Catalytic peroxidation of acrylonitrile aqueous solution by Ni-doped CeO2 catalysts: characterization, kinetics and thermodynamics

  • A. KumarEmail author
  • B. Prasad
Original Paper


Acrylonitrile is one of the major pollutants of acrylonitrile–butadiene–styrene resin industry wastewater present in high concentration. In the current study, the treatment of acrylonitrile from aqueous solution was performed by catalytic peroxidation using Ni-doped CeO2 catalysts. Various catalysts with different loadings of nickel were synthesized by co-precipitation method and further characterized by X-ray diffraction, Fourier transform infrared spectroscopy, liquid nitrogen adsorption–desorption technique, transmission electron microscopy, scanning electron microscopy with energy-dispersive X-ray, thermogravimetric analysis and X-ray photoelectron spectroscopy. The effects of various parameters such as catalyst dose, pH, nickel loading, H2O2/acrylonitrile molar ratio, initial concentration of acrylonitrile, temperature and reaction time on acrylonitrile removal were studied. Maximum acrylonitrile removal of 84.12% was observed at optimum operating conditions of pH = 6.5, catalyst dosage = 500 mg/L, nickel loading = 2.5 wt.%, stoichiometric molar ratio (H2O2/acrylonitrile) = 1, temperature = 298 K and reaction time = 3 h. Acrylonitrile degradation kinetics was investigated using power law model and non-competitive Langmuir–Hinshelwood model in which non-competitive Langmuir–Hinshelwood isotherm model better fitted for acrylonitrile degradation using Ni-doped CeO2 catalyst. Thermodynamic study of the parameters has also been presented.


Doping Optimization Toxic Oxidation Degradation 



Authors are thankful to Ministry of Human Resource Development (MHRD), Government of India, for providing the financial support for carrying out this work.


  1. Aravindhan R, Fathima NN, Rao JR, Nair BU (2006) Wet oxidation of acid brown dye by hydrogen peroxide using heterogeneous catalyst Mn-salen-Y zeolite: a potential catalyst. J Hazard Mater 138:152–159CrossRefGoogle Scholar
  2. Barrio L, Kubacka A, Zhou G (2010) Unusual physical and chemical properties of Ni in Ce1−x NixO2−y oxides: structural characterization and catalytic activity for the water gas shift reaction. J Phys Chem C 114:12689–12697CrossRefGoogle Scholar
  3. Bobrova L, Andreev D, Ivanov E (2017) Water-gas shift reaction over Ni/CeO2 catalysts. Catalysts 7:310CrossRefGoogle Scholar
  4. Chen Y, Song B, Tang X (2012) One-step synthesis of hollow porous Fe3O4 beads-reduced graphene oxide composites with superior battery performance. J Mater Chem 22:17656–17662CrossRefGoogle Scholar
  5. Cheng S, Lin Y-T, Chen S-K (1996) Enhanced biodegradation of organic nitrogenous compounds in resin manufacturing wastewater by anoxic denitrification and oxic nitrification process. Water Sci Technol 34:35–41Google Scholar
  6. Dai Y, Song Y, Tu X et al (2015) Sequential shape-selective adsorption and photocatalytic transformation of acrylonitrile production wastewater. Water Res 85:216–225CrossRefGoogle Scholar
  7. Du X, Zhang D, Shi L (2012) Morphology dependence of catalytic properties of Ni/CeO2 nanostructures for carbon dioxide reforming of methane. J Phys Chem C 116:10009–10016CrossRefGoogle Scholar
  8. Fujimori A (1983) Mixed-valent ground state of CeO2. Phys Rev B 28:2281–2283CrossRefGoogle Scholar
  9. Garg S, Srivastava VC, Singh S, Mandal TK (2015) Catalytic degradation of pyrrole in aqueous solution by Cu/SBA-15. Int J Chem React Eng. 13:437–445Google Scholar
  10. Godinho M, De F, Gonçalves R, Leite ER (2010) Gadolinium-doped cerium oxide nanorods: novel active catalysts for ethanol reforming. J Mater Sci 45:593–598CrossRefGoogle Scholar
  11. Gomathi Devi L, Girish Kumar S, Mohan Reddy K, Munikrishnappa C (2009) Photo degradation of methyl orange an azo dye by Advanced Fenton process using zero valent metallic iron: influence of various reaction parameters and its degradation mechanism. J Hazard Mater 164:459–467CrossRefGoogle Scholar
  12. Gong YM, Wang SZ, Tang XY (2014) Supercritical water oxidation of acrylic acid production wastewater. Environ Technol 35:907–916CrossRefGoogle Scholar
  13. Gosu V, Dhakar A, Sikarwar P (2018) Wet peroxidation of resorcinol catalyzed by copper impregnated granular activated carbon. J Environ Manag 223:825–833CrossRefGoogle Scholar
  14. Hsueh CL, Huang YH, Wang CC, Chen CY (2005) Degradation of azo dyes using low iron concentration of Fenton and Fenton-like system. Chemosphere 58:1409–1414CrossRefGoogle Scholar
  15. Hung WC, Chu H (2006) Surface and catalytic properties of NiO–Fe2O3 solids supported on Al2O3. J Environ Eng 132:1482–1488CrossRefGoogle Scholar
  16. Ilyas M, Sadiq M (2007) Liquid-phase aerobic oxidation of benzyl alcohol catalyzed by Pt/ZrO2. Chem Eng Technol 30:1391–1397CrossRefGoogle Scholar
  17. Inchaurrondo NS, Massa P, Fenoglio R (2012) Efficient catalytic wet peroxide oxidation of phenol at moderate temperature using a high-load supported copper catalyst. Chem Eng J 198–199:426–434CrossRefGoogle Scholar
  18. Kumar N, Srivastava VC (2018) Simple synthesis of large graphene oxide sheets via electrochemical method coupled with oxidation process. ACS Omega 3:10233–10242CrossRefGoogle Scholar
  19. Kumar A, Prasad B, Mishra IM (2008a) Adsorptive removal of acrylonitrile by commercial grade activated carbon: kinetics, equilibrium and thermodynamics. J Hazard Mater 152:589–600CrossRefGoogle Scholar
  20. Kumar A, Prasad B, Mishra IM (2008b) Optimization of process parameters for removal by a low-cost adsorbent using Box–Behnken design. J Hazard Mater 150:174–182CrossRefGoogle Scholar
  21. Kumar A, Prasad B, Mishra IM (2014) Adsorption of from aqueous solution using bagasse fly ash. J Water Process Eng 2:129–133CrossRefGoogle Scholar
  22. Kumar S, Bhunia S, Ojha AK (2015) Effect of calcination temperature on phase transformation, structural and optical properties of sol–gel derived ZrO2 nanostructures. Phys E Low Dimens Syst Nanostruct 66:74–80CrossRefGoogle Scholar
  23. Kushwaha JP, Srivastava VC, Mall ID (2010) Treatment of dairy wastewater by commercial activated carbon and bagasse fly ash: parametric, kinetic and equilibrium modelling, disposal studies. Bioresour Technol 101:3474–3483CrossRefGoogle Scholar
  24. Lai B, Zhou Y, Yang P, Wang K (2012) Comprehensive analysis of the toxic and refractory pollutants in acrylonitrile-butadiene-styrene resin manufacturing wastewater by gas chromatography spectrometry with a mass or flame ionization detector. J Chromatogr A 1244:161–167CrossRefGoogle Scholar
  25. Li Q, Huang Z, Guan P (2017) Simultaneous Ni doping at atom scale in ceria and assembling into well-defined lotus like structure for enhanced catalytic performance. ACS Appl Mater Interfaces 9:16243–16251CrossRefGoogle Scholar
  26. Li B, Zhang B, Guan Q (2018) Activity of Ni/CeO2 catalyst for gasification of phenol in supercritical water. Int J Hydrog Energy 43:19010–19018CrossRefGoogle Scholar
  27. Lu C, Lin M-R, Lin J (2003) Removal of acrylonitrile vapor from waste gases by a trickle-bed air biofilter. Bioresour Technol 75:35–41CrossRefGoogle Scholar
  28. Mai HX, Sun LD, Zhang YW (2005) Shape-selective synthesis and oxygen storage behavior of ceria nanopolyhedra, nanorods, and nanocubes. J Phys Chem B 109:24380–24385CrossRefGoogle Scholar
  29. Makwana VD, Son YC, Howell AR, Suib SL (2002) The role of lattice oxygen in selective benzyl alcohol oxidation using OMS-2 catalyst: a kinetic and isotope-labeling study. J Catal 210:46–52CrossRefGoogle Scholar
  30. Mirzajani R, Pourreza N, Zayadi A (2016) Nanoporous calcined MCM-41 silica for adsorption and removal of Victoria blue dye from different natural water samples. Desalin Water Treat 57:5903–5913CrossRefGoogle Scholar
  31. Mishra VS, Mahajani VV, Joshi JB (1995) Wet air oxidation. Ind Eng Chem Res 34:2–48CrossRefGoogle Scholar
  32. Molina CB, Casas JA, Zazo JA, Rodríguez JJ (2006) A comparison of Al–Fe and Zr–Fe pillared clays for catalytic wet peroxide oxidation. Chem Eng J 118:29–35CrossRefGoogle Scholar
  33. Murugan R, Ravi G, Vijayaprasath G (2017) Ni–CeO2 spherical nanostructures for magnetic and electrochemical supercapacitor applications. Phys Chem Chem Phys 19:4396–4404CrossRefGoogle Scholar
  34. Naganuma T, Traversa E (2012) Stability of the Ce3+ valence state in cerium oxide nanoparticle layers. Nanoscale 4:4950–4953CrossRefGoogle Scholar
  35. Pachupate NJ, Vaidya PD (2018) Catalytic wet oxidation of quinoline over Ru/C catalyst. J Environ Chem Eng 6:883–889CrossRefGoogle Scholar
  36. Parvas M, Haghighi M, Allahyari S (2014) Catalytic wet air oxidation of phenol over ultrasound-assisted synthesized Ni/CeO2–ZrO2 nanocatalyst used in wastewater treatment. Arab J Chem 35:1878–5352Google Scholar
  37. Periyat P, Laffir F, Tofail SAM, Magner E (2011) A facile aqueous sol–gel method for high surface area nanocrystalline CeO2. RSC Adv 1:1794–1798CrossRefGoogle Scholar
  38. Peymani M, Alavi S, Arandiyan H, Rezaei M (2018) Rational design of high surface area mesoporous Ni/CeO2 for partial oxidation of propane. Catalysts 8:3881CrossRefGoogle Scholar
  39. Popuri SR, Chang C-Y, Xu J (2011) A study on different addition approach of Fenton’s reagent for DCOD removal from ABS wastewater. Desalination 277:141–146CrossRefGoogle Scholar
  40. Priyanka S, Srivastava VC (2013) Photocatalytic oxidation of dye bearing wastewater by iron doped zinc oxide. Ind Eng Chem Res 52:17790–17799CrossRefGoogle Scholar
  41. Pudukudy M, Yaakob Z, Narayanan B (2014) Selective vapour phase oxidation of benzyl alcohol to benzaldehyde over mesoporous ceria-zirconia solid solution synthesized via a facile citrate route. J Clust Sci 25:1599–1614CrossRefGoogle Scholar
  42. Rao AV, Kalesh RR, Pajonk GM (2003) Hydrophobicity and physical properties of TEOS based silica aerogels using phenyl triethoxysilane as a synthesis component. J Mater Sci 38:4407–4413CrossRefGoogle Scholar
  43. Ren G, Zhou M, Su P (2018) Highly energy-efficient removal of acrylonitrile by peroxi-coagulation with modified graphite felt cathode: influence factors, possible mechanism. Chem Eng J 343:467–476CrossRefGoogle Scholar
  44. Saeed M, Ilyas M (2013) Oxidative removal of phenol from water catalyzed by nickel hydroxide. Appl Catal B Environ 129:247–254CrossRefGoogle Scholar
  45. Saeed M, Ilyas M, Siddique M, Ahmad A (2013) Oxidative degradation of oxalic acid in aqueous medium using manganese oxide as catalyst at ambient temperature and pressure. Arab J Sci Eng 38:1739–1748CrossRefGoogle Scholar
  46. Saeed M, Adeel S, Ilyas M (2016) Oxidative degradation of methyl orange catalyzed by lab prepared nickel hydroxide in aqueous medium. Desalin Water Treat 57:12804–12813CrossRefGoogle Scholar
  47. Sandhwar VK, Prasad B (2017) Comparison of phthalic acid removal from aqueous solution by electrochemical methods: optimization, kinetic and sludge study. J Environ Manag 203:476–488CrossRefGoogle Scholar
  48. Santander JA, Tonetto GM, Pedernera MN, López E (2017) Ni/CeO2–MgO catalysts supported on stainless steel plates for ethanol steam reforming. Int J Hydrog Energy 42:9482–9492CrossRefGoogle Scholar
  49. Shin YH, Lee HS, Lee YH, Kim J, Kim JD, Lee YW (2009) Synergetic effect of copper-plating wastewater as a catalyst for the destruction of wastewater in supercritical water oxidation. J Hazard Mater 167:824–829CrossRefGoogle Scholar
  50. Singh S, Lo S-L (2017) Catalytic performance of hierarchical metal oxides for per-oxidative degradation of pyridine in aqueous solution. Chem Eng J 309:753–765CrossRefGoogle Scholar
  51. Subbaramaiah V, Srivastava VC, Mall ID (2013a) Catalytic activity of Cu/SBA-15 for peroxidation of pyridine bearing wastewater at atmospheric condition. AIChE J 59:2577–2586CrossRefGoogle Scholar
  52. Subbaramaiah V, Srivastava VC, Mall ID (2013b) Catalytic wet peroxidation of pyridine bearing wastewater by cerium supported SBA-15. J Hazard Mater 248–249:355–363CrossRefGoogle Scholar
  53. Subbaramaiah V, Srivastava VC, Mall ID (2013c) Optimization of reaction parameters and kinetic modeling of catalytic wet peroxidation of picoline by Cu/SBA-15. Ind Eng Chem Res 52:9021–9029CrossRefGoogle Scholar
  54. Sun S, Mao D, Yu J (2015) Low temperature CO oxidation on CuO/CeO2 catalysts: the significant effect of copper precursor and calcination temperature. Catal Sci Technol 5:3166–3181CrossRefGoogle Scholar
  55. Trovarelli A (1996) Catalytic properties of ceria and CeO2-containing materials. Catal Rev Sci Eng 38:439–520CrossRefGoogle Scholar
  56. Vivek S, Arun Kumar P, Babu KS (2016) In situ generated nickel on cerium oxide nanoparticle for efficient catalytic reduction of 4-nitrophenol. RSC Adv 6:45947–45956CrossRefGoogle Scholar
  57. Wang C-C, Lee C-M (2001a) Denitrification with acrylamide by pure culture of bacteria isolated from acrylonitrile–butadiene–styrene resin manufactured wastewater treatment system. Chemosphere 44:1047–1053CrossRefGoogle Scholar
  58. Wang CC, Lee CM (2001b) Denitrification with acrylonitrile as a substrate using pure bacteria cultures isolated from acrylonitrile–butadiene–styrene wastewater. Environ Int 26:237–241CrossRefGoogle Scholar
  59. Wyatt JM, Knowles CJ (1995) Microbial degradation of acrylonitrile waste effluents: the degradation of effluents and condensates from the manufacture of acrylonitrile. Int Biodeterior Biodegrad 35:227–248CrossRefGoogle Scholar
  60. Xu J, Xue B, Liu YM (2011) Mesostructured Ni-doped ceria as an efficient catalyst for styrene synthesis by oxidative dehydrogenation of ethylbenzene. Appl Catal A 405:142–148CrossRefGoogle Scholar
  61. Yadav B, Srivastava VC (2017) Catalytic peroxidation of recalcitrant quinoline by ceria impregnated granular activated carbon. Clean Technol Environ Policy 19:1547–1555CrossRefGoogle Scholar
  62. Yan B, Zhu H (2008) Controlled synthesis of CeO2 nanoparticles using novel amphiphilic cerium complex precursors. J Nanopart Res 10:1279–1285CrossRefGoogle Scholar
  63. Zhan Y, Li H, Chen Y (2010) Copper hydroxyphosphate as catalyst for the wet hydrogen peroxide oxidation of azo dyes. J Hazard Mater 180:481–485CrossRefGoogle Scholar
  64. Zhang D, Fu H, Shi L (2007) Synthesis of CeO2 nanorods via ultrasonication assisted by polyethylene glycol. Inorg Chem 46:2446–2451CrossRefGoogle Scholar
  65. Zhang J, Yang H, Wang S (2014) Mesoporous CeO2 nanoparticles assembled by hollow nanostructures: formation mechanism and enhanced catalytic properties. Cryst Eng Commun 16:8777–8785CrossRefGoogle Scholar
  66. Zheng D, Cai W, Wang T (2015) Pilot-scale integrated membrane system for the treatment of acrylonitrile wastewater. Desalination 357:215–224CrossRefGoogle Scholar
  67. Zhou HP, Wu HS, Shen J (2010) Thermally stable Pt/CeO2 hetero-nanocomposites with high catalytic activity. J Am Chem Soc 132:4998–4999CrossRefGoogle Scholar

Copyright information

© Islamic Azad University (IAU) 2019

Authors and Affiliations

  1. 1.Department of Chemical EngineeringIndian Institute of Technology RoorkeeRoorkeeIndia

Personalised recommendations