Journal of Chongqing University (English Edition) [ISSN 1671-8224]

Vol. 8 No. 3 September 2009

Article ID: 1671-8224(2009)03-0165-05

To cite this article: LIU Jian-hua, WANG Huai-jun. Treating dye wastewater by TiO2 coated on coal cinder [J]. J Chongqing Univ: Eng Ed [ISSN 1671-8224], 2009, 8(3): 165169.

Treating dye wastewater by TiO2 coated on coal cinder

LIU Jian-hua 1,2,, WANG Hai-jun 2
1

Key Laboratory of Yangtze River Water Environment, Ministry of Education, Yibin University, Sichuan 644000, P. R. China
2

Department of Chemical and Material Engineering, Jiangnan University, Jiangsu 214122, P. R. China Received 21 April 2009; received in revised form 5 May 2009

Abstract: We investigated the photocatalytic degradation of dye wastewater by using titanium dioxide (TiO2) coated on a coal cinder. The coal cinder was used as the carrier, with a thin film of TiO2 coated on it by using the sol-gel method. Using the Congo red as the model pollutant for dye wastewater, we studied the decolorization efficiency, and effects of TiO2 film thickness and roasting temperature on the efficiency. We also evaluated the recycling and regeneration of the immobilized TiO2 (TiO2/cinder). Results show that the decolorization rate of Congo red solution was more than 98% after 2 h treatment when we used TiO2/cinder calcined at 500 C for 2 h and coated four times as the photocatalyst. At the same time, the TiO2/cinder remained high catalytic activity after being reused and regenerated for many times. Keywords: titanium dioxide; coal cinder; Congo red; dye wastewater; photocatalysis
CLC number: O643.36 Document code: A

Introduction a

The majority of dyes used in the textile industry are the azo dyes, accounting for more than 50% of all commercial dyes. These dyes include azo groups (N=N) mainly bound to substituted benzene or naphthalene rings [1]. Dyes are visible even of small quantities (0.005 mg), and the color of dyes can interfere with transmission of sunlight into natural streams. Furthermore, many of the azo dyes and their intermediate products, such as aromatic amines, are toxic to aquatic life, carcinogenic and mutagenic to humans. Consequently, dyes have to be removed from textile wastewater before discharge [2]. Dye wastewater is characterized by high concentration, complicated component, deep color, and difficult to biodegrade. Treatment of wastewater by conventional chemical coagulation and biological

LIU Jian-hua (): Liujianhua418@126.com. Funded by the Youth Fund Project of Yibin University (No. QJ0528).

methods to reduce biological oxygen demand (BOD), chemical oxygen demand (COD), and suspended solid are generally satisfactory, except the removal of dye color [3]. Therefore, the decolorizing treatment of dye wastewater is a difficult problem to solve. Many researchers have studied on the semiconductor as a photocatalyst in decolorization of dye wastewater [4]. Among a variety of photo catalysts, titanium dioxide (TiO2) is the most preferable due to its non-toxic, insoluble, stability, high photoactivity and inexpensive nature [5-6]. However, the technology of photocatalysis has not been industrially applied to treating wastewater. The main problem of the application is the separation and reuse of powder photocatalyst. Such difficulty is more serious with nanometer-scale ultrafine powder [7-8]. We used the coal cinder as a photocatalyst carrier to solve this problem. Its main compositions are SiO2, Al2O3, Fe2O3, and CaO [9-10]. TiO2 attached on it can act as a composite photocatalyst, which shows higher catalytic activity for facilitating the separation of electron and hole during the reaction of photocatalysis. The coal cinder has high adsorbability because it has

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many pores on the surface and inner parts. Therefore, when used as the photocatalyst carrier, it improves the effect of photodegradation of wastewater and changes from solid waste into valuables. At present, although many researchers have studied on the wastewater treatment using coal fly ash and scrap ion as photocatalyst carriers, relatively less research has been carried out on treating wastewater by using photocatalyst fixed on cinder. Congo red, which is a stable basic azo dye, is a compound that contains azo groups (N=N). Due to its high stability, Congo red is commonly used as a titration indicator and a staining agent [11]. Moreover, as a typical direct azo dye of biphenyl amine, Congo red is commonly used in textile industries. Therefore, we chose it as a model pollutant in this study. 2 Experimental details

different temperature for 2 h and cooling it at room temperature. Then the TiO2 films on the cinder of different layers and roasting temperature were formed. 2.2 Photocatalysis experiments The reactor was a glass beaker (250 mL), in which 4.5 g cinder coated with TiO2 film were settled near the surface of solution (about 1 cm). Then, 200 mL solution of Congo red (20 mg/L) was added into the beaker and stirred by a magnetic stirrer. For indoor experiments, the light source was a lamp (Philips TLD 15 W) emitting between 300 nm and 450 nm. During the reaction, the solution was sampled every 30 min. The decolorization rate (X) was determined by measuring the absorbance at 504 nm using an UVvisible spectrophotometer.
X = ( A0 A)/A0 100% ,

2.1 Preparation of TiO2 on cinder 2.1.1 Pretreatment of cinder

where A0 and A were the initial absorbance and the reacting absorbance of Congo red, respectively. 3 Results and discussion

Coal cinder was pretreated to remove the chlorine ion and other organic compounds on it. Loose and porous cinder from the stokehold of Yibin University was used, which was broken into granule with the diameter of about 1.0 cm. The granules were soaked in a solution of hydrochloric acid (H2O:HCl 1:1) for 24 h, then taken out and washed for three times with distilled water and anhydrous ethanol, respectively. After dried in an oven, the cinder was put into muffle to be calcined at 500 C for 2 h, and cooled off for further use. 2.2.2 Preparation of TiO2 film on cinder The TiO2 film on cinder was prepared by the sol-gel method. In 100 mL anhydrous ethanol, 20 mL butyl titanate and 16 mL acetic acid were dissolved under vigorous stirring for 1 h (solution A). Under stirring, a mixture of 2 mL triethanolamine, 60 mL ethanol, and 16 mL water was dropwise added into the solution A. Then, 0.2 mL polyglycol was added in the solution and stirred for 30 min to form TiO2-sol. The resulting alkoxide solution was remained in the dark for 16 h to produce TiO2-gel. The TiO2 film was coated on the cinder as follows: 1) dipping the cinder in the TiO2-sol for 30 min and drying at room temperature; 2) repeating the operation for different times; 3) heating to

3.1 Influence of preparing condition of TiO2 film on decolorizing efficiency 3.1.1 Calcination temperature of TiO2 We performed a set of tests to study the influence of the TiO2/cinder calcination temperature on the decolorization of Congo red. In these studies, we only changed the calcination temperature of TiO2/cinder while keeping the coating times of TiO2 on cinder for four times. The total decolorizing reaction time was 2 h. The calcination temperature was an important factor affecting the photocatalysis efficiency. Fig. 1 shows that the decolorization rate increased as the calcination temperature of TiO2-cinder increasing. It reached the peak at 500 C. It has been proved that the content of anatase in TiO2 arrays increases with increasing heat treatment temperature. Near 500 C, the rutile phase emerges, and the content of rutile increases as the temperature increasing [12]. It is widely accepted that the anatase phase of titania is a relatively ideal photocatalytic material among its three crystalline phases [13]. In addition, the anatase with a small fraction of rutile shows enhanced photocatalytic activity compared to the pure anatase due to the electron and hole transfer

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between the two phases [14]. Beckley et al. [15] presented that the mixed crystal has higher catalytic activity compared to the pure anatase and rutile. The catalyst treated at 500 C has better photocatalytic efficiency. The reason is that the mixed crystal can facilitate the separation and prevent the recombination of cavities with electrons.

(UV) irradiation only; 2) using the cinder only; 3) using TiO2 under UV irradiation; 4) using TiO2/cinder under UV irradiation.

Fig. 2 Relationship between coating times and the decolorization rate Fig. 1 Influence of calcination temperature of TiO2-cinder on decolorization rate

3.1.2 Coating times of TiO2 on cinder We kept the calcination temperature of TiO2/cinder at 450 C, and changed the coating times only to study the influence of the coating times of TiO2 on cinder. The total reaction time of decolorization was 2 h. The coating times of TiO2 on cinder was an important factor affecting the efficiency of the photocatalysis. Fig. 2 shows that the decolorization rate increased as more coating times, and it reached the maximum value at four times. When the coating times were zero, the decolorization rate was 42%. This means that the cinder has high adsorbability, and it can partly decolorize the Congo red without TiO2 coating because it has many pores on its surface and inner parts. Increasing the number of the catalyst layers, the amount of TiO2 coated on the cinder is increased and the activity of photocatalysis reaction is improved. However, the cinder can not be coated for too many times. Otherwise, the coating film would be uneven, and will be easily crazed and separated from the cinder surface [16-17]. 3.2 Contrast experiment We decolorized the Congo red solution under the following conditions respectively: 1) using ultraviolet

Fig. 3 shows that the Congo red could be decolorized partly using UV irradiation or cinder without any catalyst. However, the decolorization efficiency was significantly improved by using TiO2/cinder as the photocatalyst under UV irradiation, suggesting that TiO2 could catalyze the decomposition of Congo red with the exposure of UV radiation. Recently, Strataki et al. [18] investigated the photodegradation mechanism of several dyes under UV irradiation. The photocatalytic degradation of organic dyes in wastewater using TiO2 (an n-type semiconductor) is initiated by light of wavelength 390 nm (3.2 eV). Then, electrons are excited from the valence band to the conduction band, generating positive holes and free electrons. The produced electron-hole pairs can recombine or interact with other organic substrates on the surface of TiO2 particles via oxidation and reduction reactions. In an aqueous solution, positive holes are scavenged by surface hydroxyl groups to produce very reactive oxidizing hydroxyl radicals (OH), which promotes the degradation process and subsequently leads to the total mineralization of the organic substrate [6,19]. The first step of organic oxidative decomposition is the oxidation of organic molecules with hydroxyl radicals produced on the photocatalyst surface. Therefore, the adsorption process of organic pollutant on photocatalyst is very important for heterogeneous photocatalytic reactions [20]. Coating TiO2 on cinder, which has strong adsorption capacity, can improve the decolorization efficiency of the Congo red. Moreover,

J. Chongqing Univ. Eng. Ed. [ISSN 1671-8224], 2009, 8(3): 165-169

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it can also solve the problem of TiO2 particles recovery.

Conclusion

Fig. 3 Decolorization rate of Congo red under different

We presented a new method combining the effect of adsorption and photodegradation in treating dye wastewater. Results show that the coating times of TiO2 on cinder and the calcination temperature of TiO2/cinder have considerable impact on the decolorization efficiency. Coated for four times and calcined at 500 C for 2 h, TiO2/cinder had the best photocatalytic efficiency. The TiO2 coated on cinder can be recycled and the method of regeneration may be used to maintain high efficiency of the photocatalyst. The TiO2 coated on cinder can solve the problem of separating TiO2 powder from water, and improve the decolorization efficiency of dye wastewater. However, full-scale experiments in future research are needed to ensure the application of this method. The degradation mechanism should be researched by studying the end products and intermediates produced during the photodegradation process of the dye wastewater. Acknowledgements

3.3 Recycling use of the TiO2/cinder film We compared the results of reusing TiO2/cinder to decolorize the Congo red for eight times directly and ultrasonicating the TiO2/cinder in distilled water for 30 minutes after each reaction (Fig. 4). Fig. 4 shows that the decrease of decolorization efficiency was inconspicuous after the TiO2 film was used for eight times directly. The decrease may be caused by the long-term or multiple use of TiO2 film, because possible adsorption of intermediates on TiO2 active sites might make the catalyst site unusable for degradation of fresh dye molecules [21-22]. The TiO2/cinder can be recovered simply by ultrasonicating it in distilled water for 30 min.

We greatly acknowledge the Youth Fund Project of Yibin University (No. QJ05-28). References
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Edited by XUE Jing-yuan

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