Effect of pH to the Decomposition of Aqueous Phenols Mixture by Ozone
Tatyana Poznyak,1* Rocío Tapia,1 Juan Vivero1 and Isaac Chairez2
1 Escuela Superior de Ingeniería Química e Industrias Extractivas. Instituto Politécnico Nacional, Edif. 7, UPALM, C.P. 07738, México, D.F., México., e-mail: tpoznyak@mail.ru, tpoznyak@ipn.mx
2 Departamento de Control Automático, CINVESTAV-IPN, Av. Instituto Politécnico Nacional, Col. San Pedro Zacatenco, C.P. 07360, México D.F., México.
]]> Recibido el 5 de julio del 2005.
Abstract
The degradation of the mixture of phenol and its chlorinated derivatives with ozone is studied. The studied compounds are phenol (Ph), 4 - chlorophenol (4-CPh) and 2,4 - dichlorophenol (2,4-DCPh). The kinetic performances of each phenolic compound in the model mixture are examined. The pH influence to the decomposition dynamics for different phenolic compounds in the range 2 - 12 is investigated. The increase of the decomposition rate under the pH increasing was observed. In the studied pH range, phenol and chlorophenols ozonation proceeds rapidly. The UV absorvency is used for the preliminary control of the phenols decomposition degree. The HPLC analysis was used to identify intermediates and final products formed during ozonation of the phenols mixture. It is shown that the basic intermediates are muconic and fumaric acids, malonic and maleic acids, catechol and hydroquinone. The final products are oxalic acid and formic acid. In the case of alkaline media, the principal final product is oxalic acid. Furthermore, intermediates and final decomposition products obtained at the different pH are compared. According to the obtained results, the possible mechanism of ozonation by the reaction of hydroxylation and dechloration in the early stage is proposed. The BOD5/COD ratio is used as a biodegradability measure for the comparison of biodegradability of initial compounds and final products composition.
Key words: ozonation, water, phenols, decomposition, pH.
Resumen
Se estudió la degradación con ozono de la mezcla de fenol y sus derivados clorados. Los compuestos estudiados fueron fenol (Ph), 4-clorofenol (4-CPh) y 2,4-diclorofenol (2,4-DCPh). Se determinó el comportamiento cinético de cada compuesto fenólico en la mezcla modelo. Se investigó la influencia del pH en la dinámica de descomposición de los diferentes compuestos fenólicos en un intervalo de 2-12. Se observó el incremento en la velocidad de descomposición conforme aumentaba el pH. En el intervalo de pH's estudiado, la ozonación del fenol y clorofenoles se realizó eficientemente. La absorbancia en UV de cada compuesto fue utilizada como método de control preliminar del grado de descomposición de cada compuesto fenólico. Se realizó el análisis usando cromatografía de líquidos (HPLC) para identificar los productos intermediarios y finales formados durante la ozonación de la mezcla de fenoles. Dicho análisis mostró que los compuestos intermediarios principales son: los ácidos mucónico, fumárico, malónico y maléico; al igual que ácido oxálico y fórmico. En el caso del medio básico, el producto final principal es ácido oxálico. Además, se realizó una comparación de la descomposición de los productos intermediarios y finales a diferentes pH's. De acuerdo a los resultados obtenidos, se proponen las reacciones de hidroxilación y decloración como etapas iniciales del mecanismo de ozonación. La relación BOD5/COD es utilizada como una medida de la biodegradabilidad del sistema para comparar la biodegradabilidad de la mezcla inicial y la mezcla final una vez ozonada.
Palabras Clave: ozonización, agua, descomposición, fenoles, pH.
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Acknowledgements
The authors thank the Department of Graduate Study and Investigation of the National Polytechnic Institute of Mexico for the supporting of this investigation (Project # 970124).
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