Catalytic wet air oxidation of phenol, nitrobenzene and aniline over the multi-walled carbon nanotubes (MWCNTs) as catalysts

Abstract

Wet air oxidation (WAO) is one of effective technologies to eliminate hazardous, toxic and highly concentrated organic compounds in the wastewater. In the paper, multi-walled carbon nanotubes (MWCNTs), functionalized by O₃, were used as catalysts in the absence of any metals to investigate the catalytic activity in the catalytic wet air oxidation (CWAO) of phenol, nitrobenzene (NB) and aniline at the mild operating conditions (reaction temperature of 155°C and total pressure of 2.5 MPa) in a batch reactor. The MWCNTs were characterized with scanning electron microscopy (SEM), transmission electron microscopy (TEM), gas adsorption measurements (BET), fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS). The functionalized MWCNTs showed good catalytic performance. In the CWAO of phenol over the functionalized MWCNTs, total phenol removal was obtained after 90 min run, and the reaction apparent activation energy was ca. 40 kJ·mol^-1. The NB was not removed in the CWAO of single NB, while ca. 97% NB removal was obtained and 40% NB removal was attributed to the catalytic activity after 180 min run in the presence of phenol. Ca. 49% aniline conversion was achieved after 120 min run in the CWAO of aniline.

Keywords

catalytic wet air oxidation (CWAO) / carbon nanotubes (CNTs) / phenol / nitrobenzene / aniline

References

[1] Wang Y T. Effect of chemical oxidation on anerobic biodegradation of model phenolic compounds. Water Environment Research, 1992, 64(3): 268–273

[2] Lee S H, Carberry J B. Biodegradation of PCP enhanced by chemical oxidation pretreatment. Water Environment Research, 1992, 64(5): 682–690

[3] Li H B, Cao H B, Li Y P, Zhang Y, Liu H R. Effect of organic compounds on nitrite accumulation during the nitrification process for coking wastewater. Water Science & Technology, 2010, 62(9): 2096–2105

[4] Niu J F, Lin H, Xu J L, Wu H, Li Y Y. Electrochemical mineralization of perfluorocarboxylic acids (PFCAs) by Ce-doped modified porous nanocrystalline PbO₂ film electrode. Environmental Science & Technology, 2012, 46(18): 10191–10198

[5] Mishra V S, Mahajani V V, Joshi J B. Wet air oxidation. Industrial & Engineering Chemistry Research, 1995, 34(1): 2–48

[6] Luck F. Wet air oxidation: past, present and future. Catalysis Today, 1999, 53(1): 81–91

[7] Yang S X, Liu Z Q, Huang X H, Zhang B P. Wet air oxidation of epoxy acrylate monomer industrial wastewater. Journal of Hazardous Materials, 2010, 178(1–3): 786–791

[8] Oliviero L, Barbier J Jr, Duprez D. Wet air oxidation of nitrogen-containing organic compounds and ammonia in aqueous media. Applied Catalysis B: Environmental, 2003, 40(3): 163–184

[9] Benitez F J, García J, Acero J L, Real F J, Roldan G. Non-catalytic and catalytic wet air oxidation of pharmaceuticals in ultra-pure and natural waters. Process Safety and Environmental Protection, 2011, 89(5): 334–341

[10] Chen I P, Lin S S, Wang C H, Chang L, Chang J S. Preparing and characterizing an optimal supported ceria catalyst for the catalytic wet air oxidation of phenol. Applied Catalysis B: Environmental, 2004, 50(1): 49–58

[11] Yang S X, Besson M, Descorme C. Catalytic wet air oxidation of formic acid over Pt/Ce_xZr_1-xO₂ catalysts at low temperature and atmospheric pressure. Applied Catalysis B: Environmental, 2010, 100(1–2): 282–288

[12] Wang J B, Zhu W P, Yang S X, Wang W, Zhou Y R. Catalytic wet air oxidation of phenol with pelletized ruthenium catalysts. Applied Catalysis B: Environmental, 2008, 78(1–2): 30–37

[13] Tran N D, Besson M, Descorme C. TiO₂-supported gold catalysts in the catalytic wet air oxidation of succinic acid: influence of the preparation, the storage and the pre-treatment conditions. New Journal of Chemistry, 2011, 35(10): 2095–2104

[14] Bistan M, Tišler T, Pintar A. Ru/TiO₂ catalyst for efficient removal of estrogens from aqueous samples by means of wet-air oxidation. Catalysis Communications, 2012, 22(10): 74–78

[15] Serp P, Corrias M, Kalck P. Carbon nanotubes and nanofibers in catalysis. Applied Catalysis A, General, 2003, 253(2): 337–358

[16] Stüber F, Font J, Fortuny A, Bengoa C, Eftaxias A, Fabregat A. Carbon materials and catalytic wet air oxidation of organic pollutants in wastewater. Topics in Catalysis, 2005, 33(1–4): 3– 50

[17] Suarez-Ojeda M E, Stüber F, Fortuny A, Fabregat A, Carrera J, Font J. Catalytic wet air oxidation of substituted phenols using activated carbon as catalyst. Applied Catalysis B: Environmental, 2005, 58(1–2): 105–114

[18] Yang S X, Li X, Zhu W P, Wang J B, Descorme C. Catalytic activity, stability and structure of multi-walled carbon nanotubes in the wet air oxidation of phenol. Carbon, 2008, 46(3): 445–452

[19] Gomes H T, Machado B F, Ribeiro A, Moreira I, Rosário M, Silva A M T, Figueiredo J L, Faria J L. Catalytic properties of carbon materials for wet oxidation of aniline. Journal of Hazardous Materials, 2008, 159(2–3): 420–426

[20] Rocha R P, Sousa J P S, Silva A M T, Pereira M F R, Figueiredo J L. Catalytic activity and stability of multiwalled carbon nanotubes in catalytic wet air oxidation of oxalic acid: the role of the basic nature induced by the surface chemistry. Applied Catalysis B: Environmental, 2011, 104(3–4): 330–336

[21] Soria-Sánchez M, Maroto-Valiente A, Álvarez-Rodríguez J, Muñoz-Andrés V, Rodríguez-Ramos I, Guerrero-Ruíz A. Carbon nanostrutured materials as direct catalysts for phenol oxidation in aqueous phase. Applied Catalysis B: Environmental, 2011, 104(1–2): 101–109

[22] Milone C, Hameed A R S, Piperopoulos E, Santangelo S, Lanza M, Galvagno S. Catalytic wet air oxidation of p-coumaric acid over carbon nanotubes and activated carbon. Industrial & Engineering Chemistry Research, 2011, 50(15): 9043–9053

[23] Yang S X, Wang X G, Yang H W, Sun Y, Liu Y X. Influence of the different oxidation treatment on the performance of multi-walled carbon nanotubes in the catalytic wet air oxidation of phenol. Journal of Hazardous Materials, 2012, 233–234: 18–24

[24] Zhan W, Wang X C, Li D S, Ren Y Z, Liu D Q, Kang J X. Catalytic wet air oxidation of high concentration pharmaceutical wastewater. Water Science & Technology, 2013, 67(10): 2281–2286

[25] Martín-Hernández M, Carrera J, Suárez-Ojeda M E, Besson M, Descorme C. Catalytic wet air oxidation of a high strength p-nitrophenol wastewater over Ru and Pt catalysts: Influence of the reaction conditions on biodegradability enhancement. Applied Catalysis B: Environmental, 2012, 123–24: 141–150

[26] Zhu W P, Bin Y J, Li Z H, Jiang Z P, Yin T. Application of catalytic wet air oxidation for the treatment of H-acid manufacturing process wastewater. Water Research, 2002, 36(8): 1947–1954

[27] Lin S S, Chang D J, Wang C H, Chen C C. Catalytic wet air oxidation of phenol by CeO₂ catalyst-effect of reaction conditions. Water Research, 2003, 37(4): 793–800

[28] Sadana A, Katzer J R. Catalytic oxidation of phenol in aqueous solution over copper oxide. Industrial & Engineering Chemistry Fundamentals, 1974, 13(2): 127–134

[29] Li N, Descorme C, Besson M. Catalytic wet air oxidation of aqueous solution of 2-chlorophenol over Ru/zirconia catalysts. Applied Catalysis B: Environmental, 2007, 71(3–4): 262–270

[30] Kolaczkowski S T, Plucinski P, Beltran F J, Rivas F J, McLurgh D B. Wet air oxidation: a review of process technologies and aspects in reactor design. Chemical Engineering Journal, 1999, 73(2): 143–160

[31] Arslan-Alaton I, Ferry J L. H₄SiW₁₂O₄₀-catalyzed oxidation of nitrobenzene in supercritical water: kinetic and mechanistic aspects. Applied Catalysis B: Environmental, 2002, 38(4): 283–293

[32] Fu D M, Chen J P, Liang X M. Wet air oxidation of nitrobenzene enhanced by phenol. Chemosphere, 2005, 59(6): 905–908

[33] Ji L L, Shao Y, Xu Z Y, Zheng S R, Zhu D Q. Adsorption of monoaromatic compounds and pharmaceutical antibiotics on carbon nanotubes activated by KOH etching. Environmental Science & Technology, 2010, 44(16): 6429–6436

[34] Zhao L, Sun Z Z, Ma J, Liu H L. Influencing mechanism of bicarbonate on the catalytic ozonation of nitrobenzene in aqueous solution by ceramic honeycomb supported manganese. Journal of Molecular Catalysis A Chemical, 2010, 322(1–2): 26–32

[35] Mestl G, Maksimova N I, Keller N, Roddatis V V, Schlögl R. Carbon nanofilaments in heterogeneous catalysis: an industrial application for new carbon materials? Angewandte Chemie (International Edition in English), 2001, 40(11): 2066–2068

Acknowledgements

This research is supported by the National Natural Science Foundation of China (Grant No. 51078143). Moreover, the authors are sincerely grateful to special fund of State Key Joint Laboratory of Environment Simulation and Pollution Control (12K10ESPCT), the Fundamental Research Funds for the Central Universities (KJ2012071) and the Natural Science Foundation of Heilongjiang Province (B201104) for financial support. In addition, the authors also wish to acknowledge Beijing Cnano Technology Limited Company for kindly supplying the MWCNTs in our study.

Supplementary material is available in the online version of this article at http://dx.doi.org/10.1007/s11783-014-0681-x and is accessible for authorized users.

RIGHTS & PERMISSIONS

2014 Higher Education Press and Springer-Verlag Berlin Heidelberg