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Advances in Ma terials Physics and Che mist ry, 2012, 2, 274-276 doi:10.4236/ampc.2012.24B070 Published Online December 2012 (http://www.SciRP.org/journal/ampc) Copyright © 2012 SciRes. AMPC Photocatalytic Degradation of Ethylene Dichloride in Water Using Nano TiO2 Supported on Clinoptilolite as a Photocatalys t Mano uc he hr Nikaza r, Soheil Jalali Farahani, Mastan eh R ez a Soltan i Chemical Engineering Department of Amirkabir University of Technology, Tehran, Iran Email: nikazar@aut.ac.ir Received 2012 ABSTRACT In this article one of the advanced oxidation processes (AOP) combined methods, photocatalyst /H2O2, is utilized in order to study photodegradation of ethylene dichloride (EDC) in water. Nano Titanium (IV) Oxide, supported on Clinoptilolite (CP) (Iranian natural zeolite) using solid-state dispersion (SSD) method for improvement of its photocatalytic properties. The results show that the TiO2/Clinoptilolite (SSD) is an active photocatalyst. The effects of five important photocatalytic reaction parameters including the initial concentration of ethylene dichloride, the ratio of TiO2/Clinoptilolite, the catalyst concentration, H2O2 concentration and pH in photodegradation of ethylene dichloride were examined. In this experiments, the design and also the optimum parameters were ob- tained by Taguchi Method, using Design Expert8® software. Taguchi's L27 (5^3) orthogonal array design was employed for the experimental plan. Four parameters were found to be significant whereas, pH was found to be an insignificant parameter after con- ducting experiments. A first order reaction with K = 0.007 min-1 was observed for the photocatalytic degradation reaction. Keywords: Photodegrada tion; Photocatalysts; TiO2/Clinoptilolite; Ethylene Dichloride 1. Introduction Effects of several different pollutions such as phenol com- pounds, alcohols, organic acids, hydro-carbonic sulfur com- pounds, pesticides and insecticides compounds, dyes, output wastewater from various industries and et c. using p hotocatal yt- ic oxidation has been investigated on sewage treatment. All of these experiments show high efficiency in degradation and removal of these pollutions from water and sewage by this me- thod [1,2]. Usual biological treatment methods for hazardous compounds such as chlorinated hydrocarbons are not efficient, because of high toxicity of these compounds which results in destroying microorganisms. TiO2 is one of the most effective photocatalysts due to its biological and chemical inertness and photo stability in near- UV band ener gy gap, and can be u s ed as a fine powder or crystals dispersed in water and wastewater treatment applications. However, the need to filter TiO2 par- ticles after reaction makes such a process troublesome and costly. Thus, in order to solve this problem, many researchers have examined several methods for fixing TiO2 on supporting materials including glass beads [3-5], fiber glass [6-8], silica [9,10], and zeolite [11,12]. When using zeolite as TiO2 support, care should be taken that TiO2 does not lose its photo activity and the adsorption properties of zeolite are not affected. Mat- thews [4] showed that the photo efficiency of TiO2 is sup- pressed when TiO2 is in interaction with the zeolite. In this work TiO2 was supported on a zeolite without losing photo efficiency and affecting the adsorption properties of zeo- lite u sing the exact metho d suggest ed by Nikazar et. al. [13] for supporting TiO2 on Clinoptilolite. This mixture was used for photodegradation of aqueous EDC. 2. Experimental 2.1. Materials Degussa P-25 titanium dioxide with a crystallographic mode of 80% anatase and 20% rutile, a 50 m2g-1 BET surface area and an average p article si ze of 30 n m (accord ing to the manufactur- er’s specifications) and the raw material was an Iranian com- mercial Clinoptilolite (CP) (Afrand Tuska, Iran) from deposits in the region of Semnan. According to the supplier’s specifica- tions, it contains about 90 wt% CP (based on XRD internal standard quantitative analysis) and the Si/Al molar ratio is 5.78. The concentration of Fe2O3, TiO2, MnO and P2O5 impurities has been reported to be 1.30, 0.30, 0.04 and 0.01 wt% respec- tively, and were used for preparation of the photocatalyst. Merck H2O2 with 30% purity, and Ethylene dichloride (EDC) produced by Bandar Imam Petrochemical Comlex, with 96% purity for making reacting solution. 2.2. Preparation of TiO2-supported on C P Catalysts The Solid State Dispersion (SSD) method was applied for sup- porting photocatalyst on zeolite. In this method, nano titanium peroxide was mixed with CP using ethanol as a solvent and mixture was grinded for 3 hours. Ethanol was then removed by evaporation. Samples were dried at 110°C in the oven and cal- cined at 450°C in the furnace for 5 hours to obtain TiO2-supported zeolite photocatalysts [13]. 2.3. Apparatus Photocatalytic reaction was performed in a batch Pyrex double M. NIKAZAR ET AL. Copyright © 2012 SciRes. AMPC 275 wall reactor of 1.5 L in volume with two 8-W UV-C mercury lamps locat ed in qu artz tub es inside th e reactor. The tub es were made from quartz because UV-C light cannot pass through glass and Pyrex.The photo reactor used in this experiment is shown in Figure 1. Circulator has been used for temperature adjustment and GC VARIAN CP-3800 was used for EDC con- centration measur ement. 2.4. Procedures A solution containing known concentration of EDC was pre- pared; subsequently 800 cc of this solution was poured into the reactor. The solution pH value was adjusted at desired level using dilute NaOH and H2SO4. Then certain amount of pre- pared photocatalyst and H2O2 was added to the solution. Pho- tocatalytic reaction took place under the radiation of mercury lamps while agitation and aeration was maintained to keep the suspension homogeneous and oxygenized. Sampling was per- formed at specified times and concentration of EDC was de- termined using GC. 3. Design of Experiments Effects of five parameters that influence the efficiency of pho- tocatalytic reaction have been studied in these experiments. Initial concentration of pollutant (EDC), H2O2 concentration, catalyst amount, TiO2% and pH, each of them in three levels, are shown in Table 1. Because of numerous studying parameters, each at 3 differ- ent levels, Taguchi method for design of experiments using Figure 1. Schematic of photo reactor. Table 1. Experimental parameters and their levels. Process Parameters Level 1 Level 2 L evel 3 Catalyst Concentration g/L A 0.1 0.25 0.5 H2O2 Concentration (ppm) B 0 50 100 Initial Concentration of EDC (ppm) C 200 400 600 pH D 4 7 10 TiO2% E 10 15 20 Design Expert 8.0.5® was employed to decrease the number of experiments to 27 for obtaining optimum terms. Temperature is one of the effective parameters on photocatalytic reactions that are usually set at ambient temperature, but due to high volatility of ethylene dichloride in the ambient temperature and aeration during process, large amount of EDC would be vaporized from the solution. Therefore, reaction’s temperature was set at 5°C using circulator. Temperature is one of the effective parameters on photoca- talytic reactions that are usually set at ambient temperature, but due to high volatility of ethylene dichloride in the ambient temperature and aeration during process, large amount of EDC would be vaporized from the solution. Therefore, reaction’s temperature was set at 5°C usi ng circulator. 4. Results and Discussion 4.1. Taguchi Method ANOVA analysis is shown in the Table 2. SUM of Squares: sum the squared differences between the average val ues for the blocks and the overall mean. DF: degrees of freedom attributed to the blocks, generally equal to one less than the number of blocks. Mean square: estimate of the block variance, calculated by the bock sum of squares divided by block degrees of freedom. The F -value of 33.10 implies the model is significant Values of “Prob > F” less than 0.0500 indicate mod el terms are si gnif- icant. In this case A, B, C, E are sign ificant model terms. In the Figure 2 we can see a grap h of the predict ed response Table 2. ANOVA analysis report. Source Sum of Squares DF Mean Squa re F Value Prob. > F Model 52.27853 8 6.5348162 33.101924 < 10-4 A-[Catal] 10.67263 2 5.336314 27.030945 < 10-4 B-[H2O2] 4.036541 2 2.018270 4 10.223491 0.0011 C-[EDC]0 31.6 9998 2 1 5.849991 80.287672 < 10-4 E-TiO2% 5.86938 2 2.9346898 14.865587 0.0002 Residual 3.55 347 18 0.197415 Cor Total 55.832 26 7.88595 2.3486 Actual Predicted Predicted vs. Actual 2.00 3.00 4.00 5.00 6.00 7.00 8.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 Figure 2. Predicted vs. Actual plot. M. NIKAZAR ET AL. Copyright © 2012 SciRes. AMPC 276 values versus the actual response values. It is clear that all of the values are predicted by the model. Responses should be assigned as “larger is better” for en- hanci ng optimized parameters as showed below: [Catal] [H2O2] [ EDC]0 pH TiO2% R1 Desirability 0.25 50 200 7 15 0.739634 1 4.2. Kinetics of Photocatalytic Degradation of EDC Several experiment al res ul ts ind icated t hat the d egradat ion rates of photocatalytic oxidation over illuminated TiO2 fitted by the fir st-order kinetic model [14-16]. Figure 3 shows the plot of ln([EDC]0/[EDC]) vs. irradiation time for EDC. The linearity of plot suggests that the photodegradation reaction approximately follows the pseudo-first order kinetics with K = 0.007 min-1. 4.3. Effects of UV Irradiation and Photocatalyst Ingredient In Figure 4 the comparison of four experiments is shown. First column is degradation efficiency of EDC using only UV light without photocatalyst, this column shows the importance of photocatalyst because eliminating photocatalyst from reaction caused decrease in efficiency about 47%. Second column is about degradation efficiency of EDC employing 15% wt TiO2 photocatalyst without UV irradiation, this column shows influ- ence of UV light in activating photocatalyst, reaction efficiency with elimination of UV light cause 45% efficiency reduction. Third column is shown degradation efficiency of EDC using pure TiO2 (degussa P25 without zeolite) catalyst with UV ir- radiation, supporting catalyst on zeolite increase reaction effi- ciency about 37%. In last column degradation efficiency of EDC with optimum parameters has been brought for compari- son. All of the other parameters are the same. Figure 3. Plot of reciprocal of pseudo-first order rate constant against initial concentration of EDC = 200 ppm, concentration of photocatalyst (15 wt% TiO2/CP) = 0.25 g/L, [H2O2]=50 ppm, T = 278 K, pH = 7. Figure 4. Comparison of degradation efficiency in four different experiment in T= 278 K, pH=7, [H2O2]=50 ppm, [EDC] 0=200 ppm, [catalys t] = 0.25 g/ L. 5. Conclusion 1. SSD method is an effective method for supporting TiO2 on Clinoptololite. 2. The following optimum terms obtained with Taguchi method : Initial concentration of EDC 200 ppm, catalyst concentration 0.25 g/L, H2O2 concentration 50 ppm, TiO2% 15 and effect of pH and two parameters interactions were not significant enough. 3. Initial concentration of EDC, Catalyst concentration, TiO2% and H2O2 concentration were effective in reaction effi- cienc y, respectively. 4. Maximum efficiency of 74% for photocatalytic degrada- tion of EDC was obtained with optimized parameters. 5. The kinetic of photocatalytic degradation of EDC is of the pseudo-first order with K = 0.007 min-1. REFERENCES [1] A. Shafai, M. Nikazar, et al., ”Petrochemical wastewater treatment containing heavy metals and TPA using EC and nano photocatalyst processes”, PhD Thesis (2009). [2] M. R. Hoffmann, S. T. Martin, W. Choi and D. W. Bahnemann, “Environmental application of semicondustor photocatalysis”, Chem. 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