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The use of electrochemistry for oil waste degradation

Marcos R.G. dos Santos, Marlia O. F. Goulart, J. Tonholo, Carmem L.P.S. Zanta* Departamento de Qumica da Universidade Federal de Alagoas, Macei, Brazil, 57072-970, clp@qui.ufal.br
Electrochemical technology has been successfully used for purification and remediation of contaminated air and water. This work approach the degradation of petroleum industry effluents, produced in exploration and production area, using the electrochemical technology. The waste generated in the industry of the petroleum contains, besides dissolved organic matter, a great amount of oils in emulsion. Usually, they are treated with addition of chemical products as, for example, polymeric agents flocculats and/or salts of metals, as iron and aluminum. As those processes are very expensive and increase the operational costs, some alternatives have being in study, among of which electroflotation is probabily the most promising one. The electroflotation is an electrolytic process that already have been adopted by countries such as United States, Canada, Norway, presenting advantages in the waste treatment, mainly in the oil removal in platform of petroleum, drilling dikes, treatment of waste of ships and treatment of some currents of refineries1. About the dissolved organic matter, electro-oxidation appears as way to promote the degradation of the organic compounds. The electro-oxidation processes and electroflotation can be like this together applied toward to increase the efficiency of the treatment of waste. The tasks have been realized at dimensionally stable anodes (DSA) which nominal composition is Ti/Ru0,34Ti0,66O2, commercially utilized in chlor-alkalis industry. The analyzed residue, obtained from the water/oil separation tank, in PETROBRAS Company (Alagoas State, Brazil) was pre-treated with sulfuric acid. Voltammetric studies indicate that DSA presents catalytic activity for oxidation of the petroleum residue at potential overlapping similar to the oxygen evolution reaction (OER) in 1,1 E 1,4 V vs. Ag/AgCl, Cl- (0,1 mol.l-1). Even so, beside oxidation it happened the phenomenon of adsorption. In inferior potentials to that of OER, 0,2 E 1,1 V vs. Ag/AgCl, Cl- (0,1 mol.l-1), no catalytic activity has been observed. Oxidation of the substratum at OER potentials was corroborated through the electrolyses, in which oxidation of the organic substratum was verified in high potentials. In addition, the possibility of change in the double layer originated by adsorption was checked through the following studies: effect of the cleaning of the electrode and continuous ciclization of potential, both using the cyclic voltammetry technique, and cronoamperometric studies. Controlled current electrolysis was conducted in acidic medium until the electrode deactivation. During electrolysis, samples were collected to evaluate oxidation process efficiency. The samples were submitted to chemical oxygen demand (COD) analysis using digestive (HgSO4, K2Cr2O7, H2SO4) and catalytic (AgSO4, H2SO4) solutions and were quantified by UV/Vis spectroscopy. In this experiments, the influence of current density and temperature toward oxidation efficiency (COD decrease) was also analyzed. The effect of the current density was studied applying 5.103, 7.5.103 and 1.104 A.m-2, at 298 K. The 3 3 -2 results of the COD analysis revealed that, at 5.10 and 7.5.10 A.m , the electrolysis developed both in the same way presenting a reduction of COD of up to 40 %. Already at 1.104 A.m-2, reduction tendency was uniform along the electrolytic process and the removal of the organic compounds was larger, reaching 48 % in 60 hours of electrolysis. Reduction of COD through the electrode process was associated to two factors: 1) oxidation of the organic matter at surface electrode (electrodegradation of the carbon at CO2); 2) the agglomeration of the particles in suspension over the surface of the solution due to the evolution of electrochemically generated gases (electroflotation)2: oxygen at anode and hydrogen at cathode. Through electrolytic method it has been possible to generate very fine bubbles (8 to 15 m) which promote the removal of

particles suspended by flotation. The electroflotation was observed during electrolysis by intense formation of foam in the surface of the solution. Experimentally it was not still possible to determine the contribution of each one of the factors for reduction of COD. Visually, it was observed that the increase of the current density intensified the electroflotation process (formation of more intense foam). Studies accomplished by Ferreira et al.3 with goal to study degradation of petroleum residues using toluene as model substratum was informed that the current density does not influence the efficiency of oxidation process. As the toluene is totally soluble, the electroflotation does not contribute to the efficiency of the process. Transferring these information for this study, we can conclude that at 1.104 A.m-2 the largest efficiency of the process for reduction of COD occurred due to increase of the intensity of the generated gases, optimizing the eletroflotation step. The effect of the temperature on the electrolyses was evaluated at 283, 298 and 323 K, applying the current density of 1.104 A.m-2. In this study, it was observed that the temperature increase contributed significantly to reduction of organic substratum presents in solution. In the basis of 60 hours electrolysis, it was observed a COD reduction of only 24 % at 283 K, while at 298 and 323 K, it was of until 48 and 57 %, respectively. The significant influence of the temperature in COD reduction was associated to the increase of the speed of gases generation and, possibly, oxidation of the organic substratum. In this case, the temperature contributes so much to the electroflotation process as for the electrodegradation. Results induce to the applicability of electrochemical technology for the treatment of organic petroleum waste. We can propose that electrodegradation is a promising methodology for the removal of organics compounds and it can be used in association with the electroflotation processes. CNPq/CTPETRO/FINEP. 1- DELGADINHO, A.M. and ALEGRE, R.M. Estudo de Eletrlise Aplicada ao Tratamento de Efluentes de Refinarias de Petrleo. In: IV SIMPSIO LUSO BRASILEIRO DE ENGENHARIA SANITRIA E AMBIENTAL. Belo Horizonte, 1990. Abstracts book. 2- SCOTT, K. Electrochemical Process for Clean Technology. Cambridge, The Royal Society of Chemistry, 1995. p.167-171, 174-179, 214-215. 3- FERREIRA, L. C.; GOULART, M. O. F.; TONHOLO, J.; ZANTA, C. L. P. S. Oxidao eletroqumica de tolueno: um modelo mecanstico para eletro degradao de derivados de petrleo. In: CONGRESSO BRASILEIRO DE P&D EM PETRLEO E GS, 1., Natal, 2001. Abstracts book. Natal, Sociedade Brasileira de Qumica, 2001, Ref. QA/QUI-053, p.308.