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Catalysis Today 209 (2013) 79–83

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Photodegradation of petrol station wastewater after coagulation/flocculation with tannin-based coagulant
A.M. Ferrari-Lima ∗ , R.G. Marques, N.R.C. Fernandes-Machado, M.L. Gimenes
Universidade Estadual de Maringá, Av. Colombo, 5790 Maringá, Brazil

a r t i c l e

i n f o

a b s t r a c t
This work investigates the combined treatment of petrol station wastewater by coupling coagulation/flocculation and heterogeneous photocatalysis processes. Coagulation/flocculation was performed using a tannin-based coagulant, Tanfloc. Commercial TiO2 , ZnO and Nb2 O5 were applied as photocatalysts, after calcination at 500 ◦ C/5 h. In order to evaluate synergic effects, the semiconductor oxides were mixed (50 wt%) and their activities were investigated under UV and VIS radiations. High reductions of absorbance, chemical oxygen demand and elimination of toxicity to Artemia salina was achieved with TiO2 –ZnO under UV radiation. Chemical oxygen demand was reduced from 1363 mg L−1 (untreated) to 362 mg L−1 after coagulation/flocculation and finally to 104 mg L−1 after photocatalytic treatment. © 2012 Elsevier B.V. All rights reserved.

Article history: Received 29 June 2012 Received in revised form 6 September 2012 Accepted 22 October 2012 Available online 11 December 2012 Keywords: Photocatalysis TiO2 catalyst ZnO catalyst Petrol station wastewater

1. Introduction Generated by spills during fuel supply, forecourt washing, car washing systems and convenience stores, petrol station wastewater (PSW) has a huge amount of hydrocarbons that are not removed by oil–water separators, which is the unique treatment system required for petrol stations. These hydrocarbons are formed by the soluble fraction of petrol and diesel in water, derived mainly from spills during fuel supply. Moreover, the presence of ethanol can contribute by increasing the solubility of these hydrocarbons in water [1], raising the toxicity of PSW. Many efforts have been applied in order to eliminate several types of hydrocarbons present in wastewater such as phenolic and other aromatic compounds [2–4]. Owing to the high toxicity of these compounds the oxidation of the hydrocarbons to CO2 and H2 O by means of advanced oxidation processes (AOPs) are of particular interest when compared to conventional processes of wastewater treatment. Among the AOPs, heterogeneous photocatalysis has been the subject of several studies on the degradation of toxic effluents [5–8] and has shown good results in the removal of several contaminants from wastewater. When a semiconductor is subjected to radiation whose energy is equal to or greater than its band gap energy, the excitation promotes a valence band electron to the conduction band, creating a gap in the valence band with enough positive potential to generate OH• radicals from adsorbed water molecules. These radicals are

highly oxidising and react with organic compounds mineralising them. Among the huge variety of catalysts that have been investigated, TiO2 is undoubtedly the most used due to its well known structure and high activity [9–11]. However, TiO2 activity is still not high enough to be suitable for commercial application [12], especially due to the charge recombination and the need of ultraviolet radiation for the activation of the catalyst. In this sense, many efforts have been dedicated in order to enhance its activity by mixing semiconductor oxides to achieve better charge separation and avoid recombination centres [12–14]. With this background, the aim of this work was to investigate the activity of mixed semiconductor oxides (TiO2 , ZnO and Nb2 O5 ) in the photodegradation of petrol station wastewater under ultraviolet and visible light radiations after pre-treatment by coagulation/flocculation process using a tannin-based coagulant. The reduction of chemical oxygen demand and toxicity were discussed as well as the kinetics of the photodegradation and the overall efficiency of the combined treatment. 2. Experimental 2.1. Wastewater collection and characterisation PSW samples were collected after oil–water separation in a petrol station located in an urban area of Maringa-Parana-Brazil and characterised following the Standard Methods for Examination of Water and Wastewater [15]. The petrol station offers fuel supply (ethanol, gasoline, and diesel), oil change services, vehicle washing and convenience store.

∗ Corresponding author. Tel.: +55 44 3011 4777; fax: +55 44 3261 4792. E-mail address: ana (A.M. Ferrari-Lima). 0920-5861/$ – see front matter © 2012 Elsevier B.V. All rights reserved.

12 3. 310 and 500 nm (HACH DR5000 spectrophotometer). 50. Xray diffraction (XRD) was performed in a Bruker D8 Advance X-ray diffractometer with Cu 40 K␣ radiation. corresponding to percent concentrations of 100. The light beam was modulated with a mechanical modulator (Stanford Research Systems SR540). The distance between the lamp and the surface of the suspension was 15 cm. PAS analysis showed that all the catalysts have similar bandgap energies. 12. Results 3. 2. 10. The mortality of the nauplii for each dilution was evaluated and the lethal concentration for 50% of the nauplii (LC50) after 24 h of exposition was determined by probit analysis. Artemia saline (brine shrimp) was used as bioindicator of the toxicity. Cysts of Artemia saline were incubated in a 35 g L−1 marine salt solution for 24 h at 28 ◦ C with continuous illumination and aeration.3. around 3. 2 mL Table 1 Surface area and band gap of the catalysts. Emission spectra of the lamps were acquired in a VS140 Linear Array UV-VIS & VIS Spectrometer (HORIBA). 30 mA and Ni filter.17 3. Coagulation/flocculation process Coagulation/flocculation was performed in jar test Milan JT101.25. 1. 40 and 60 mL L−1 . the supernatant aqueous phase was separated for characterisation. A slight reduction on the surface area with the thermal treatment means an increase in the crystal size by the sintering of small particles.17]. After 2 h flocs settling down. 25. 2. The photoacoustic spectrum was obtained on modulation frequency of 21 Hz at wavelength from 200 to 800 nm. 2.6 8. aliquots of 2 mL (before and after treatment) were added to the wells at the following dilutions in saline solution: 0. Catalysts characterisation Textural analysis (Table 1) showed that surface area and pore size distributions of mixed catalysts were approximately the average of those for plain oxides.12 and 0% of wastewater.6 6. Biotoxicity tests Toxicity tests were performed following the methodology described in Santana and Fernandes-Machado [14]. the catalysts were submitted to agglomeration process (particle size 0.5. Catalyst Surface area BET (m2 g−1 ) As prepared After annealing at 500 ◦ C/5 h 8.1. Photocatalytic assays were performed with 1 g L−1 of catalyst concentration. 280.7 49. Photograph of the photocatalytic reactor.15 3. a high sensitivity capacitive microphone (Bruel and Kjaer) and a lock-in amplifier (EG & G 5110). aliquots of these solutions were added to the wells. ZnO (Dynamics) and Nb2 O5 (Companhia Brasileira de Minerac ¸ ão e Metalurgia) were used plain and in simple mixture (50 wt%) after calcination at 500 ◦ C/5 h. biotoxicity to Artemia salina and absorbance reductions after 300 min of irradiation. it means that the catalysts need TiO2 ZnO Nb2 O5 TiO2 –ZnO Nb2 O5 –ZnO TiO2 –Nb2 O5 10. respectively. after adding Tanfloc at 500 mg L−1 concentration and followed by 30 min of slow agitation (50 rpm).0 47. / Catalysis Today 209 (2013) 79–83 2. conjugated aromatic rings and light-absorbing molecules.20 3.4.2 eV (Fig. After 24 h the most active organisms were transferred to a new marine salt solution at the same concentration of the previous one and maintained for more 24 h at the same conditions. 3.0 Band gap (eV) 3. 3).5 39. 20. Scanning electron microscopy (SEM) analysis was carried out on Shimadzu SS-550 Superscan Microscope.5. 1/16 and 1/32 and 1. 1/2. Textural analysis was carried out by nitrogen adsorption isotherm at 77 K using QuantaChrome Nova 1200 equipment.80 A. 6. aromatic groups.8 6.17 3. hexagonal structure for Nb2 O5 and wurzita phase for ZnO after calcination at 500 ◦ C/5 h. a monochromator (Oriel Instruments 77.8 69.250). About 10 nauplii were added to each well and maintained in these solutions for 24 h under illumination (triplicate). For the wastewater. 1/8. The UV light intensity was measured by an Instrutherm UV light meter MRU-201 and the VIS light intensity was measured by an Instrutherm luximeter LD300. Photocatalytic reactions The reaction system was formed by a 500 mL glass beaker equipped with magnetic agitation.5 47. 1. 2) identified anatase phase for TiO2 .6 33. Catalysts preparation and characterisation The photocatalysts TiO2 (Kronos).21 Absorption threshold (nm) 388 397 391 391 394 386 Fig. The observed peaks were compared with the data published by JCPDS (10).M. respectively [16.8 8. 3. in accordance with previous work [16]. a solution of potassium dichromate (1 g L−1 ) was prepared and diluted in saline solution at the concentrations of 0. Photoacoustic spectroscopy (PAS) was performed in equipment consisting of a monochromatic light provided by a xenon lamp of 1000 W (Oriel Corporation 68820). 1/4. Catalyst activity was evaluated by chemical oxygen demand (COD).300 mm). XRD analysis (Fig. Ferrari-Lima et al. Radiation was provided by a 250 W low pressure mercury lamp (EMPALUX) whose bulb has been removed to obtain UV radiation or maintained to obtain VIS radiation. New phases were not identified by mixing the oxides.5 . Wastewater was stirred (100 rpm) for 1 min. temperature control and radiation isolation. the following solutions were prepared: for the control.2. corresponding to aliphatic groups.150–0. For toxicity testing. Absorbance was measured at 254. The photographic illustration of the reactor is showed in Fig. Prior to calcination.

Some authors report that for successful photocatalysis. the initial and final COD concentrations (mg L−1 ). 4. the equation gave a q value of 2002 mg of COD per g of Tanfloc for PSW coagulation/flocculaltion while other authors achieved q values of 490 mg and 359 mg for dye and surfactant removal. This energy is located in the ultraviolet region of the electromagnetic spectra.2. ZnO and Nb2 O5 oxides (Table 1). the supernatant was separated from sludge and submitted to photodegradation under UV and VIS radiations with an irradiation time of 300 min. Photocatalytic degradation After coagulation/flocculation process. respectively.150–0. organic and colloidal matter from the effluent. Although the reduction of COD was 68% for both TiO2 Table 2 PSW characterisation before and after coagulation/flocculation with Tanfloc. where C0 and C1 are. When the bulb is maintained the majority of the peaks are found at the visible region with two peaks corresponding to the ultraviolet region. By measuring the emission spectra of the lamps (Fig. 3. given that high turbidity and organic matter concentration can affect the scattering of light into the solution.300 mm. mixing TiO2 and ZnO enhanced both TiO2 and ZnO activities under UV radiation (Fig. Ferrari-Lima et al. Reductions in all the parameters after coagulation/flocculation certify the capability of Tanfloc to remove Fig. as depicted in Table 2. and biodegradable sludge generation [22] can represent a promising use of organic coagulants in wastewater treatment. COD values must be lower than 800 mg L−1 [16. 5). Tanfloc can be considered a good alternative to inorganic coagulants since the coagulant did not drastically reduce the pH of the effluent and showed satisfactory COD. Additionally. In the present work. In this way. UV/VIS and VIS lamps emission spectra.A. 365 and 410 nm. Parameter pH COD (mg L−1 ) TOC (mg L−1 ) Turbidity (NTU) Total solids (mg L−1 ) Grease (mg L−1 ) In natura 6. 3. . consisting of well distributed spherical grains. 2. Some grain agglomerates were found and can be associated with the sintering caused by the heat treatment. around the same amount of energy to promote the electron. 550 and 580 nm (visible region).3. the emission provided by the lamp with and without the bulb was called VIS and UV radiations. no addition of metal ions to the system.9 1363 187 326 1287 56 After coagulation 6. Despite the similarity of the catalysts characteristics. SEM analysis showed that all the catalysts have similar morphology. Radiation intensity on the suspension surface was 3570 ␮W cm−2 at 390 nm for the UV light and for the VIS light it was 700 ␮W cm−2 at 390 nm and 15.21]. 3. Beltrán-Heredia and Sánchez-Martín [18] determined the adsorption capacity (q) as being an efficiency parameter for the coagulation process. / Catalysis Today 209 (2013) 79–83 81 Fig. TOC and turbidity removal capability. Wastewater characterisation and coagulation In general. the effluent has neutral pH. Pre-treatment can represent a fundamental step in heterogeneous photocatalysis systems. It was defined as q = (C0 − C1 )V/W. 4) it is possible to note that when the bulb is removed both UV and VIS radiations are emitted with main peaks located at the ultraviolet region and also strong peaks located at 440. o = ZnO. respectively. The particle size inside the reactor was in the interval of 0. respectively.780 lx.8 362 90 34 632 45 Reduction (%) – 73 52 90 51 18 Fig. * = Nb2 O5 ). V is the volume of solution (L) and W is Tanfloc mass (g).M. as it is well known for TiO2 . Comparing the peaks of the lamps with the absorption threshold of the catalysts (Table 1) it can be proposed that the 365 nm peak is the responsible for the activation of the catalysts whereas at this wavelength the minimum energy required by the semiconductors to promote the electron is provided. XRD of the catalysts (x = TiO2 anatase.20].17. the advantages associated with the use of organic coagulants such as no pH adjustment requirements. high turbidity and COD. UV/VIS photoacoustic spectra of the catalysts. applying the same coagulant [19.

TiO2 –ZnO/UV and TiO2 /VIS. Nevertheless. For the selected systems.M. . increasing the absorbance in the wavelengths related to these compounds. Residual absorbance of pre-clarified PSW after 300 min of VIS radiation. Herrmann [28] points out that the aromatics rings are easily dearomatised and if there are aliphatic groups attached to the rings. Kinetics of COD reduction Kinetics studies were performed with the following systems: TiO2 /UV. values with different letters are statistically different while values with the same letter are statistically identical. biotoxicity assays were carried out with A. The total irradiation time considered for kinetic studies was 300 min. Toxicity reduction and combined treatment It is known that photocatalysis can generate side-compounds that are toxic to aquatic environment. The toxicity was measured only after the end of the reaction (after 300 min of irradiation). A slight reduction in COD and absorbance was observed when reaction was carried out without the catalyst.34 t1/2 (min) 291 121 296 R2 0. This fact is clearly related to the band gaps of the catalysts which according to Table 1 are located in the UV region. 5. In the case of TiO2 and TiO2 –ZnO catalysts applied under UV radiation. 3.34–37].4. indicating that UVabsorbing compounds are probably present in the PSW and can compete with catalyst for absorption of radiation [25]. This synergic behaviour can be attributed to the electron transfer from the conduction band of ZnO to the conduction band of TiO2 under illumination and the hole transfer from the valence band of TiO2 to the valence band of ZnO. Absorbance reductions greater than 40% were achieved for all the wavelengths monitored for both TiO2 and TiO2 –ZnO catalysts.38 5. half-life time (t1/2 ) and R2 for COD reduction of PSW. 280. salina has been successfully employed to detect the toxicity of several media including vinasse. keeping the catalyst usually precipitated in water [26. [33] for COD removal from reactive dye-containing wastewater applying TiO2 .29–32]. The more active catalyst was TiO2 –ZnO/UV which showed the shortest half-life time for COD reduction (121 min). 81 and 88% for the wavelengths of 254. 3. aromatic rings are broken down into smaller compounds (single rings or aliphatic groups). thus the lower activity of the Nb2 O5 containing catalysts even with its higher surface area. salina (brine shrimp) in order to evaluate the final toxicity of the treated water after the combined treatment. Residual absorbance of pre-clarified PSW after 300 min of UV irradiation. The same behaviour has been reported for the photodegradation of several compounds [2. absorbance reduction occurs at the following order: 500 nm > 310 nm > 280 nm > 254 nm.9986 0. This fact occurs because as the aromatic hydrocarbons are degraded. 53% of COD reduction was reached with TiO2 and VIS radiation.5.82 A. which corresponds to the lethal concentration in percentage of wastewater that causes death of 50% of Artemia nauplii after 24 h of exposition. Some authors associate the lower activity of Nb2 O5 to the low stability of its hydrocolloid. this bond is quickly broken. Other authors have also reported synergic effect between semiconductor oxides at the same proportion of 50% [14]. and TiO2 –ZnO catalysts. 0. In general. These values show that the hydrocarbons are being degraded and the organic matter is being removed from the wastewater by means of photocatalysis. 78. the reduction of absorbance was higher for TiO2 –ZnO. improving the occurrence of redox processes [23. Toxicity was evaluated in terms of LC50 percentage. The cited authors reported a rate constant of 0.0023 min−1 for the systems TiO2 /UV. This fact indicates that when the nauplii were submitted to the effluent treated with these catalysts the percentage of deaths was lower Fig. the LC50 was greater than 100% after 300 min of irradiation (Table 4). aldehydes and biocides [14. Therefore. TiO2 –ZnO/UV and TiO2 /VIS. Ferrari-Lima et al. 6). 6. Furthermore.0024. / Catalysis Today 209 (2013) 79–83 Table 3 Rate constants of apparent first order (k1 ). reaching 76.73 2. Selected system TiO2 /UV TiO2 –ZnO/UV TiO2 /VIS k1 (×103 min−1 ) 2.9974 0.0057 and 0. the oxidation process preferentially occurs at the highest electronic density positions [16].27].24].9823 Fig. respectively. 310 and 500 nm. The brine shrimp A. so there is no toxicity data to predict the behaviour of the formation of more or less toxic oxidation intermediates throughout the photodegradation. the data fit the Langmuir–Hinshelwood kinetics model for reactions of apparent first order for COD oxidation (Table 3). respectively.0046 min−1 for the mentioned process while in the present work the rate constants were 0. When the pre-clarified wastewater was submitted to VIS radiation the reductions of COD and absorbance were lower than that obtained when UV radiation was applied (Fig. leading to an decrease in the recombination rate and increase in the lifetime of the electron-hole pair. cyanobacteria. The rate constants showed the same magnitude found by An et al.

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