The ozonation of extremely polluted petrochemical wastewater: Effect of catalysts, initial pH, volumetric flow rate and concentration of ozone on oxidation rate

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Research Paper 01/01/2015
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The ozonation of extremely polluted petrochemical wastewater: Effect of catalysts, initial pH, volumetric flow rate and concentration of ozone on oxidation rate

Quyen Ngo, Linh Dao, Evgeniy Grigoriev, Alexandr Petukhov
J. Bio. Env. Sci.6( 1), 587-598, January 2015.
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Ozonation of an extremely polluted petrochemical wastewater from styrene and propylene oxide production and the influence of different factors on the treatment efficiency were investigated. The treatment efficiency was the highest under alkaline conditions and with the use of catalysts. Optimal values of ozone concentration and volumetric flow rate of the ozone-oxygen mixture were 20 mg L–1 and 400 L (L × h)–1, respectively. The use of H2O2 (0.075 wt%) as a catalyst allowed the maximum COD conversion (93%) and acetophenone removal (98%) to be achieved after 60 min. In the meantime, at an optimal concentration of MnSO4.5H2O (0.1 wt%), the treatment efficiency in terms of COD and acetophenone removal increased up to 85% and 84%, respectively. Acetophenone was completely removed from the wastewater when the ozonation time was increased to 90 min, using H2O2 or MnSO4.5H2O as a catalyst, while phenol, styrene, and ethylbenzene were entirely removed after 60 min. During the ozonation process an abnormal increase in pH appeared due to OH-radical formation. This interesting phenomenon resulted in the possibility of increasing the treatment efficiency by lengthening the time during which the maximum pH as well as the maximum quantity of OH-radicals were observed.


Battaglin W, Furlong E, Burkhardt M. 2001. Concentration of selected sulfonylurea, sulfonamide, and imadazolinone herbicides, other pesticides, and nutrients in 71 streams, 5 reservoir outflows, and 25 wells in the Midwestern United States, 1998. U.S. Geological Survey Water-Resources Investigations Report, Denver, Colorado, U.S. Available online:

Bedient PB, Rifai HS, Newell CJ. 1999. Ground water contamination: transport and remediation, 3rd ed. PTR Prentice Hall upper saddle river, New Jersey.

Beltrán FJ. 2004. Ozone Reaction Kinetics for Water and Wastewater Systems. CRC Press, Florida.

Biń AK. 2006. Ozone Solubility in Liquids. Ozone: Science & Engineering. The Journal of the International Ozone Association 28, 67-75.

Buxton GV, Greenstock CL, Helman WP, Ross AB. 1988. Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (OH/O) in aqueous solution. Journal of Physical and Chemical Reference Data 17, 513–886.

Catalkaya EC, Kargi F. 2007. Color, TOC and AOX removals from pulp mill effluent by advanced oxidation processes: a comparative study. Journal of Hazardous Materials 139, 244-253.

Dao L, Grigoryeva T, Laikov A, Devjatijarov R, Ilinskaya O. 2014. Full-scale bioreactor pretreatment of highly toxic wastewater from styrene and propylene oxide production. Ecotoxicology and Environmental Safety. Saf. 108, 195–202.

Dhandapani B, Oyama ST. 1997. Gas phase ozone decomposition catalysts. Applied Catalysis B: Environmental 11, 129–166.

Einaga H, Futamura S. 2004. Comparative study on the catalytic activities of aluminasupported metal oxides for oxidation of benzene and cyclohexane with ozone. Reaction Kinetics and Catalysis Letters 81, 121–128.

Einaga H, Harada M, Ogata A. 2009. Relationship between the structure of manganese oxides on alumina and catalytic activities for benzene oxidation with ozone, Catalysis Letters 129, 422–427.

Einaga H, Ogata A. 2009. Benzene oxidation with ozone over supported manganese oxide catalysts: Effect of catalyst support and reaction conditions. Journal of Hazardous Materials. 164, 1236–1241.

Einaga H, Teraoka Y, Ogata A. Benzene oxidation with ozone over manganese oxide supported on zeolite catalysts. Catalysis Today. 164, 571–574.

Gallego JP, Lopez SR, Maugans CB. 2002. The Use of Wet Oxidation and PACT® for the Treatment of Propylene Oxide/Styrene Monomer (PO/SM) Industrial Wastewaters at the Repsol PO/SM Plant in Tarragona,  Spain. Praha, The Czech Republic. Available online:

Glaze WH, Kang JW. 1988. Advanced oxidation processes for treating groundwater contaminated with TCE and PCE: laboratory studies. Journal – American Water Works Association 80, 57-63.

Gogate PR, Pandit AB. 2004. A review of imperative technologies for wastewater treatment I: oxidation technologies at ambient conditions. Advances in Environmental Research 8, 501–551.

Gunten U. 2003. Ozonation of drinking water: Part I. Oxidation kinetics and product formation. Water Research. 37, 1443–1467.

Hellström T. 2000. Brominated Flame Retardants (PBDE and PBB) in Sludge a Problem. The Swedish Water and Wastewater Association, Bromma, Sweden. Available

Hoigne J. 1998. Chemistry of Aqueous Ozone and Transformation of Pollutants by Ozonation and Advanced Oxidation Processes, in: Quality and Treatment of Drinking Water. Springver-Verlag, Berlin.

Huang L, Li L, Dong W, Liu Y, Hou H. 2008. Removal of Ammonia by OH Radical in Aqueous Phase. Environmental Science & Technology 42, 8070–8075.

Jagadevan S, Graham NJ, Thompson IP. 2013. Treatment of waste metalworking fluid by a hybrid ozone-biological process. Journal of Hazardous Materials 245(2013), 394–402.

Kavanaugh M, Chowdhury Z, Kommineni S, Liang S, Min J, Corin N, Amy G, Simon E, Cooper W, Tornatore P, Nickelsen M. 2004. Removal of MTBE with Advanced Oxidation Processes. IWA Publishing, London.

Lin AYC, Panchangam SC, Chang CY, Hong PKA, Hsueh HF. 2012. Removal of perfluorooctanoic acid and perfluorooctane sulfonate via ozonation under alkaline condition. Journal of Hazardous Materials 243, 272–277.

Merayo N, Hermosilla D, Blanco L, Cortijo L, Blanco A. 2013. Assessing the application of advanced oxidation processes, and their combination with biological treatment, to effluents from pulp and paper industry. Journal of Hazardous Materials 262, 420–427.

Miller LM. 1979. Investigation of selected potential environmental contaminants: ethylene glycol, propylene glycols and butylene glycols. Final Report, EPA 68-01-3893, US EPA, Office of Toxic Substances, Washington DC., U.S.

Munter R. 2001. Advanced oxidation processes – current status and prospects. Proceedings of the Estonian Academy of Sciences. Chemistry 50, 59–80.

Naydenov A, Mehandjiev D. 1993. Complete oxidation of benzene on manganese dioxide by ozone. Applied Catalysis A: General 97, 17–22.

Nilvebrant  NO,  Jansson  MB.  2005.  Hydroxyl radical formation during hydrogen peroxide bleaching.  STFI-PACKFORSK,  Stockholm,  Sweden. Available online:

Oyama ST. 2000. Chemical and catalytic properties of ozone. Catalysis Reviews. 42, 279–322.

Parsons S, Williams M. 2004. Advanced Oxidation Processes for Water and Wastewater Treatment. Iwa Publishing, London.

Peixoto ALC, Silvia MB, Izário Filho HJ. 2009. Leachate treatment process at a municipial stabilized landfill by catalytic ozonation: An exploratory study from taguchi orthogonal array. Brazilian Journal of Chemical Engineering 26, 481–492.

Petty JD, Huckins JN, Alvarez DA, Brumbaugh WG, Cranor WL, Gale RW, Rastall AC, Jones-Lepp TL, Leiker TJ, Rostad CE, Furlong ET. 2004. A holistic passive integrative sampling approach for assessing the presence and potential impacts of waterborne environmental contaminants. Chemosphere 54, 695-705.

Rettich TR, Battino R, Wilhelm E. 2000. Solubility of gases in liquids. 22. High-precision determination of Henry’s law constants of oxygen in liquid water from T = 274 K to T = 328 K. The Journal of Chemical Thermodynamics 32, 1145–1156.

Safarzadeh-Amiri A. 2001. O3/H2O2 treatment of methyl-tert-butyl ether (MTBE) in contaminated waters. Water Research 35, 3706-3714.

Sittig M. 1985. Handbook of Toxic and Hazardous Chemicals and Carcinogens. 2nd ed. Noyes Publications, Park Ridge, New Jersey.

Somensi CA, Simionatto EL, Bertoli SL, Wisniewski AJ, Radetski CM. 2010. Use of ozone in a pilot-scale plant for textile wastewater pre-treatment: Physico-chemical efficiency, degradation by-products identification and environmental toxicity of treated wastewater. Journal of Hazardous Materials 175, 235–240.

Sumegová L, Derco J, Melicher M. 2013. Influence of reaction conditions on the ozonation process. Acta Chimica Slovaca 6, 168—172.

Swietlik J, Dabrowska A, Raczyk-Stanisiawiak U, Nawrocki J. 2004. Reactivity of natural organic matter fractions with chlorine dioxide and ozone. Water Research 38, 547–558.

Zhao DZ, Ding TY, Li XS, Liu JL, Shi C, Zhu AM. 2012. Ozone catalytic oxidation of HCHO in air over MnOx at room temperature. Chinese Journal of Catalysis 33, 396–401.