Available online at www.sciencedirect.

com

Chinese Chemical Letters 21 (2010) 101104 www.elsevier.com/locate/cclet

Application of advanced oxidation processes for removing salicylic acid from synthetic wastewaters
nez-Huitle b,c,** Xue Ming Chen a,*, Djalma Ribeiro da Silva b, Carlos A. Mart
b

Environmental Engineering Department, Zhejiang University, Hangzhou 310027, China mica, Lagoa Nova CEP 59.072-970, Brazil Universidade Federal do Rio Grande do Norte, CCET Departamento de Qu c University of Milan, Department of Chemistry, Celoria 2, 20133 Milan, Italy Received 17 February 2009

Abstract In this study, advanced oxidation processes (AOPs) such as anodic oxidation (AO), UV/H2O2 and Fenton processes (FP) were investigated for the degradation of salicylic acid (SA) in lab-scale experiments. Boron-doped diamond (BDD) lm electrodes using Ta as substrates were employed for AO of SA. In the case of FP and UV/H2O2, most favorable experimental conditions were determined for each process and these were used for comparing with AO process. The study showed that the FP was the most effective process under acidic conditions, leading to the highest rate of SA degradation in a very short time interval. However, the results showed that Ta/BDD lms had high electrocatalytic activity for complete degradation of SA; even if it employs more time for complete elimination of the SA respect to FP. Additionally, AO led to a sixfold acceleration of the oxidation rate compared with the UV/H2O2 process. Finally a rough comparison of the specic energy consumption shows that AO process reduced the energy consumption by at least 90% compared with the UV/H2O2 process. # 2009 Xue Ming Chen. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
Keywords: Advanced oxidation processes; Salicylic acid (SA); Anodic oxidation; Ta/BDD; Electrocatalytic activity

Different AOPs for the elimination of organic pollutants from wastewater, such as the FP, the photo-assisted FP, UV/Fe3+-oxalate/H2O2, photocatalysis, ozone water system, Mn2+/oxalic acid/ozone, H2O2 photolysis, O3/UV and AO, have been developed and investigated by several research groups as alternatives for treating industrial wastewater containing organic pollutants [13]. These technologies consist mainly in destroying the contaminants by chemical oxidation, so that mineralization of the contaminants to CO2 and H2O, or at least the transformation of these compounds into harmless products, is achieved. Oxidation process using liquid hydrogen peroxide (H2O2) in the presence of ferrous ion (Fe2+) produces free hydroxyl radicals (OH) (Fenton process [3]). These strong oxidants can rapidly degrade a variety of organic compounds. Whereas, other processes such as UV/H2O2, the OH are generated through photolysis of H2O2 under ultraviolet radiation [4]. In recent years, there is growing interest in AO for toxic and refractory organic pollutants degradation [2]. It has many advantages including high oxidation efciency, compactness

* Corresponding author. mica, Lagoa Nova CEP 59.072-970, ** Corresponding author at: Universidade Federal do Rio Grande do Norte, CCET Departamento de Qu Brazil. nez-Huitle). E-mail addresses: chenxm@zju.edu.cn (X.M. Chen), carlosmh@quimica.ufrn.br (C.A. Mart 1001-8417/$ see front matter # 2009 Xue Ming Chen. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved. doi:10.1016/j.cclet.2009.08.001

102

X.M. Chen et al. / Chinese Chemical Letters 21 (2010) 101104

in equipment, and simplicity in operation. This process has been effectively used to degrade several pollutants [5,6], oxidizing them, not only to CO2 and H2O, but to biodegradable products using mediated and/or direct electrochemical oxidation (EO). SA is a key ingredient in many skin-care products. This aromatic organic compound is very toxic and it is widely present in pharmaceutical industrial efuents, so-called pharmaceutical pollution. SA can stimulate skin and mucous membrane, and reacts with protein, and it can bring about tinnitus, qualm, naupathia and electrolytic turbulence. Therefore, effective removal of SA from wastewaters is very important. 1. Experimental FP and UV/H2O2 experiments were performed in the same degradation system, applying or not radiation, containing with a high pressure mercury lamp TQ 718 of 250 W (Heraeus Noblelight Company in Germany). The reactor was cylindrical (25 cm 5 cm of diameter), capacity of 0.5 L, and it was made of quartz glass available for radiation transfer. Different [H2O2]/[SA] molar ratios, [Fe2+] and pH were used to establish the most favorable experimental conditions in this work. The electrochemical reactor (ER) was 130 mm high and 30 mm in diameter, and was operated in batch. More details about the ER can be found elsewhere [6]. The current density (J = 200 A m2) was applied with a Tacussel model PJT24-1 (24 V1 A) potentiostatgalvanostat at 25 8C and 0.2 mol/L Na2SO4 as supporting electrolyte. Ta/BDD was used as anode, and a stainless steel plate was used as cathode. Samples were analyzed for determining the concentration changes of SA and by-products by High Performance Liquid Chromatograph (Varian Model 9050/9012 HPLC equipped with a Nucleosil C18 column (4.6 mm 250 mm); mobile phase: phosphoric acid (solution at pH 2): acetonitrile 35:65, at a ow rate of 0.4 mL/min; the UV detector was set at 300 nm). Chromatographic retention times were compared with those of commercially available standards. Chemical oxygen demand (COD) was measured using COD reactor and direct reading spectrophotometer. SA solutions of 1000 or 800 mg/L (Fluka reagent) were prepared using ultrapure deionized water. For each experiment, the pH was adjusted to around 4 with NaOH. H2O2 was added as a concentrated solution (3%). Fe2+ solutions were prepared with FeSO46H2O. In the case of the FP, pH was set at the desired value before the startup, and then a given amount of iron salt was added and mixed very well with SA before the addition of H2O2. For runs using the UV/H2O2 system, H2O2 was injected into the reactor before the beginning of each run. The temperature of the solution during the reaction was xed at 25 8C and maintained constant by using a water thermostat. 2. Results and discussion To determine the most favorable concentrations of Fe2+ and H2O2 in the FP, experiments were carried out at 14 different [H2O2]/[SA] molar ratios. After that, subsequent experiments were performed at the best [H2O2]/[SA] molar ratio for ve different Fe2+ molar concentrations (0.2, 0.4, 0.6, 0.8 and 1.0 mmol/L), obtaining that at [Fe2+] = 0.6 mmol/L and [H2O2]/[SA] = 7 were achieved the better performances. pH effect on the SA removal efciency for FP and UV/H2O2 was studied, experiments were carried out in the pH range 214, under the abovementioned conditions, showed that pH $45 were achieved high SA removal. Fig. 1A shows the elimination of SA as well as the formation and partial disappearance of the main reaction intermediates (2,3-dihydroxy benzoic acid (2,3DHBA); 2,5-dihydroxy benzoic acid (2,5-DHBA); and catechol (CT)) by FP. Complete elimination of SA was achieved after 180 min. As for the intermediates, only 2,5-DHBA and CT were almost completely eliminated; an amount of 2,3-DHBA remained in solution increasing the time of the complete elimination (adding more Fe2+ or H2O2 for the reaction). Further intermediates (malic, maleic, and fumaric acids) [7] were oxidized to oxalic acid. Oxalic acid is slowly transformed into CO2, but it forms Fe/oxalate complexes mainly. In the case of UV/H2O2, it occurs under irradiation (280 nm) of the pollutant solution containing H2O2. This causes the homolytic cleavage of H2O2 [1,7]. Different [H2O2]/[SA] molar radio and pH were tested in order to determine the most favorable conditions, obtaining that [H2O2]/[SA] = 6 and pH 4 achieved the best performances (next experiments were performed under these experimental conditions). Then, during the UV/H2O2 oxidation of SA, the main product was 2,3-DHBA, whereas CT and 2,5-DHBA were produced in minor amounts. The complete elimination of SA was not achieved (Fig. 1B). Complete elimination (SA and malic, maleic and fumaric acids) was veried by analytical techniques after 23.5 h. In the AO at Ta/BDD electrode, several experiments were realized for 200 A m2 and pH $4. Fig. 2A shows that the AO of SA is completely achieved after 8 h of electrolysis, showing that insignicant amounts of CT, 2,3 and 2,5-DBHA were detected. Based on HPLC measurements, the rate of SA and by-products oxidation is faster due to the reactivity

X.M. Chen et al. / Chinese Chemical Letters 21 (2010) 101104

103

Fig. 1. Elimination of SA as function of time: (A) FP and (B) UV/H2O2. pH 4 adjusted with NaOH. Evolution of the main intermediates: 2,3-DHBA; 2,5-DHBA; and CT.

of OH formed at BDD surface. Marselli et al. [8] proposed a reaction mechanism for this process that involves the participation of OH generated at the electrode surface through the EO of water. The elimination step should occur with the organic molecules in the proximity of the surface layer of OH and via homogeneous reaction between the organic molecules and the OH conned within a reaction cage nearby the electrode surface. These OH impede the evolution of higher concentration of aromatics compounds and increasing the rate of transformation of possible intermediates to aliphatic acids, and nally CO2. Analogous results were obtained and reported by Guinea et al. [9]. Other oxidants formed at the diamond surface (H2S2O8, O3) can participate in the oxidation of the SA and intermediates formed [2]. These reagents can oxidize organic matter leading to an increase in removal rates [2]. SA concentration in industrial wastewaters may vary from time to time, it is necessary to investigate AO of SA under different initial concentrations. It was found that low residual COD level could be achieved for all solutions after oxidation. COD was reduced from 166830 to 142 mg/L, with removal efciency of over 95%, indicating that this anode can mineralize SA effectively. In contrast, low removal SA was mineralized by other processes [10]. On the other hand, the variation of the instantaneous current efciency (ICE) with COD for oxidation of different concentrations of SA was studied. Clearly, ICE decreased with COD. This behavior can be ascribed to mass transfer limitation due to the gradual decay in pollutant concentration [11].

Fig. 2. (A) AO of SA as function of time at Ta/BDD anode. pH 4 (adjusted with NaOH), J = 200 A m2 and 25 8C. Inset: Reaction of SA with the hydroxyl radicals to form hydroxylated aromatic compounds. (B) COD removal as function of time, depending on AOPs used. Values of constants reaction rate for SA degradation: UV/H2O2: 1.29 103 0.00003 min1; AO: 5.49 103 0.00007 min1; FP: 10.10 103 0.00068 min1.

104

X.M. Chen et al. / Chinese Chemical Letters 21 (2010) 101104

The residual COD variation with different values of J for AO of SA at a given charge loading and it was observed that the residual COD increased as the J increased at a given charge loading. The residual COD was 10 mg/L at 50 A m2, but increased to 190 mg/L when the J increased to 300 A m2. This is consistent with that reported by Panizza et al. [12]. The increased current beyond the limiting J is not for oxidizing pollutants but for producing O2, resulting in a decrease in CE, and a process determined by the mass transfer rate. For comparing all oxidation methods, SA solutions with a content of 800 ppm of COD were used. For FP and UV/ H2O2, time processes to complete the elimination of SA were substantially different; shorter times for FP; and longer times for UV/H2O2. However, as can be seen in Fig. 2B, at FP was necessary to provide an amount of H2O2 or/and Fe2+ for removing completely the intermediates formed (after 150 min and nal stages). On contrary for AO, a complete elimination was attained, without addition of other class of chemical reagents in solution. COD removal was about 98%. Finally, data were tted to a rst-order rate model, ln(Ct/C0 = k0t), where C0 and Ct are the concentration of SA at times 0 and t, respectively; k0 is a rst-order rate constant (in min1), and t is the time (in min). The values of k0 are reported in the inset of Fig. 2B, in agreement with the data discussed above about the removal rates processes. Energy required for removing 95% of 800 mg dm3 of COD of SA by UV/H2O2 and AO processes was obtained. UV/H2O2 is less economical than the AO process (13.05 kWh kg1 of COD by UV/H2O2, during 23.5 h (total time used for complete SA oxidation)); with an energy increase of 200% for removing SA from wastewaters (consumed energy estimated from the UV radiation used which represented only a part of the total electrical energy). The output UV energy amount of the lamp is about 250 W. Energy consumption for AO was about 4.45 kWh kg1 of COD. This energy consumption could be reduced using J values below 200 A m2. It is important to remark that, FP is more economical than other two processes; however, several conditions must be considered to obtain good performances. 3. Conclusions Based on the preliminary results, it is possible to ascertain that the FP and AO processes can be viable techniques for the treatment of industrial wastewater containing SA due to its efciency and low operational cost. FP rate is inuenced by many factors, but [SA] removal efciencies about 96%, were achieved after 150 min and 80% of COD removal. For UV/H2O2 oxidation, [SA] removal efciencies were about 54% and 63% of COD removal after 700 min of treatment. Finally, AO achieved good removal efciencies on [SA] and COD respect to other methods, and a complete elimination of SA was attained by AO without including other class of chemical reagents in solution, converting this method an important alternative in the wastewater treatment. Further AO runs of SA will be performed in order to have kinetic information and to optimize the electrolysis parameters. Detailed data and discussions will be reported in a separate paper in a near future. References
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] R. Andreozzi, V. Caprio, A. Insola, et al. Catal. Today 53 (1999) 51. C.A. Martinez-Huitle, S. Ferro, Chem. Soc. Rev. 35 (2006) 1324. E. Brillas, R. Sauleda, J. Casado, J. Electrochem. Soc. 145 (1998) 759. O. Legrini, E. Olivieros, A.M. Braun, Chem. Rev. 93 (1993) 671. X.M. Chen, G.H. Chen, F.R. Gao, et al. Environ. Sci. Technol. 37 (2003) 5021. X.M. Chen, G.H. Chen, P.L. Yue, Chem. Eng. Sci. 58 (2003) 995. J.J. Pignatello, E. Oliveros, A. MacKay, Crit. Rev. Environ. Sci. Technol. 36 (2006) 1. B. Marselli, J. Garcia-Gomez, P.A. Michaud, et al. J. Electrochem. Soc. 150 (2003) D79. E. Guinea, C. Arias, P.L. Cabot, et al. Water Res. 42 (2008) 499. n, J.M. Coronado, R. Bellod, et al. Appl. Catal. A: Gen. 303 (2006) 199. C. Ada X.M. Chen, G.H. Chen, Sep. Purif. Technol. 48 (2006) 45. M. Panizza, P.A. Michaud, G. Cerisola, et al. J. Electroanal. Chem. 507 (2001) 206.