal of Cu (II) and Cr (VI) ions from petroleum refinery wastewater using ZnO/Fe₃O₄ nanocomposite

Abstract

The presence and removal of heavy metals such as Cu(II) as well as Cr(VI) in petroleum refinery wastewater calls for concerted efforts due to their mobility, toxicity, bioaccumulation, and non-biodegradability in the environment. In this present work, zinc oxide (ZnO), iron oxide (Fe₃O₄) nanoparticles and ZnO/Fe₃O₄ nanocomposites were synthesized via simple sol-gel and chemical reduction methods; characterized using different analytical tools and then applied as nanoadsorbent to sequester Cu(II) and Cr(VI) ions from Petroleum Refinery wastewater via batch adsorption process. Cu(II) and Cr(VI) adsorption processes were examined with respect to contact time (kinetic effect), nanoadsorbent dosage, isotherm equilibrium, and thermodynamic parameters. ZnO/Fe₃O₄ nanocomposites with higher surface area (39.450 m²/g) have a mixture of rod-like and spherical shapes as compared to ZnO and Fe₃O₄ nanoparticles with spherical shape only and surface areas of 8.62 m²/g and 7.86 m²/g) according to the high-resolution scanning electron microscopy (HRSEM) and Brunauer–Emmett–Teller (BET) analysis. The X-ray diffractometer (XRD) results revealed the formation of hexagonal wurtzite structure of ZnO and the face-centered cubic structure phase of Fe₃O₄ nanoparticles, after the formation of the ZnO/Fe₃O₄ nanocomposites the phases of the nanoparticles were not affected but the diffraction peaks shifted to higher 2θ degree. The average crystallite size of ZnO and Fe₃O₄ nanoparticles and ZnO/Fe₃O₄ nanocomposites were 20.12, 26.36 and 14.50 nm respectively. The maximum removal efficiency of Cu (II) (92.99%) and Cr (VI) (77.60%) by ZnO/Fe₃O₄ nanocomposites was higher than 85.83%; 65.19% for Cu (II) and 80.57%; 62.53 for Cr (VI) using ZnO and Fe₃O₄ nanoadsorbents individually under the following conditions: contact time (15), dosage (0.08 g) and temperature (30 °C). The experimental data for Cu (II) and Cr (VI) ion removal fitted well to the pseudo-second-order kinetic and Langmuir isotherm models. The thermodynamic study suggested that the removal of the two metal ions from petroleum wastewater was endothermic. The reusability study after the fourth adsorption-desorption cycle indicated the stability of ZnO/Fe₃O₄ nanocomposites with 85.51% and 69.42% removal efficiency of Cu (II) and Cr (VI). The results showed that ZnO/Fe₃O₄ nanocomposite achieves higher performance than ZnO and Fe₃O₄ alone in the removal of Cu (II) and Cr (VI) ions from the petroleum refinery wastewater.

Keywords:

• ZnO/Fe₃O₄ nanocomposite
• sol-gel
• heavy metal
• adsorption
• regeneration
• kinetic and isotherm model

Acknowledgments

The authors appreciate the contribution of the following people for their technical assistance: Dr. Remy Bucher (XRD analysis, iThemba Labs, South Africa); Dr. Franscious Cummings (HRSEM/HRTEM/SAED/EDS) analysis, Physics department, University of the Western Cape (UWC), South Africa); and Prof. W.D. Roos for XPS analysis. Mr. Sandeeran Govender (BET analysis), Chemical Engineering Department, University of Cape Town, South Africa.

Declaration of competing interest

There are no conflicts to declare

Data availability statement

The authors confirm that the data supporting the findings of this study are available within the article.

Funding

The author(s) reported there is no funding associated with the work featured in this article.