0872-1904

S0872-19042008000100002

Spain

00 00 2008

26 1 15 46

Wastewaters by Electrochemical Advanced Oxidation Processes Using a BDD Anode and Electrogenerated H₂O₂ with Fe(II) and UVA Light as Catalysts

**E. Brillas,* J.A. Garrido, R.M. Rodríguez, C. Arias, P.L. Cabot, F. Centellas**

Laboratori d’Electroquímica dels Materials i del Medi Ambient, Departament de Química Física, Facultat de Química, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona, Spain

Received 18^th July 2007

Abstract

]]> This paper reports the mineralization of an aromatic pharmaceutical as clofibric acid and the dye indigo carmine in 0.05 M Na₂SO₄ of pH 3.0 by electrochemical advanced oxidation processes such as anodic oxidation without and with electrogenerated H₂O₂, electro-Fenton and photoelectro-Fenton using a boron-doped diamond (BDD) anode. These procedures produce the strong oxidant hydroxyl radical in the form of BDD(^·OH) from water oxidation at BDD and/or ^·OH from Fenton’s reaction between added Fe²⁺ and H₂O₂ generated at the cathode by two-electron O₂ reduction. Comparative degradation of both compounds is performed with an undivided electrolytic cell of 100 mL with an O₂-diffusion cathode. The effect of current density and pollutant concentration on the degradation rate and current efficiency of the different methods is discussed. The decay kinetics of clofibric acid and indigo carmine and the evolution of their aromatic by-products and final carboxylic acids like oxalic and/or oxamic are described to clarify their reaction sequences. Anodic oxidation is able to completely mineralize both compounds mainly with BDD(^·OH). Aromatic pollutants are more rapidly destroyed in electro-Fenton due to their faster reaction with ^·OH, but final Fe(III)-oxalate and Fe(III)-oxamate can only be oxidized with BDD(^·OH). The most efficient method is photoelectro-Fenton due to the parallel photolysis of Fe(III)-oxalate complexes with UVA light, although Fe(III)-oxamate complexes are not photodecomposed. Under these conditions, the degradation rate can be enhanced using Cu²⁺ as co-catalyst because Cu(II)-oxalate and Cu(II)-oxamate complexes are quickly destroyed by ^·OH. Results on the fast mineralization of 2.5 L of cresols solutions of pH 3.0 by solar photoelectro-Fenton using a flow plant coupled to a solar photoreactor are also reported. The high efficiency and very low operational cost found for this procedure make it useful for the treatment of industrial wastewaters

Keywords: clofibric acid, indigo carmine, cresols, anodic oxidation, electro-Fenton, photoelectro-Fenton, solar photoelectro-Fenton.

Texto disponível em PDF

Full text only in PDF format

References

]]>

1. C.G. Daughton, T.L. Jones-Lepp (Eds.), Pharmaceuticals and personal care products in the environment. Scientific and regulatory issues, ACS Symposium Series, Washington, 2001. [ Links ]

2. K. Kümmerer (Ed.), Pharmaceuticals in the environment. Sources, fate and risks, Springer, Berlin, 2001.

3. T. Heberer, Toxicol. Lett. 131 (2002) 5.

4. R. Andreozzi, R. Marotta, P. Nicklas, Chemosphere 50 (2003) 1319.

5. N. Nakada, T. Tanishima, H. Shinohara, K. Kiri, H. Takada, Water Res. 40 (2006) 3297.

6. A.I. Balcioglu, M. Ötker, Chemosphere 50 (2003) 85.

7. M. Vautier, C. Guillard, J.M. Hermann, J. Cat. 201 (2001) 46.

8. A.H. Gemeay, I.A. Mansour, R.G. El-Sharkawy, A.B. Zaki, J. Mol. Cat. A: Chem. 193 (2003) 109.

9. M.A. Sanromán, M. Pazos, M.T. Ricart, C. Cameselle, Chemosphere 57 (2004) 233.

10. A. Fernandes, A. Morao, M. Magrinho, A. Lopes, I. Goncalves, Dyes Pigments 61 (2004) 287.

]]> 11. E. Brillas, M.A. Oturan, Procédé électro-Fenton: développements récents et applications à l'élimination des pesticides en milieux aqueux, in: M.A. Oturan, J.M. Mouchel (Eds.), Pesticides: Impacts environmentaux, gestion et traitements, Presses de l'École Nationale des Ponts et Chaussées, Paris, 2007, pp. 61-73.

12. A. Tauxe-Wuersch, L.F. De Alencastro, D. Grandjean, J. Tarradellas, Water Res. 39 (2005) 1761.

13. J.P. Emblidge, M.E. DeLorenzo, Environ. Res. 100 (2006) 216.

14. C. Tixier, H.P. Singer, S. Oellers, S.R. Müller, Environ. Sci. Technol. 37 (2003) 1061.

15. T.A. Ternes, M. Meisenheimer, D. McDowell, F. Sacher, H.J. Brauch, B. Haist-Gulde, G. Preuss, U. Wilme, N. Zulei-Seibert, Environ. Sci. Technol. 36 (2002) 3855.

16. R. Andreozzi, V. Caprio, R. Marotta, A. Radovnikovic, J. Hazard. Mat. B103 (2003) 233.

17. J.L. Packer, J.J. Werner, D.E. Latch, K. McNeill, W.A. Arnold, Aq. Sci. 65 (2003) 342.

18. T. Doll, F.H. Frimmel, Water Res. 38 (2004) 955.

19. Z. Ruo-bing, W. Yan, L. Guofeng, Plasma Sources Sci. Technol. 14 (2005) 308.

20. J.A. Kettle, B.M. Clark, C.C. Winterbourn, J. Biol. Chem. 279 (2004) 18521.

]]> 21. C. Galindo, P. Jacques, A. Kalt, J. Photochem. Photobiol. A: Chem. 141 (2001) 47.

22. B.H. Rao, S.R. Asolekar, Water Res. 35 (2001) 3391.

23. V. Kavitha, K. Palanivelu, Water Res. 39 (2005) 3062.

24. K.H. Wang, Y.H. Hsieh, L.J. Chen, J. Hazard. Mater. 59 (1998) 251.

25. G. Sivalingam, M.H. Priya, G. Madras, Appl. Catal. B: Environ. 51 (2004) 67.

26. A. Hatipoğlu, N. San, Z. Çinar, J. Photochem.Photobiol. A: Chem. 165 (2004) 119.

27. D. Rajkumar, K. Palanivelu, Ind. Eng. Chem. Res. 42 (2003) 1833.

28. J.L. Nava, F. Núñez, I. González, Electrochim. Acta 52 (2007) 3229.

29. B. Marselli, J. García-Gomez, P.A. Michaud, M.A. Rodrigo, Ch. Comninellis, J. Electrochem. Soc. 150 (2003) D79.

30. M. Panizza, G. Cerisola, Electrochim. Acta 51 (2005) 191.

]]> 31. E. Brillas, C. Arias, P.L. Cabot, F. Centellas, J.A. Garrido, R.M. Rodríguez, Port. Electrochim. Acta 24 (2006) 159.

32. D. Gandini, E. Mahé, P.A. Michaud, W. Haenni, A. Perret, Ch. Comninellis, J. Appl. Electrochem. 30 (2000) 1345.

33. M.A. Rodrigo, P.A. Michaud, I. Duo, M. Panizza, G. Cerisola, Ch. Comninellis, J. Electrochem. Soc. 148 (2001) D60.

34. J. Iniesta, P.A. Michaud, M. Panizza, G. Cerisola, A. Aldaz, Ch. Comninellis, Electrochim. Acta 46 (2001) 3573.

35. F. Montilla, P.A. Michaud, E. Morallon, J.L. Vazquez, Ch. Comninellis, Electrochim. Acta 47 (2002) 3509.

36. B. Boye, P.A. Michaud, B. Marselli, M.M. Dieng, E. Brillas, Ch. Comninellis, New Diamond Frontier Carbon Technol. 12 (2002) 63.

37. A. Kraft, M. Stadelmann, M. Blaschke, J. Hazard. Mat. 103 (2003) 247.

38. S. Hattori, M. Doi, E. Takahashi, T. Kurosu, M. Nara, S. Nakamatsu, Y. Nishiki, T. Furuta, M. Iida, J. Appl. Electrochem. 33 (2003) 85.

39. P. Cañizares, J. García-Gómez, C. Sáez, M.A. Rodrigo, Ind. Eng. Chem. Res. 42 (2003) 956.

40. E. Brillas, B. Boye, I. Sirés, J.A. Garrido, R.M. Rodríguez, C. Arias, P.L. Cabot, Ch. Comninellis, Electrochim. Acta 49 (2004) 4487.

]]> 41. M. Panizza, G. Cerisola, Electrochim. Acta 49 (2004) 3221.

42. P. Cañizares, C. Sáez, J. Lobato, M.A. Rodrigo, Ind. Eng. Chem. Res. 43 (2004) 1944.

43. C.A. Martinez-Huitle, S. Ferro, A. De Battisti, Electrochim. Acta 49 (2004) 4027.

44. P. Cañizares, J. Lobato, R. Paz, M.A. Rodrigo, C. Sáez, Water Res. 39 (2005) 2687.

45. B. Nasr, G. Abdellatif, P. Cañizares, C. Sáez, J. Lobato, M.A. Rodrigo, Environ. Sci. Technol. 39 (2005) 7234.

46. E. Brillas, I. Sirés, C. Arias, P.L. Cabot, F. Centellas, R.M. Rodríguez, J.A. Garrido, Chemosphere 58 (2005) 399.

47. C. Flox, J.A. Garrido, R.M. Rodríguez, F. Centellas, P.L. Cabot, C. Arias, E. Brillas, Electrochim. Acta 50 (2005) 3685.

48. X. Chen, G. Chen, Sep. Purif. Technol. 48 (2006) 45.

49. C. Flox, P.L. Cabot, F. Centellas, J.A. Garrido, R.M. Rodríguez, C. Arias, E. Brillas, Chemosphere 64 (2006) 892.

50. B. Boye, E. Brillas, B. Marselli, P.A. Michaud, Ch. Comninellis, G. Farnia, G. Sandonà,Electrochim. Acta 51 (2006) 2872.

]]> 51. S. Ammar, R. Abdelhedi, C. Flox, C. Arias, E. Brillas, Environ. Chem. Lett. 4 (2006) 229.

52. M.A. Oturan, J. Appl. Electrochem. 30 (2000) 475.

53. M.A. Oturan, N. Oturan, C. Lahitte, S. Trevin, J. Electroanal. Chem. 507 (2001) 96.

54. B. Gözmen, M.A. Oturan, N. Oturan, O. Erbatur, Environ. Sci. Technol. 37 (2003) 3716.

55. E. Guivarch, N. Oturan, M.A. Oturan, Environ. Chem. Lett. 1 (2003)165.

56. G. Kaichouh, N. Oturan, M.A. Oturan, K. El Kacemi, A. El Hourch, Environ. Chem. Lett. 2 (2004) 31.

57. K. Hanna, S. Chiron, M.A. Oturan, Water Res. 39 (2005) 2763.

58. A. Wang, J. Qu, J. Ru, H. Liu, J. Ge, Dyes Pigments 65 (2005) 227.

59. S. Irmak, H.I. Yavuz, O. Erbatur, Appl. Catal. B: Environ. 63 (2006) 243.

60. N. Bellakhal, M.A. Oturan, N. Oturan, M. Dachraoui, Environ. Chem. 3 (2006) 345.

]]> 61. M. Dieng, N. Oturan, M. Oturan, Chemosphere 66 (2007) 841.

62. I. Sirés, J.A. Garrido, R.M. Rodríguez, E. Brillas, N. Oturan, M.A. Oturan, Appl. Catal. B: Environ. 72 (2007) 382.

63. E. Brillas, J.C. Calpe, J. Casado, Water Res. 34 (2000) 2253.

64. E. Brillas, J. Casado, Chemosphere 47 (2002) 241.

65. B. Boye, M.M. Dieng, E. Brillas, Environ. Sci. Technol. 36 (2002) 3030.

66. E. Brillas, B. Boye, M.M. Dieng, J. Electrochem. Soc. 150 (2003) E583.

67. B. Boye, M.M. Dieng, E. Brillas, J. Electroanal. Chem. 557 (2003) 135.

68. E. Brillas, M.A. Baños, S. Camps, C. Arias, P.L. Cabot, J.A. Garrido, R.M. Rodríguez, New J. Chem. 28 (2004) 314.

69. A. Da Pozzo, C. Merli, I. Sirés, J.A. Garrido, R.M. Rodríguez, E. Brillas, Environ. Chem. Lett. 3 (2005) 7.

70. C. Flox, S. Ammar, C. Arias, E. Brillas, A.V. Vargas-Zavala, R. Abdelhedi, Appl. Catal. B: Environ. 67 (2006) 93.

]]> 71. C. Flox, P.L. Cabot, F. Centellas, J.A. Garrido, R.M. Rodríguez, C. Arias, E. Brillas, Appl. Catal. B: Environ. 75 (2007) 17.

72. I. Sirés, F. Centellas, J.A. Garrido, R.M. Rodríguez, C. Arias, P.L. Cabot, E. Brillas, Appl. Catal. B: Environ. 72 (2007) 373.

73. C. Flox, J.A. Garrido, R.M. Rodríguez, P.L. Cabot, F. Centellas, C. Arias, E. Brillas, Catal. Today in press.

74. J.J. Pignatello, Environ. Sci. Technol. 2 (1992) 944.

75. Y. Sun, J.J. Pignatello, Environ. Sci. Technol. 27 (1993) 304.

76. Y. Sun, J.J. Pignatello, J. Agric. Food Chem. 41 (1993) 308.

77. J. De Laat, H. Gallard, Environ. Sci. Technol. 33 (1999) 2726.

78. J.D. Rush, B.H.J. Bielski, J. Phys. Chem. 89 (1985) 5062.

79. Y. Zuo, J. Hoigné, Environ. Sci. Technol. 26 (1992) 1014.

80. F.J. Welcher (Ed.), Standard Methods of Chemical Analysis, R.E. Krieger Pub. Co., Huntington, New York, 1975, Vol. 2 (Part B), 6th ed., p. 1827.

]]> 81. N.H. Furman (Ed.), Standard Methods of Chemical Analysis, R.E. Krieger Pub. Co., Huntington, New York, 1975, Vol. 1, 6th ed., p. 553.

82. E.B. Sandell, in: B.L. Clarke, P.J. Elving, I.M. Kolthoff (Eds.), Chemical Analysis, Interscience Publishers, Inc., New York, 1959, Vol. III, 3rd ed., p.522.

83. G.U. Buxton, C.L. Greenstock, W.P. Helman, A.B. Ross, J. Phys. Chem. Data Ref. 17 (1988) 513.

84. H. Gallard, J. De Laat, B. Legube, Rev. Sci. Eau 12 (1999) 715.

85. J. De Laat, H. Gallard, Environ. Sci. Technol. 33 (1999) 2726.

* Corresponding author. E-mail address: brillas@ub.edu.

]]>

2001