Solar Energy 77 (2004) 591600 www.elsevier.

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Solar photocatalytic treatment of simulated dyestu euents

M. Kositzi
a

a,*

, A. Antoniadis a, I. Poulios a, I. Kiridis b, S. Malato

Laboratory Physical Chemistry, Department of Chemistry, University of Thessaloniki, 54124 Thessaloniki, Greece b Viostamp S.A.-Thessaloniki Dyeing Mills S.A., Industrial Area, of Thessaloniki, 57022 Sindos, Greece c Plataforma Solar de Almeria (CIEMAT), 04200 Tabernas, Spain Received 2 December 2003; received in revised form 2 April 2004; accepted 2 April 2004 Available online 22 July 2004 Communicated by: Associate Editor Claudio Estrada-Gasca

Abstract The photocatalytic organic content reduction of two selected synthetic wastewater from the textile dyeing industry, by the use of heterogeneous and homogeneous photocatalytic methods under solar irradiation, has been studied at a pilot plant scale at the Plataforma Solar de Almeria. The eect of two dierent TiO2 modications with oxidants such as H2O2 and Na2S2O8 on the decolourisation and the dissolved organic content reduction (DOC) of the wastewater was examined. The TiO2/H2O2 system seems to be more ecient in comparison to the synergetic action that appears when using persulphate and TiO2 in this specic wastewater. By an accumulated energy of 50 kJ l1 the synergetic eect of TiO2 P-25 with H2O2 and Na2S2O8 leads to a 70% and 57% DOC reduction, respectively, in the case of cotton synthetic wastewater, while the decolourisation was almost complete. The photocatalytic decolourisation, as well as the DOC reduction in the case of nylon simulated wastewater is a slower process and an accumulated energy of 50 kJ l1 leads to almost 54% mineralisation in both cases. The photo-Fenton process in both types of wastewater was more ecient in comparison to the TiO2/oxidant system. An accumulated energy of 50 kJ l1 leads to 90% reduction of the organic content. 2004 Elsevier Ltd. All rights reserved.
Keywords: Solar detoxication; Photocatalysis; Dyestu euents

1. Introduction The elimination of toxic chemicals from wastewater is presently one of the most important subjects in pollution control. These pollutants may originate from industrial applications (petroleum rening, textile processing, etc.) or from household and personal care areas (pesti-

* Corresponding author. Tel.: +30 2310 99 77 85; fax: +30 2310 99 77 84. E-mail address: mkositzi@chem.auth.gr (M. Kositzi).

cides and fertilizers, detergents, etc.); several of them are resistant to conventional chemical and biological treatment methods. The search for eective means of removing these compounds is of interest to regulating authorities everywhere. Heterogeneous and homogeneous solar photocatalytic detoxication methods (TiO2/H2O2, Fe+3/H2O2) have shown recently great promise for the treatment of industrial wastewater, groundwater and contaminated air. Additionally, the semiconductor mediated photocatalytic process has shown also great potential for disinfection of air and water, thus making possible a

0038-092X/$ - see front matter 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.solener.2004.04.018

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number of applications (Peral et al., 1997; Alfano et al., 2000; Malato et al., 2003; Fujishima et al., 2000). General description of heterogeneous photocatalysis under articial or solar irradiation is presented in several excellent review articles (Bahnemann et al., 1994; Homan et al., 1995; Herrmann, 1999; Serpone and Emeline, 2002). A brief summary is presented here only for the sake of completeness. It is well established, that by the irradiation of an aqueous TiO2 suspension with light energy greater than the band gap energy of the semiconductor (Eg > 3.2 eV), conduction band electrons (e) and valence band holes (h+) are generated. Part of the photogenerated carriers recombine in the bulk of the semiconductor, while the rest reach the surface, where the holes, as well as the electrons, act as powerful oxidants and reductants respectively. The photogenerated electrons react with the adsorbed molecular O2 on the Ti(III)-sites, reducing it to superoxide radical anion O , while the photogen2 erated holes can oxidize either the organic molecules directly, or the OH ions and the H2O molecules adsorbed at the TiO2 surface to OH radicals. These radicals together with other highly oxidant species (e.g. peroxide radicals) are reported to be responsible for the primary oxidizing step in photocatalysis. The OH radicals formed on the illuminated semiconductor surface are very strong oxidizing agents, with a standard reduction potential of 2.8 V. These can easily attack the adsorbed organic molecules or those located close to the surface of the catalyst, thus leading nally to their complete mineralisation. Although it is well known for some time that the Fenton reagent, a mixture of Fe+2 salts and H2O2, can easily oxidize organic compounds, it has been applied for water and soil treatment only during the last years (Chamarro et al., 2001; Bidga, 1995; Lee and Hosomi, 2001). This reagent which produces in a very simple way OH radicals (Eq. (1)) for wastewater treatment, is an attractive oxidative system, due to the fact that iron is a very abundant and nontoxic element and hydrogen peroxide is easy to handle and environmentally safe. Furthermore, it was found that the reaction can be enhanced by UV/VIS light (articial or natural), producing additional OH radicals and leading to the regeneration of the catalyst (Eq. (2)) (Photo-Fenton reaction) (Oliveros et al., 1997; Fallmann et al., 1999; Arana et al., 2001). Fe2 H2 O2 ! Fe3 OH OH Fe3 H2 O hv ! Fe2 H OH 1 2

ern dyes are characterized by great stability and by a large degree of aromatics in their structure. Almost 30% of the amount of dyes used is released in the wastewater, so these are highly coloured and with a great organic matter (Easton, 1995). The nonbiodegradability of textile wastewater is due to their high content of dyestus, surfactants and other additives. Due to the stability of modern dyes, conventional biological treatment methods for industrial wastewater are ineective, frequently resulting in an intense coloured discharge from the treatment facilities. Additionally, they are readily reduced under anaerobic conditions to potentially hazardous aromatics. Thus, there is a need for developing more eective treatment methods in eliminating dyes from a waste stream at its source. Recently, a number of research groups have dealt with the photocatalytic decomposition of this class of materials in the presence of articial or solar light (Matthews, 1991; Poulios and Tsachpinis, 1999; Fernan dez-Ibanez et al., 1999; Augugliaro et al., 2002; Sauer et al., 2002) with very encouraging results. Additionally, studies dealing with real textile wastewater have revealed that it is possible to degrade them completely or at least to some extent via a homogeneous or a heterogeneous photocatalytic method (Davis et al., 1994; Kang et al., 2000; Arslan et al., 2000; Perez et al., 2002). In the present work, the eciency of TiO2 and photoFenton reagent under solar irradiation was evaluated by the decolourisation and dissolved organic content reduction (DOC) of two dierent synthetic textile dyeing wastewater, which are produced during the dyeing process in a textile mill industry. During the heterogeneous photocatalytic experiments the eect of the type of catalyst, as well as the inuence of oxidizing agents such as H2O2 and Na2S2O8 was studied, concerning the decolourisation and the decrease of the dissolved organic content of the textile dyeing wastewater, while in the case of photo-Fenton reagent the eect of Fe+3 and H2O2 on the DOC reduction has been studied.

2. Experimental All photocatalytic experiments carried out in this work, have been contacted in Almeria (latitude 37N, longitude 2,4W)/Spain from 1.07.02 to 30.07.02 using natural light irradiation. During this time the UV-A intensity ranged between 10 and 35 W m2. 2.1. Materials Two dierent synthetic wastewater were used, made according to recipes used in Viostamp Company for the dyeing of cotton and nylon fabrics. The cotton synthetic wastewater (CSW) was of the following composition: 0.1 g l1 HCOOH, 0.250 g l1 Perydrol FHB 15%,

These reactions are known to be the primary forces of the photochemical self-cleaning of atmospheric and aquatic environment (Faust and Zepp, 1993). The textile dyeing and nishing industry is one of the major pollutants among the industrial sector, since mod-

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0.375 g l1 Sequion, 0.5 g l1 Na2CO3, 0.5 g l1 NaOH, 0.1125 g l1 Black-GR-Triactive, 0.0019 g l1 Yellow3RS-Triactive, 0.0076 g l1 Red-3BS-Triactive, 3 g l1 NaCl. The nylon synthetic wastewater (NSW), which was used during the photocatalytic experiments, contained: 0.140 g l1 HCOOH, 0.2 g l1 Perydrol, 0.2 g l1 Extra Antipariro, 0.065 g l1 Black-MSRL-Erionyl, 0.028 g l1 Yellow-2R-Lanaset and 0.042 g l1 OrangeRN-Lanaset. The above mentioned dyes are mixtures of monoazo and monoazo metal complex compounds, although their molecular types are not known, since they are industrial materials and the ingredients are still protected by patents. The NSW has an initial pH value of 3.3 and a DOC of 0.15 g l1 (0.5 g l1 COD and 0.12 g l1 BOD5) and the CSW an initial pH of 12 and a DOC of 0.15 g l1 (0.55 g l1 COD and 0.12 g l1 BOD5). TiO2 P-25 of Degussa (anatase/rutile = 3.6/1, surface area 56 m2 g1 nonporous) and a commercially available TiO2 (A) (Tronox A, McGee, 100% anatase) were used for all heterogeneous photocatalytic experiments. The TiO2 (A) was chosen due to its considerably good photocatalytic properties and because of its lower price, in relation to TiO2 P-25 (Kositzi et al., 2004). All other reagent-grade chemicals, such as FeCl 6H2O, H2O2, Na2S2O8, etc., were purchased 3 through Merck and were used without further purication. The water used in the pilot plant experiments was laboratory-equivalent quality (Type IIIIV ASTM), with a DOC content of <0.5 mg l1.

2.2. Photocatalytic reactor The experiments were carried out using the Compound Parabolic Collector (CPC) modules of the Plataforma Solar de Almeria (PSA). The pilot plant is made up of twin systems, each having three collectors, one tank and one pump. One collector consists of eight parallel CPC reectors with UV transparent tubular receivers. Each collector (ACPC = 3.09 m2) has eight Pyrex tubes connected in series and mounted on a xed platform inclined at a 37 angle (the local latitude) for maximum solar irradiation. The water ows at 20 L min1 directly from one module to another and nally into a tank. Polished aluminium is used as the reective material because of its high UV-reectivity in the concerning UV-range of 300400 nm (Hermann et al., 1998). The schematic conguration of the system is shown in Fig. 1 (Malato et al., 2001). The three modules are connected in series and the water ows directly from one to the other and nally to a tank. A centrifugal pump, then, returns the wastewater to the collectors. The total volume of the irradiation sample was 35 l. Before starting the photocatalytic experiments, the CPC collectors were covered with a black plastic sheet as a protection against sunlight. After the wastewater circulated through the whole system, the catalyst and the oxidants has been added to the tank. After 30 min of mixing, the sheets were removed and samples were collected in regular time intervals at the exit of the CPC. To remove the TiO2 particles, the solution was ltered through a 0.45 lm lter (Millipore).

CPCs 3 x 1.03 m2
20 L /min 20 L /min

CPCs 3 x 1.03 m2

Sampling Valve 2

Sampling Valve 1

T2

T1

Tank 2

Tank 1

Pump 2

Pump 1

Fig. 1. The compound parabolic collector (CPC) modules of the Plataforma Solar de Almeria (PSA).

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A global UV radiometer (Kipp and Zonen, model CUV3) with typical sensitivity of 264 lV W1 m2, mounted on a platform tilted 37 (the same angle as the CPCs) provided data in terms of incident WUV m2. The temperature in the reactors was in the range of 2548 C. 2.3. Analysis Dissolved organic carbon (DOC) measurements were performed using a TOC analyser (Shimadzu, model 5050A) provided with an Autosampler ASI-5000A Shimadzu. Changes in the absorbance were observed using a UVvisible spectrophotometer (Unicam, UV/ VIS Spectrometer CV2). The needed amount of Na2S2O8 was monitored by measuring the pH of the samples with a GLP21 Crison pHmeter, while the consumption of H2O2 during the reaction was followed by iodometry. 2.4. Comparison of daily solar UV-power The global UV radiometer used in the Plataforma Solar of Almeria, provides data in terms of incident WUV m2, which gives the energy reaching the surface of the reactors. Obviously, solar-UV power varies during the experiments. For this reason the following Eq. (3) was used for the treatment of data obtained during the experiments. Eq. (3) allows the comparison of experiments of dierent days, as well as their comparison with data from other photocatalytic experiments, which have been done in the given photocatalytic reactors (Malato et al., 2000); QUV;n QUV;n1 Dtn UVG;n ACPC V TOT 3

ues are similar to the DOC and COD values of the Viostamp wastewater, after the dyeing and rinsing processes. 3.1. Decolourisation and organic content reduction of cotton simulated wastewater (CSW) At rst, some preliminary experiments were performed, concerning the photocatalytic oxidation of 0.1126 g l1 Black-HFGR-Triactive (BGT) dye, one of the substitutes of CSW. The quantity of BGT was the same used for the preparation of the CSW, and experiments were carried out in the presence and absence of NaCl. Results of the photocatalytic decolourisation of a BGT solution containing 0.5 g l1 TiO2 P-25 under solar irradiation are shown in Fig. 2. The amount of the BGT in the supernatant as determined from the spectrophotometric measurements is plotted as a function of the accumulated solar energy. Since there is a linear dependence between the initial concentration of the dye and the absorption at 611 nm, during the experimental procedure, the photodecomposition is monitored spectrophotometrically at this wavelength. As laboratory blank experiments by articial illumination had shown, in the absence of any catalyst a very small decrease in the concentration of BGT was observed, while the dark adsorption of the dye onto the TiO2 surface under the given experimental conditions led to a decrease of less than 15% of its concentration. As it appears in Fig. 2, the presence of an oxidant such as H2O2 enhances signicantly the reaction rate, while the inuence of NaCl under the given experimental conditions has almost no eect in the decolourisation

abs/abs0 (at 611 nm)

where tn is the experimental time for each sample, UVG,n is the average UVG during Dtn, ACPC is the collectors surface (3.09 m2), VTOT is the total plant volume (35 l) and QUV,n is the accumulated energy (per unit of volume) in kJ l1 incident on the reactor for each sample taken during the experiment.

1.0 0.8 0.6 0.4 0.2 0.0 0 10 20 30

-1

max error

3. Results and discussion During the photocatalytic experiments, the eect of two dierent TiO2 catalysts, in the presence or absence of some oxidizing agents such as H2O2 and Na2S2O8 was studied, as well as the inuence of the photo-Fenton reagent on the decolourisation, and the decrease of the dissolved organic content of the two simulated dyestu euents. In all the experiments 35 l of the synthetic wastewater were used with an initial organic carbon content of 0.15 g l1 (0.5 g l1 COD) and of 0.15 g l1 (0.55 g l1 COD) for NSW and CSW, respectively. These val-

40

50

Q UV (kJ L )
Fig. 2. Decolourisation of a Black-HFGR-Triactive dye solution (0.1126 g l1) as a function of the accumulated solar energy under various experimental conditions at pH = 5.7: (m) 0.5 g l1 TiO2 P-25; (.) 0.5 g l1 TiO2 P-25, +3 g l1 NaCl; () 0.5 g l1 TiO2 P-25 + 0.51 g l1 H2O2, (+) 0.5 g l1 TiO2 P-25 + 0.51 g l1 H2O2 + 3 g l1 NaCl.

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process. Experiments concerning the decolourisation of a BGT solution in the presence of the photo-Fenton reagent (0.056 g l1 Fe+3/0.51 g l1 H2O2) showed that this process is faster in comparison to the TiO2/H2O2 system (data not shown in Fig. 2). The DOC reduction as a function of the accumulated solar energy during the photocatalytic oxidation of Black-HFGR-Triactive is shown in Fig. 3. From these ndings it is clear that the addition of oxidants accelerates also the mineralisation in comparison to TiO2 alone, while the photocatalytic oxidation in the presence of the photo-Fenton reagent, as can be seen in Fig. 3, is a faster and more eective process in terms of decolourisation and DOC reduction, in comparison to the analogous TiO2/oxidant system. From the standpoint of solar collecting technology, the treatment with TiO2 alone is a rather inecient process, even for a high added-value application (Hermann et al., 1998). Solar advanced oxidation processes have, over other advanced oxidation technologies (AOPs), the advantage of using natural sunlight and having as its main characteristic, the fact that they are environmentally friendly technologies. In principle, the process involves a mild catalyst working with mild oxidants under mild conditions. However, as the concentration and the number of contaminants increase, the process becomes more complicated and challenging problems such as slow kinetics, low photoeciency and unpredictable mechanisms need to be solved. For these reasons, it is clear that naked TiO2 needs extra help to undertake practical applications of industrial and environmental interest. The addition of other powerful oxidizing spe-

cies, such as hydrogen peroxide (H2O2) or potassium peroxydisulphate (Na2S2O8) to TiO2 suspensions, is a well-known procedure and in many cases leads to an increase in the rate of photooxidation (Malato et al., 2000; Wolfrum and Ollis, 1994; Poulios and Tsachpinis, 1999; Malato et al., 2001). H2O2 is considered to have two functions in the process of photocatalytic oxidation. It accepts a photogenerated electron from the conduction band of the semiconductor (Eq. (4)) and thus promotes the charge separation. Also it forms OH radicals according to Eq. (5), while a possible reaction of H2O2 with the parent compounds or the intermediates cannot be excluded H2 O2 e ! OH OH CB H2 O2 O2 ! OH OH O2 4 5

The eect of this electron acceptor deserves some further comments. In some cases, the addition was found to be benecial since it is increasing the degradation rate. The eect depends on H2O2 concentration, generally showing an optimum range. Whereas the acceleration eect can easily be explained in terms of prevention of electron/hole recombination and additional OH production through reactions 4 and 5, inhibition could be explained in terms of TiO2 surface modication by H2O2 adsorption, scavenging of photoproduced holes (Eq. (6)) and reacting with hydroxyl radicals (Eq. (7)) or with TiO2 and formating peroxo compounds, which are detrimental to the photocatalytic action H2 O2 2h ! O2 2H VB H2 O2 OH ! H2 O HO2 6 7

1.0 0.8

max error

DOC/DOC0

0.6 0.4 0.2 0.0 0 10 20 30

-1

tn=4.5 h

Na2S2O8 on the other hand, can also trap the photogenerated conduction band electrons producing simultaneously the sulphate radical, a very strong oxidant (standard potential of persulphate reduction, EO = 2.6 V), which can participate in the degradation process. The reactions where peroxydisulphate is involved and is responsible of its eciency are the following; S2 O2 e ! SO2 SO4 CB 8 4 8 9 10 11 12

40

50

SO e ! SO2 CB 4 4 SO H2 O ! SO2 OH H 4 4 SO DOC0 ! SO2 DOC1 4 4 SO DOC1 ! ! SO2 CO2 4 4

Q UV (kJ L )
Fig. 3. Photocatalytic reduction of the dissolved organic carbon of a Black-HFGR-Triactive solution (0.1126 g l1) as a function of the accumulated solar energy under various experimental conditions at pH = 5.7: (j) 0.056 g l1 Fe+3 + 0.51 g l1 H2O2, pH = 3.3; (d) 0.056 g l1 Fe+3 + 0.51 g l1 H2O2 + 3 g l1 NaCl, pH = 3.3; (m) 0.5 g l1 TiO2 P-25, pH = 5.7; (.) 0.5 g l1 TiO2 P-25, +3 g l1 NaCl, pH = 5.7, () 0.5 g1 TiO2 P-25 + 0.51 g l1 H2O2, pH = 5.7; (+) 0.5 g l1 TiO2 P-25 + 0.51 g l1 H2O2 + 3 g l1 NaCl, pH = 5.7.

where e is the electron generated in the TiO2 conducCB tion band and DOC1 symbolises the organics partially transformed previously to the total oxidation until carbon dioxide. Obviously, the reactions in Eqs. (8) and

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(9) enhanced the photocatalytic reaction rate by avoiding e/h+ recombination. As shown in Fig. 3, the high concentration of Cl ions leads to a reduction of the eectiveness of the heterogeneous and the homogeneous photocatalytic oxidation, although its inuence on the decolourisation of BGT is negligible. The inhibition of the oxidation process due to the presence of NaCl, that are usually in the textile industry wastewater in high concentrations, can be explained as a result of the reaction of photoproduced OH with the Cl ions (Eq. (13)). Cl OH ! Cl OH 13 Cl h ! Cl Cl Cl ! Cl 2 14

below 300 nm indicates that the aromatic rings of the various organic compounds contained in CSW, are also breaking down. In Fig. 5 and Fig. 6 the results of the photocatalytic decolourisation and dissolved organic carbon (DOC) reduction of the CSW, respectively, are presented. All the experiments were performed at an initial pH value of 3.3, in order to remove the inorganic carbon, originating from Na2CO3 contained in the simulated wastewater. The oxidants were added in 5 portions in each experiment. The rst portion was added in the dark

1.0

15
abs/abs 0 (611nm)
0.8 0.6 0.4 0.2 0.0 0 10 20 30 40
-1

max error

The Cl and Cl radicals are in principle also capable 2 of oxidizing pollutants, but at lower rates than the OH radicals, due to their lower oxidation power (Kiwi et al., 2000). The generation of Cl radicals leads also to the formation of chlorinated organic compounds (AOX) (Arslan et al., 2000), which are known as very harmful substances and therefore longer treatment periods are needed. Fig. 4 shows the change in the absorption spectra of an aqueous solution of CSW with 0.15 g l1 initial DOC, containing 0.5 g l1 TiO2 P-25 and 0.15 g l1 H2O2 at pH = 3.3. The absorption spectrum seems to decrease in intensity with increasing irradiation time, vanishing almost completely within 27 kJ l1, which corresponds to 3 h of illumination. The rapid disappearance of the absorption bands in the visible regions suggests that the chromophore groups responsible for the characteristic colour of the wastewater are breaking down, while the reduction of the intensity of the absorption bands

50

60

Q UV (kJ L )
Fig. 5. Photocatalytic decolourisation of the cotton simulated dyestu euent (CSW) under various experimental conditions; ( ) 0.5 g l1 TiO2 P-25, pH = 3.3: (j) 0.5 g l1 TiO2 P-25 + 1.5 g l1 H2O2, pH = 3.3, (d) 0.5 g l1 TiO2 (A) + 1.5 g l1 H2O2, pH = 3.3; (m) 0.5 g l1 TiO2 P-25 + 2.6 g l1 Na2S2O8, pH0 = 8; (.) 0.5 g l1 TiO2 (A) + 2.6 g l1 Na2S2O8, pH0 = 8; () 0.056 g l1 Fe+3 + 1.5 g l1 H2O2, pH = 3.3.

1.4

150

max error

DOC (mg L-1)

1.2

Optical Density

1.0 0.8 0.6 0.4 0.2 0.0 200 300 400 500

before photocatalysis after 3 kJ -1L of Q UV after 7 kJ -1L of Q UV after 17 kJ-1L of Q UV after 27 kJ-1L of Q UV

100

t n=5

50

0 0 10 20 30 40
-1

50

60

Q UV (kJ L )
600 700 800

Wavelength (nm)

Fig. 4. Change in absorption spectrum of the cotton simulated dyestu euent (CSW) at dierent quantities of accumulated solar energy, in the presence of 0.5 g l1 TiO2 P-25 and 1.5 g l1 H2O2 (pH =3.3).

Fig. 6. Photocatalytic reduction of the dissolved organic carbon of the cotton simulated dyestu euent (CSW) under various experimental conditions: (j) 0.5 g l1 TiO2 P-25 + 1.5 g l1 H2O2, pH0 = 3.3; (d) 0.5 g l1 TiO2 (A) + 1.5 g l1 H2O2, pH = 3.3, (m) 0.5 g l1 TiO2 P-25 + 2.6 g l1 Na2S2O8, pH0 = 8; (.) 0.5 g l1 TiO2 (A) + 2.6 g l1 Na2 S2O8, pH0 = 8, () 0.056 g l1 Fe+3 + 1.5 g l1 H2O2, pH = 3.3.

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Table 1 Comparison of the apparent rate constant of decolourisation (kapp), the initial mineralisation rate (r0) and the accumulated energy (Q0.5) by photocatalytic treatment of the cotton simulated wastewater (CSW) under various experimental conditions Experimental conditions 0.5 g l TiO2 P-25, pH = 3.3 0.5 g l1 TiO2 P-25 + 1.5 g l1 H2O2, pH = 3.3 0.5 g l1 TiO2 P-25 + 2.8 g l1 Na2S2O8, pH = 8 0.5 g l1 TiO2 (A) + 1.5 g l1 H2O2, pH = 3.3 0.5 g l1 TiO2 (A) + 2.8 g l1 Na2S2O8, pH = 8 0.056 g l1 Fe+3 + 1.5 g l1 H2O2, pH = 3.3
1

kapp (l kJ1) 0.010 0.001 0.270 0.009 0.084 0.003 0.120 0.002 0.042 0.001 0.463 0.08

r0 (mg kJ1) 9.82 2.28 3.5 1.0 4.51 1.26 1.02 0.15 12.77 2.86

Q0.5 (kJ l1) 7.26 32.2 50.6 4.1

and the others every hour of illumination of the synthetic wastewater. The apparent rate constant (kapp) of decolourisation, the maximal initial mineralisation rate (r0), as well as the accumulated energy necessary for the mineralisation of 50% (Q0.5) of the initial dilute organic content of the simulated wastewater, under various experimental conditions, are shown in Table 1. Taking into account that the decolourisation follows a rst order reaction, an empirical rate constant (kapp) can be obtained from the slope of ln(abs/abs0) as a function of the accumulated solar energy (abs is the absorbance of the CSW at 611 nm wavelength, at dierent reaction times). On the other hand, since DOC is a sum parameter including several products, the mineralisation does not follow simple kinetic models, therefore the overall reaction rate constants cannot be calculated. For this reason the parameters r0, Q0.5 have been chosen (Malato et al., 2000) in order to obtain a practical grip on the experiments for their comparison. The r0 values, under various experimental conditions, were independently obtained by a linear t of the DOC concentrationQUV data, taking into account a reduction of the initial DOC reaching $30%. Results of the decolourisation of 0.15 g l1 DOC of a CSW solution under various experimental conditions are shown in Fig. 5. The colour changes in the supernatant are expressed as abs/abs0 as a function of the accumulated solar energy. Since there is a linear dependence between the initial concentration of the CSW and the absorbance of the CSW at 611 nm, during the experimental procedure the decolourisation is monitored spectrophotometrically at this wavelength. From Fig. 5 it is clear that in the case of heterogeneous photocatalytic oxidation the presence of TiO2 alone leads to a small decrease of the absorption of the CSW solution. After an accumulated energy of 50 kJ l1 ($5 h of illumination) 54% of the colour and 80% of the organic content (not shown in Fig. 6) remains in the solution. As shown in Figs. 5, 6 and Table 1, the addition of oxidants enhances signicantly the decolourisation and mineralisation process, with TiO2/H2O2 being more ecient in comparison to the synergetic action which ap-

pears when using persulphate and TiO2, in this specic wastewater. Under these experimental conditions the addition of Na2S2O8 enhances the decolourisation and the initial rate of DOC reduction, while in the presence of H2O2 an accumulation energy of $50 kJ l1 results in a 70% decrease of the initial DOC value in the case of TiO2 P-25 and 49% in the case of TiO2 (A). Additionally the results in Figs. 5, 6 and in Table 1 demonstrate that TiO2 (A) represents a catalyst with good photocatalytic properties, perhaps more suitable to use in real wastewater applications from an economical point of view, since it gives similar results and costs much less than TiO2 P-25, which in most cases represents the best commercially available catalyst for photocatalytic applications. As presented in Figs. 5, 6 and Table 1 the homogeneous photocatalytic oxidation (photo-Fenton reagent) is more ecient in comparison to the heterogeneous one, in terms of colour and DOC reduction in this specic wastewater. In the presence of photo-Fenton reagent complete decolourisation is achieved by an accumulated energy of 8.2 kJ l1, while an accumulated energy of 50 kJ l1 leads to a 90% DOC reduction. 3.2. Decolourisation and organic content reduction of nylon simulated wastewater (NSW) Fig. 7 shows the change in the absorption spectra of an aqueous solution of NSW with 0.15 g l1 initial DOC, containing 0.5 g l1 TiO2 P-25 and 1.5 g l1 H2O2 (pH = 3.3). The absorption spectrum decreases in intensity with increasing irradiation time, vanishing almost completely in the visible region within 10 kJ l1 of accumulated solar energy (1 h of irradiation). As in the case of CSW, the breaking down of the chromophore groups of the dyes, is responsible for the rapid disappearance of the absorption bands in the visible region, while reduction of the latter below 300 nm indicates breaking down of the aromatic rings of the dierent compounds in the wastewater. In Figs. 8 and 9 the results of the photocatalytic decolourisation and organic content reduction, respectively, of the simulated nylon dyestu euent are given, while

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1.5

Optical Density

DOC (mg L-1 )

before photocatalysis after 10 kJ-1 L of QUV after 22 kJ-1 L of QUV after 34 kJ-1 L of QUV

150

max error

1.0

100

tn=5 h

0.5

50

0.0 250 300 350 400 450 500 550 600 0 0 10 20 30 40

-1

Wavelength (nm)
Fig. 7. Change in absorption spectrum of the nylon simulated dyestu euent (NSW) at dierent quantities of irradiated solar energy, in the presence of 0.5 g l1 TiO2 P-25 and 1.5 g l1 H2O2 (pH = 3.3).

50

60

Q UV (kJ L )

Fig. 9. Photocatalytic reduction of the dissolved organic carbon of the nylon simulated dyestu euent (NSW) under various experimental conditions: (j) 0.5 g l1 TiO2 P-25 + 1.5 g l1 H2O2, pH = 3.3; (d) 0.5 g l1 TiO2 (A) + 1.5 g l1 H2O2, pH = 3.3; (m) 0.5 g l1 TiO2 P-25 + 2.6 g l1 Na2S2O8, pH0 = 3; (.) 0.5 g l1 TiO2 (A) + 2.6 g l1 Na2S2O8, pHo = 3, () 0.056 g l1 Fe+3 + 1.5 g l1 H2O2, pH = 3.3.

1.0 0.8 0.6 0.4 0.2 0.0 0 10 20 30 Q UV (kJ L )

-1

max error

40

50

60

Fig. 8. Photocatalytic decolourisation of the nylon simulated dyestu euent (NSW) under various experimental conditions: ( ) 0.5 g l1 TiO2 P25; (j) 0.5 g l1 TiO2 P-25 + 1.5 g l1 H2O2, pH = 3.3 (d) 0.5 g l1 TiO2 (A) + 1.5 g l1 H2O2, pH = 3.3, (m) 0.5 g l1 TiO2 P-25 + 2.6 g l1 Na2 S2O8, pH0 = 3, (.) 0.5 g l1 TiO2 (A) + 2.6 g l1 Na2S2O8, pH0 = 3; () 0.056 g l1 Fe+3 + 1.5 g l1 H2O2, pH = 3.3.

Table 2 shows the apparent rate constant (kapp) of decolourisation, the maximal initial mineralisation rate (r0), as well as the accumulated energy necessary for the mineralisation of 50% (Q0.5) of the initial dilute organic content of the nylon synthetic wastewater under various experimental conditions. Fig. 8 presents the decolourisation of NSW, which in this case has been followed spectrophotometrically by the absorbance at 440 nm, while Fig. 9 presents the corresponding DOC reduction. Both the decolourisation and the DOC reduction, follow the same course as with the CSW wastewater, but the overall eciency of the photocatalytic process in this wastewater is denitely lower that the one in the case of CSW, especially in the DOC reduction. By an accumulated energy of 50 kJ l1 a 54% and 47% DOC reduction has been achieved in the case of TiO2 P-25/H2O2 and TiO2 (A)/H2O2, respectively, while also in this case the photo-Fenton reagent is more eective in comparison to the TiO2/oxidant system. In the presence of photo-Fenton reagent

Table 2 Comparison of the apparent rate constant of decolourisation (kapp), the initial mineralisation rate (r0) and the accumulated energy (Q0.5) by the photocatalytic treatment of the nylon simulated wastewater (NSW) under various experimental conditions Experimental conditions 0.5 g l1 TiO2 P-25, pH = 3.3 0.5 g l1 TiO2 P-25 + 1.5 g l1 H2O2, pH = 3.3 0.5 g l1 TiO2 P-25 + 2.8 g l1 Na2S2O8, pH = 3 0.5 g l1 TiO2 (A) + 1.5 g l1 H2O2, pH = 3.3 0.5 g l1 TiO2 (A) + 2.8 g l1 Na2S2O8, pH = 3 0.056 g l1 Fe+3 + 1.5 g l1 H2O2, pH = 3.3 kapp (l kJ1) 0.017 0.002 0.202 0.019 0.113 0.02 0.047 0.004 0.034 0.006 0.100 0.016 r0 (mg kJ1) 3.64 0.745 3.51 0.26 3.00 3.48 0.28 9.14 0.47 Q0.5 (kJ l1) 40.3 32.8 53.7 36.2 8.2

abs/abs 0 (440nm)

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complete decolourisation is achieved by an accumulated energy of 15 kJ l1, while an accumulated energy of 50 kJ l1 leads to a 75% DOC reduction.

Research and Development, Improving Human Potential programme, Contract HPRI-CT1999-00013.

References 4. Conclusions In this study, the decolourisation and the reduction of the organic content of two synthetic dyestu euents have been studied by applying a heterogeneous and a homogeneous solar photocatalytic method. From the results reported above it is clear that, under the specic experimental conditions of this work: (a) the synergetic action of TiO2 with oxidants such as H2O2 and Na2S2O8 leads to complete decolourisation and to a substantial increase of the initial reaction rate and the extent of mineralisation in comparison to the TiO2 alone. (b) the photo-Fenton experiments were considerably faster than those with TiO2, but a detailed experimental and economical analysis has to be made in order to reach at a conclusion about the most appropriate method for application. An increase in the eciency of the decolourisation and DOC reduction in this type of wastewater could be reached by optimising further the experimental conditions. From the results of the present work and relevant reports in the literature one could claim that the solar photocatalytic treatment of dyestu euents could be employed as a powerful alternative tool for the decolourisation and reduction of the organic content of this liquid waste. The use of solar light, combined with the simple technology required for this method, can oer economically reasonable and practical solutions to the processing of this liquid waste. The textile industry wastewater, apart from the nonbiodegradable compounds, also includes large amounts of salts such as NaCl, etc. Since the daily euents of such an industry are of great volume, it is very important from both ecological and economical point of view, to nd a way to recycle and reuse the water of these euents. An oxidation process such as solar detoxication, in conjunction with a ltration method (e.g. nanoltration), would probably lead to environmentally acceptable and economical solutions, in the context of the dyestu euents treatment, which follow the European Union directions of wastewater treatment and reuse.
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