Ultrasonics Sonochemistry 14 (2007) 615620 www.elsevier.

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Treatment of dye wastewater by using photo-catalytic oxidation with sonication

Akinori Maezawa
a

a,*

, Hiroya Nakadoi a, Keiko Suzuki a, Tsubasa Furusawa a, Yasuyuki Suzuki b, Shigeo Uchida c

Department of Materials Science and Chemical Engineering, Shizuoka University, 3-5-1, Johoku, Hamamatsu 432-8561, Japan b Suzuki Pump Mfg. Co. Ltd., 13-6, Shimoikegawa, Hamamatsu 430-0905, Japan c Polytechnic College Hamamatsu, 693 Norieda-cho, Hamamatsu 432-8053, Japan Received 10 August 2006; received in revised form 26 October 2006; accepted 6 November 2006 Available online 2 February 2007

Abstract The degradation of Acid Orange 52 in aqueous solutions was investigated by using three processes (photocatalysis, sonolysis, and photocatalysis with sonication). In the case of photocatalysis, although the concentration of Acid Orange 52 decreased to 35% in 480 min, the color of the solution was not disappeared. In the case of sonolysis, it was decomposed completely in 300 min, but the total organic carbon concentration decreased down by only about 13% in 480 min. In the case of photocatalysis with sonication, the concentration of Acid Orange 52 reached to 0 in 240 min and the total organic carbon concentration decreased by about 87% in 480 min. These results indicate that the ultrasonic irradiation enhanced the photocatalytic degradation. The addition of chloride ion (50 ppm) into Acid Orange 52 solution decreased the decomposition eciency for photocatalysis. In the cases of sonolysis and photocatalysis with sonication, the decomposition eciency did not change signicantly by the addition of chloride ion. These results indicate that chloride ion disturbs the photocatalysis of dye, but the decomposition of dye using the irradiation of ultrasound is not inuenced by chloride ion. From these results, it is considered that the photocatalysis with sonication is most eective for the decomposition of dye in the three processes in this study. 2007 Published by Elsevier B.V.
Keywords: Waste water treatment; Decomposition of dye; Photocatalysis; Sonolysis

1. Introduction The treatment of waste water containing the organic carbon has been one of the most important subjects as the environmental protection. The euent of dye works is often colored. This indicates that the dye is a persistent chemical substance and it is not decomposed by the conventional method such as the activated sludge method. Therefore, there is an image that the colored water is considerably polluted though the concentrations of polluting

Corresponding author. E-mail addresses: tcamaez@ipc.shizuoka.ac.jp (A. Maezawa), shacho@suzukipump.com (Y. Suzuki), s2.uchida@ehdo.go.jp (S. Uchida). 1350-4177/$ - see front matter 2007 Published by Elsevier B.V. doi:10.1016/j.ultsonch.2006.11.002

materials in wastewater are below the regulation values. The decomposition of organic pollutants such as dye and the recycle of puried waste water are also desirable for environmental conservation. Photocatalysis is one of the harmless waste water purication methods. The ultraviolet and titanium oxide are commonly used as the light source and the photocatalyst in the photocatalytic process, respectively. Ultraviolet has the disinfectant eect and decomposes the organic compounds to inorganic materials such as carbon dioxide and water. Some researchers have studied on the decomposition of dye by photocatalysis [1,9]. However, the decomposition eciency is low when the organic concentration in the wastewater is high, and some kinds of organic compounds are hardly decomposed.

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The oxidation by the irradiation of the ultrasound (called sonolysis) is another method which decomposes the organic compounds to inorganics. This attracts the attention as a new harmless treatment process. Several researchers have studied on the sonolysis [3,5,11,4]. One of the problems with sonolysis is the low decomposition eciency. However, it has been reported by several researchers that the ultrasonic irradiation enhances photocatalysis. Stock et al. [10] carried out the decomposition of naphthol blue black. They have reported the improvement of mass transfer rates of reactants and products between the bulk solution and the catalyst surface. Davydov et al. [2] have reported that the eect of ultrasound irradiation on the decomposition rate of salicylic acid is attributed to the catalyst deaggregation and the ulilization of species produced by ultrasound. Ragaini et al. [6] have reported that the surface area of the photocatalyst increased after ultrasonic irradiation for 6 h. This means that the ultra ron et al. sound irradiation decreases the particle size. The [12] have reported that the rate constant of rhenyltriuoromethylketone decomposition by the photocatalysis with sonication is higher than the summation of the reaction rate constants in the photocatalysis and the sonolysis and this attribute to the formation of OH radical from H2O2 produced by the ultrasound on the surface of photocatalyst. Seli [7] has also reported that the enhancement eect of the ultrasound on the photocatalysis of Acid Orange 8 is due to an increased concentration of radicals. The reason of the enhancement eect of ultrasound irradiation on the photocatalysis has been unable to come to an agreement. These researchers used the titan oxide particles as photocatalyst.

When the catalytic particle is used, the separation process in which the particle is removed from the treatment water is needed in industry. The costs of the equipment and operation become expensive. In the case of the use of the xed catalyst, the separation process is no needed. In this study, we use the xed catalyst of titanium oxide using solgel method and investigate the eciencies of three processes for dye decomposition. And the eect of the ultrasound irradiation on the photocatalysis is discussed. Not only the dye but also the dyeing auxiliaries are included in the euent of dye works. One of the typical dyeing auxiliaries is sodium chloride. The chromophoric group of dye is anion in the solution. Therefore, the inuence of chloride ion on the decomposition eciency is also discussed. 2. Experimental Fig. 1 illustrates the experimental apparatus which consists mainly of a reactor, a low-pressure mercury lamp, an ultrasound transducer, a bath and a stirrer. The reactor is made of a Pyrex glass cylinder of 110 mm in diameter. It is placed in the temperature constant bath at 298 K. The volume of solution is 1000 mL. The ultrasonic transducer (Kaijo Co., Japan, 200 kHz, 600 W) is installed at the bottom of the reactor. An air pump, a ow meter and a sparger are set up for aeration. Air is used as the aeration gas. Fixed TiO2 catalyst was prepared on a Pyrex glass pipe (i.d. = 60 mm, height = 100 mm) which was used as a support material by dip-coating method using solgel titania made from titanium isopropoxide. After the dip-coating treatment, the catalyst was calcined at 823 K for 1 h.

4 1 5

2 6

11 10 3 8

Fig. 1. Experimental apparatus. (1) UV lamp (20 W), (2) xed catalyst, (3) sparger, (4) stirrer, (5) reactor (1000 mL), (6) thermometer (298 K), (7) ultrasonic transducer (200 kHz), (8) ultrasonic generator (600 W), (9) heater (500 rpm), (10) air cylinder and (11) pump.

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Low-pressure mercury lamp (Sen Light Co., Japan, spectral median wavelength of 253.6 nm, 20 W) is placed at the center of the reactor. The concentration of dye is calculated from the absorption intensity of 460 nm by the UVVIS spectrometer (Shimazu Co., Japan, UV-2450) and the concentration of total organic carbon (TOC) is measured by using the TOC meter (Shimazu Co., Japan, TOC-VCHS). Reagent grade Acid Orange 52 is used as a model dye. Reagent grade sodium chloride and potassium chloride are used as additives. All chemicals are used without purication. 3. Results and discussion Fig. 2 shows the change of the color of Acid Orange 52 in solution with time in three decomposition methods (photocatalysis, sonolysis, and photocatalysis with sonication (called Hybrid method)). For all methods, the color of the solution of Acid Orange 52 became light and the peak position of the UV spectra of the dye solution was not changed. These results indicate that all the methods used in this study have the ability to decompose the Acid Orange 52. However, for the photocatalysis, the color of Acid Orange 52 solutions did not disappear in 480 min. This means that the part of the molecular structure of Acid Orange 52 was not decomposed by the photocatalysis method and was remained in the solution. While, in the cases of sonolysis and Hybrid, the color of the solution was clear in 300 min and 240 min, respectively. This means that Acid Orange 52 was decomposed completely. The time dependencies of the concentration of Acid Orange 52 in three methods are shown in Fig. 3. In the case of photocatalysis, the concentration decreased linearly and the Acid Orange 52 of 35% was decomposed in 480 min. In the case of sonolysis, the concentration of Acid Orange 52

steeply decreased in the rst 60 min and became to zero in 300 min. It can be said that the irradiation of ultrasound decomposed the dye molecules. The decomposition rate of Acid Orange 52 for the sonolysis was considerably faster than that for the photocatalysis. This result indicates that the sonolysis is more eective than photocatalysis. In the case of the Hybrid, the concentration of Acid Orange 52 steeply decreased and reached to zero at 240 min. The decomposition rate for the Hybrid was a little faster than that for the sonolysis. It can be said that the decomposition of Acid Orange 52 by the sonolysis is predominant in the Hybrid method. The time dependency of the normalized TOC (total organic carbon) concentration is also shown in Fig. 4. In the case of the photocatalysis, about 10% TOC decomposed to inorganic compounds in 480 min. In the case of the sonolysis, about 30% TOC was decomposed. Taking account of this result with above results, it is concluded that most of the dye decomposed but the organic intermediates were remained without being decomposed to inorganic compounds. In the case of the Hybrid method, the initial degradation rate of TOC was slow and was similar to those for the photocatalysis and the sonolysis. And then, the degradation rate became rapid after reaction time of 240 min. The TOC of about 35% was decomposed in 480 min. It is thought that the molecular weights of the organic intermediates as decomposition product of dye gradually decrease but the complete mineralization hardly occurs when the reaction time is short. Hence, the degradation rate of TOC is slow. However, after 120 min, the organic intermediates which have small molecular weight decompose to the inorganic compounds. Therefore, the degradation rate becomes higher. Stock et al. [10] have reported that the irradiation of ultrasound promotes the rapture of azo bond and the oxidation of reaction intermediate is promoted by photocatalysis.

Fig. 2. Time change of solution color (initial concentration of Acid Orange 52 = 25 ppm, 500 rpm, air 50 mL/min, 298 K). (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

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25

Table 1 Decomposition eciency of Acid Orange 52 in 240 min Photocatalysis (%) Without chloride ion With chloride ion
Photocatalysis

Concentration of Acid Orange 52 / ppm

20

Sonolysis (%) 99 98 99 98 98

Hybrid (%) 100 99 99 99 98

20 NaCl, [Cl] = 25 ppm NaCl, [Cl] = 50 ppm KCl, [Cl] = 25 ppm KCl, [Cl] = 50 ppm 12 9 6 7

15

10

Sonolysis Hybrid

120

240 Time / min

360

480

Table 2 Decomposition eciency of TOC in 480 min Photocatalysis (%) Without chloride ion With chloride ion 9 NaCl, [Cl] = 25 ppm NaCl, [Cl] = 50 ppm KCl, [Cl] = 25 ppm KCl, [Cl] = 50 ppm 6 5 4 4 Sonolysis (%) 30 24 26 22 29 Hybrid (%) 65 64 62 64 56

Fig. 3. Time dependency of concentration of Acid Orange 52 (500 rpm, air 50 mL/min, 298 K).

100

Normalized TOC Concentration [TOC] / [TOC]0

80

60

40

20

Photocatalysis Sonolysis Hybrid

120

240 Time / min

360

480

Fig. 4. Time dependency of TOC concentration (500 rpm, air 50 mL/min, 298 K).

From these results, it is said that the ultrasonic irradiation with the photocatalysis enhances the decomposition of dye. The some reasons of this eect are reported by several researchers. (1) Catalyst particles physical dispersion by ultrasonic irradiation [2,6,8]. (2) Enhancement of mass transfer between the bulk liquid and the surface of the catalyst and the renewal of uid lm near the surface of catalyst [8,10]. (3) Formation of OH radicals from hydrogen peroxide which is produced by photocatalyst ([12,7]).

It is unable to come to an agreement on these reasons. However, in this study, the xed catalyst was used and the enhancement eect of ultrasonic irradiation was observed. Therefore, it is at least cleared that the enhancement by the irradiation of ultrasound is not due to the physical dispersion of catalyst particle. Table 1 shows the decomposition eciency of Acid Orange 52 in 240 min with and without chloride ion. The decomposition eciency of TOC in 480 min is shown in Table 2. In the case of the photocatalysis, by the addition of chloride ion, the decomposition eciency of Acid Orange 52 was decreased from 20% to 126% and the eciency of TOC was decreased from 10% to about 5%. The decomposition eciency of Acid Orange 52 with the addition of potassium chloride was lower than that with the addition of sodium chloride at the same chloride ion concentration. While, in the case of the sonolysis, the addition of chloride ion hardly aects the eciency. Furthermore, in the case of the Hybrid method, the similar result was obtained. The absorption experiment of Acid Orange 52 under the dark condition without the irradiation of ultrasound was conducted with and without chloride ion. The powder of titanium oxide (P-25, anatase type, Nihon Aerogil Co., Japan, BET surface area: 55 m2/g) was used as catalyst. Acid Orange 52 disassociates into Na+ and anion in the aqueous solution as follows:

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CH3 2 N C6 H6 N N C6 H6 SO3 Na CH3 2 N C6 H6 N N C6 H6 SO 3 Na

25

1
Concentration of Acid Orange 52 / ppm 24.5

Fig. 5 shows the time dependency of the concentration of Acid Orange 52. Without chloride ion, the concentration of Acid Orange 52 decreased and became constant in about 30 min. This indicates that Acid Orange 52 ion adsorbed on the catalyst surface and the adsorption equilibrium was reached in about 30 min. Furthermore, the decomposition of Acid Orange 52 was not occurred under the dark condition without the irradiation of ultrasound. In the case of the addition of chloride ion, the concentration of Acid Orange 52 decreased slightly. The Acid Orange 52 and chloride ion are both anions. And it must be that the adsorption sites for these anions are the same. Therefore, the chloride ion disturbs the adsorption of Acid Orange 52. At the same chloride ion concentration, the amount of adsorbed Acid Orange 52 in the case of sodium chloride was larger than that in the case of potassium chloride. This is due to the dierent inuence of cation to adsorption of Acid Orange 52. Fig. 6 shows the inuence of the amount of catalyst on the concentration of Acid Orange 52 in 30 min with and without chloride ion of 50 ppm. The equilibrium concentration of Acid Orange 52 with chloride ion is higher than that without the chloride ion. Furthermore, the concentration of Acid Orange 52 decreased about linearly with the increase in the amount of catalyst. It must be that the similar results are obtained in the case of xed catalyst though the above results were obtained by using powder catalyst. Therefore, the chloride ion adsorbs on the surface of the catalyst and disturbs the catalytic eect.

24

23.5

22

Without chloride ion With NaCl 50 ppm With KCl 50 ppm

22.5 0

20

40

60
2

80

Surface area of catalyst / m

Fig. 6. Concentration of Acid Orange 52 vs. surface area of catalyst in the dark experiments without irradiation of ultrasound (500 rpm, 298 K).

25

Concentration of Acid Orange 52 / ppm

24.5

24

The hole produced on the valence band by the motion of excited electron reacts with the chloride ion adsorbed on the catalyst surface and disappears [9]. Therefore, the production of OH radical to react with the organic compounds is limited. By this reason, the decomposition eciencies of Acid Orange 52 and TOC in the case of the photocatalysis were decreased. In the sonolysis, there exist no catalyst in the reactor, that is, there are no adsorption sites for Acid Orange 52 and chloride ion. Therefore, it is observed that the decomposition of dye in the sonolysis is not inuenced by the chloride ion. In spite of the existence of catalyst, the decomposition eciency in the Hybrid method was higher than those in the photocatalysis. Because the sonolytic decomposition is predominant in the Hybrid method, though the decomposition rate of photocatalysis was decreased by the chloride ion, the dye was decomposed by the sonolysis which is not inuenced by the chloride ion. Therefore, it must be that the inuence of chloride ion was small in the Hybrid method. 4. Conclusion

23.5 0 ppm NaCl KCl 23 0 10 20 30 Time / min 40 50 60 25 ppm 50 ppm

Fig. 5. Time dependency of concentration of Acid Orange 52 in the dark experiments without irradiation of ultrasound (TiO2 particle 0.6 g/L, 500 rpm, 298 K).

The photocatalysis is applicable to the dye containing waste water treatment. The irradiation of the ultrasound increased the dye and TOC decomposition eciencies of the photocatalysis. However, the eciency of the photocatalysis decreased in the addition of chloride ion in order to the absorption of that ion on the surface of the catalyst. The decomposition of dye using the ultrasonic irradiation (that is, the sonolysis and the Hybrid method) is not inuenced by the chloride ion. And it is found that the sonolysis is the dominant decomposition in the Hybrid method.

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A. Maezawa et al. / Ultrasonics Sonochemistry 14 (2007) 615620 comparison with other techniques, Ultrason. Sonochem. 8 (2001) 251258. E. Selli, Synergistic eects of sonolysis combined with photocatalysis in the degradation of an azo dye, Phys. Chem. Chem. Phys. 4 (2002) 61236128. I.Z. Shirgaonkar, A.B. Pandit, Sonophotochemical destruction of aqueous solution of 2,4,6-trichlorophenol, Ultrason. Sonochem. 5 (1998) 5361. zkan, Decolouring textile wastewater with modied M. So kem, A. O titania: the eect of inorganic anions on the photocatalysis, J. Photochem. Photobio. A: Chem. 147 (2002) 7781. N.L. Stock, J. Peller, K. Vinodgopal, P.V. Kamat, Combinative sonolysis and photocatalysis for textile dye degradation, Environ. Sci. Technol. 34 (2000) 17471750. Y. Suzuki, A. Maezawa, S. Uchida, Eect of frequency and aeration rate on ultrasonic oxidation of surfactant, Chem. Eng. Technol. 22 (1999) 507510. ron, P. Pichat, C. Guillard, C. Pe trier, T. Chopin, Degradation P. The of phenyltriuoromethylketone in water by separate or simultaneous use of TiO2 photocatalysis and 30 or 515 kHz ultrasound, Phys. Chem. Chem. Phys. 1 (1999) 46634668.

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