Ozone Initiated Oxidation of Cresol Isomers Using γ-Al2O3 and SiO2 as Adsorbents

  • Z. S. Ncanana
  • V. S. R. Rajasekhar Pullabhotla
Article
  • 19 Downloads

Abstract

Ozone initiated oxidation of environmentally unfriendly organic compounds is one of the powerful tools that is utilized to convert and/or completely mineralize these substances. Here we have adopted the adsorption phenomenon in combination with ozonation (0.123 mg/L) of the hazardous cresol isomers mounted in a glass column. An oxide of aluminum (γ-Al2O3) or silicon (SiO2) was used as an adsorbent material. These materials were characterized using XRD, SEM and TEM techniques. Various cresols (m-, o-, p-cresol) were oxidized for different time intervals, viz. 1, 3 and 5 h. The γ-Al2O3 adsorbent was found to have a relatively high catalytic effect towards conversion of m-cresol (52%) into oxidation products, whereas SiO2 promoted the conversion of o-cresol (57%) and p-cresol (62%) the most. The resultant oxidation products that were identified using GC–MS were dominantly isomeric from all three cresols. Oxidation of m-cresol produced m-tolyl acetate (m-TA), 2,3-dihydroxytoluene (2,3-DT) and diethyl maleate (DM) whereas o-cresol produced o-tolyl acetate (o-TA), 2,5-dihydroxytoluene (2,5-DT) and DM. Finally, the oxidation of p-cresol produced p-tolyl acetate (p-TA), 3,4-dihydroxytoluene (3,4-DT) and DM. Amongst all identified oxidation products, tolyl acetates recorded highest percentage selectivities from all adsorbates especially in 1 h reactions.

Graphical Abstract

The ozone initiated oxidation of various cresol isomers was explored using various metal oxide (γ-Al2O3 or SiO2) material as adsorbents. The metal oxide adsorbent materials were characterized using XRD, SEM and TEM techniques. The effect of adsorption and ozonation time on percentage conversion and selectivity towards reaction products upon ozonation of various cresols is emphasised. The positively identified oxidation products contains various tolyl acetates, dihydroxytoluenes and diethyl maleates that are isomeric to the cresol isomer used. The ethanol mediated esterification of carboxylic acid to produce tolyl acetate as product is reported.

Keywords

Cresols Ozonation Adsorbent Conversion Selectivity 

Notes

Acknowledgements

The Authors would like to acknowledge Sasol Inzalo Foundation and NRF for financial support in the form of fellowship. Rajasekhar Pullabhotla would like to acknowledge the Research and Innovation Office, University of Zululand for the financial support in the form of project S125/13. The authors would also like to acknowledge the Electron Microscopy Unit at the University of KwaZulu-Natal, Westville campus, for providing support by letting us use the TEM and SEM-EDX facilities for the characterization of materials and UJ for providing support by letting us use the HPLC facility.

Supplementary material

10562_2018_2360_MOESM1_ESM.docx (2 mb)
Supplementary material 1 (DOCX 2096 KB)

References

  1. 1.
    Jiazhen Z, Wuhua D, Jinquan X, Yiyan Y (2007) Experimental and simulation study on the extraction of p-cresol using centrifugal extractors. Chin J Chem Eng 15(2):209–214CrossRefGoogle Scholar
  2. 2.
    Sanders JM, Bucher JR, Peckham JC, Kissling GE, Hejtmancik MR, Chhabra RS (2009) Carcinogenesis studies of cresols in rats and mice. Toxicology 257:33–39CrossRefGoogle Scholar
  3. 3.
    Lin CH, Yang JY (1992) Chemical burn with cresol intoxication and multiple organ failure. Burns 18(2):162–166CrossRefGoogle Scholar
  4. 4.
    Nehéz M, Selypes A, Mazzag E, Berencsi G (1984) Additional data on the mutagenic effect of dinitro-o-cresol containing herbicides. Ecotoxicol Environ Saf 8:75–79CrossRefGoogle Scholar
  5. 5.
    Pegg SP, Campbell DC (1985) Children’s burns due to cresol. Burns 11:294–296CrossRefGoogle Scholar
  6. 6.
    EPA (United States Environmental Protection Agency) (2015) The Clean Air Act amendments of 1990 List of hazardous air pollutants. https://www3.epa.gov/airtoxics/orig189.html Accessed 26 Nov 2015
  7. 7.
    Sad ME, Padró CL, Apesteguía CR (2008) Synthesis of cresols by alkylation of phenol with methanol on solid acids. Catal Today 133–135:720–728CrossRefGoogle Scholar
  8. 8.
    Terzian R, Serpone N, Minero C, Pelizzetti E (1991) Photocatalyzed mineralization of cresols in aqueous media with irradiated titania. J Catal 128:352–365CrossRefGoogle Scholar
  9. 9.
    Zheng Y, Hill DO, Kuo CH (1993) Destruction of cresols by chemical oxidation. J Hazard Mater 34:245–260CrossRefGoogle Scholar
  10. 10.
    She Y, Wang W, Li G (2012) Oxidation of p/o-cresol to p/o-hydroxybenzaldehydes catalyzed by metalloporphyrins with molecular oxygen. Chin J Chem Eng 20(2):262–266CrossRefGoogle Scholar
  11. 11.
    Kavitha V, Palanivelu K (2005) Destruction of cresols by Fenton oxidation process. Water Res 39:3062–3072CrossRefGoogle Scholar
  12. 12.
    Grootboom N, Nyokong T (2001) Electrooxidation of cresols on carbon electrodes modified with phthalocyaninato and octabutoxyphthalocyaninato cobalt(II) complexes. Anal Chim Acta 432:49–57CrossRefGoogle Scholar
  13. 13.
    Valsania MC, Fasano F, Richardson SD, Vincenti M (2012) Investigation of the degradation of cresols in the treatment with ozone. Water Res 46:2795–2804CrossRefGoogle Scholar
  14. 14.
    Fiessinger F, Rook JJ, Duguet JP (1985) Alternative methods for chlorination. Sci Total Environ 47:299–315CrossRefGoogle Scholar
  15. 15.
    Criegee R (1975) Mechanism of ozonolysis. Angew Chem Int Ed 14(11):745–752CrossRefGoogle Scholar
  16. 16.
    Védrine VC (2017) Heterogeneous catalysis on metal oxides. Catalysts 7:341–366CrossRefGoogle Scholar
  17. 17.
    Gupta VK, Carrot PJM, Ribeiro MML, Carrot, Sahas (2009) Low-cost adsorbents: growing approach to wastewater treatment: a review. Crit Rev Environ Sci Technol 39:783–842CrossRefGoogle Scholar
  18. 18.
    Vincenti M, Fasano F, Valsania MC, Guarda P, Richardson SD (2010) Application of the novel 5-chloro-2,2:3,3,4,4,5,5-octafluoro-1-pentyl chloroformate derivatizing agent for the direct determination of highly polar water disinfection products. Anal Bioanal Chem 397 43–54CrossRefGoogle Scholar
  19. 19.
    Chetty EC, Dasireddy VB, Maddila S, Jonnalagadda SB (2012) Efficient conversion of 1,2-dichlorobenzene to mucochloric acid with ozonation catalyzed by V2O5 loaded metal oxides. Appl Catal B 117–118:18–28CrossRefGoogle Scholar
  20. 20.
    Rozita Y, Brydson R, Scott AJ (2010) An investigation of commercial gamma-Al2O3 nanoparticles. J Phys 241:1–4Google Scholar
  21. 21.
    Samain L, Jaworski A, Eden M, Ladd DM, Seo D-K, Garcia-Garcia FJ, Haussermann U (2014) Structural analysis of highly porous γ-Al2O3. J Solid State Chem 217:1–8CrossRefGoogle Scholar
  22. 22.
    Pullabhotla VSRR, Rahman A, Jonnalagadda SB (2009) Selective catalytic Knoevenagel condensation by Ni-SiO2 supported heterogeneous catalysts: an environmental benign approach. Catal Commun 10:365–369CrossRefGoogle Scholar
  23. 23.
    de Faria CLL Jr, de Oliveira TKR, dos Santos VL, Rosa CA, Ardisson JD, de Almeida WA, Macêdo A, Santos (2009) Usage of the sol-gel process on the fabrication of macroporous adsorbent activated-gamma alumina spheres. Microporous Mesoporous Mater 120:228–238CrossRefGoogle Scholar
  24. 24.
    Oyama ST, Li W, Zhang W (1999) A comparative study of ethanol oxidation with ozone on supported molybdenum and manganese oxide catalysts. Stud Surf Sci Catal 121:105–110CrossRefGoogle Scholar
  25. 25.
    Richard LS, Bernardes CES, Diogo HP, Leal JP, Minas da Piedade ME (2007) Energetics of cresols and of methylphenoxyl radicals. J Phys Chem A 111:8741–8748CrossRefGoogle Scholar
  26. 26.
    Santos A, Yustos P, Rodriguez S, Garcia-Ochoa F (2006) Wet oxidation of phenol, cresols and nitrophenols catalyzed by activated carbon in acid and basic media. Appl Catal B 65:269–281CrossRefGoogle Scholar
  27. 27.
    Bounab L, Iglesias O, González-Romero E, Pazos M, Sanromán M (2015) Effective heterogeneous electro-Fenton process of m-cresol with iron loaded active carbon. RSC Adv 5:31049–31056CrossRefGoogle Scholar
  28. 28.
    Chu Y, Zhang D, Liu L, Qian Y, Li L (2013) Electrochemical degradation of m-cresol using porous carbon-nanotube-containing cathode and Ti/SnO2-Sb2O5-IrO2 anode: kinetics, byproducts and biodegradability. J Hazard Mater 252–253:306–312CrossRefGoogle Scholar
  29. 29.
    Yadav GD, Thathagar MB (2002) Esterification of maleic acid with ethanol over cation-exchange resin catalysts. React Funct Polym 52(2):99–110CrossRefGoogle Scholar
  30. 30.
    Batakliev T, Georgiev V, Anachkov M, Rakovsky S, Zaikov GE (2014) Ozone decomposition. Interdiscip Toxicol 7(2):47–59CrossRefGoogle Scholar
  31. 31.
    Kalmaz EE (1986) Kinetics of ozone decomposition and oxidation of a model organic compound in water. Chemosphere 15(2):183–194CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  • Z. S. Ncanana
    • 1
  • V. S. R. Rajasekhar Pullabhotla
    • 1
  1. 1.Department of ChemistryUniversity of ZululandKwa-DlangezwaSouth Africa

Personalised recommendations