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C.-H. Hung*, P.-C. Chiang**, C. Yuan***, C.-Y. Chou*

* Department of Environmental Engineering, Foo-Yin Institute of Technology, 151 Chung-Hsueh Road,
Taliao 831, Kaoshiung Hsien, Taiwan
** Graduate Institute of Environmental Engineering, National Taiwan University, Taipei, Taiwan
*** Department of Civil Engineering, I-Shou University, Kaoshiung Hsien, Taiwan
Current address: Department of Safety, Health and Environmental Engineering, National Kaohsiung First
University of Science and Technology, Yanchau, Kaohsiung 824, Taiwan
Abstract The photocatalysis of azo dye, Orange G, by P-25 anatase TiO2 was investigated in this research.
The experiments were conducted in a batch reactor with TiO2 powder suspension. Four near-UV lamps
were used as the light source. The experimental variables included solution pH level, amount of TiO2,
illumination light intensity, and reaction time. A pseudo-first order reaction kinetic was proposed to simulate
the photocatalytic degradation of Orange G in the batch reactor. More than 80% of 10 mg/L Orange G
decomposition in 60-minute reaction time was observed in this study and fast decomposition of Orange G
only occurred in the presence of both TiO2 and suitable light energy. Faster degradation of Orange G was
achieved under acid conditions. The degradation rates of Orange G at pH = 3.0 were about two times faster
than those at pH = 7.0. Faster degradation of azo dye was observed for greater irradiated light intensity and
more TiO2 present during the reaction. The reaction rates were proportional to TiO2 concentration and light
intensity with the power order of 0.726 and 0.734, respectively.
Keywords Liquid phase photocatalysis; TiO2; azo dye; dyeing wastewater; Orange G

Water Science and Technology Vol 43 No2 pp 313320 IWA Publishing 2001

Photocatalytic degradation of azo dye in TiO2 suspended

solution

Introduction

The discharge of textile dyeing wastewater has been a pollution problem of great concern in
Taiwan. High COD and grease concentrations, low BOD/COD ratio, containing many
toxic substances, variety of wastewater, with color, and relatively higher temperature are
the general properties of dyeing wastewater. Most dyeing wastewater is difficult to
biodegrade and is toxic to most aqueous organisms. The observation of many toxic
substances, such as, nitrobenzene, azoheterozole, benzidine, stilbene, aminonaphthol,
p-diaminobenzene, quaternary amines, and azo dyes has been reported (Taiwan EPA,
1992, Horning, 1968). There are more than 300 major textile companies in Taiwan while
most of their wastewater is not well treated before discharge (Taiwan EPA, 1998 & 1992).
Many advanced treatment technologies have been developed for reducing the pollution
from textile wastewater (Leu, 1997; Gregor, 1990; Sedlak & Ander, 1991). Among these
treatment processes, advanced oxidation processes (AOPs) are the most common unit operations that are generally investigated by recent researchers and show superior treatment
efficiencies for textile wastewater. AOPs have been attracting more and more research
efforts on dyeing waste treatment. Photocatalytic oxidation that uses semiconductor material (e.g., TiO2) as catalyst to destroy organic pollutants in a short reaction time is one of the
emerging processes (Bahnemann et al., 1994). Fast reaction, high destruction efficiencies,
lower energy requirement, easy operation, and complete mineralization are the reported
advantages of the photocatalysis process. The formation of highly reactive species (e.g.,
OH), which can decompose organic pollutants, is observed on the surfaces of photocatalysts. Reactant concentrations, amount of photocatalyst dosages, illumination light

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intensity, reaction temperature, and solution pH levels are the major reaction variables for
photocatalytic reactions (Ollis, 1985; Hung & Marias, 1997).
The photocatalytic degradation of typical azo dye, Orange G, in titanium dioxide suspended solution was the main research objective of this study. The experimental parameters of reaction time, solution pH level, TiO2 dosages, and illuminated light intensity were
examined in this investigation. The reaction kinetics and degradation reaction rate constants were also discussed in this research.
Experimental methods and apparatus

The experiments of photocatalytic oxidation of Orange G (C16H10N2Na2O7S2, Merck,

reagent grade) were conducted in a 1L-Pyrex glass batch photocatalytic reactor with TiO2
(P-25, Japan Company) suspended solution applied as the photocatalyst. The TiO2 powder
is in the anatase form and its purity, average diameter, specific surface area, and pHzpc are
99.9 %, 3.002 mm, 8.275 m2/g, and < 2.5, respectively. Constant temperature (35C) and
pH level (pH=3~11) of solution were maintained during the experiments. Four near ultraviolet lamps (F10 TBLB, Fluorescent Black Light, GE Company) with the main emission
light wavelength at 365 nm were provided as the light source. The light intensity for the
reaction was determined with a radiometer (UVX Digital Radiometer, UVX-36, CA,
USA). Concentrations of Orange G were determined with a UV spectrophotometer
(Lambda 12, UV/VIS Spectrometer, Perkin Elmer) and the scanning wavelength of 480
nm. Because the UV absorbance of Orange G can be interfered with in the presence of suspended particles, the samples of TiO2 suspended solution were centrifuged to separate
TiO2 powder from solution before determining Orange G concentrations. In addition,
because the absorbance of Orange G changes in different pH level solution, the calibration
curves of Orange G at different pH level were prepared for correctly measuring the concentrations of Orange G at specific pH level.
The experimental parameters included reaction time, solution pH level, TiO2 dosage,
and irradiation light intensity. Samples (about 20 mL each time) were collected from the
photocatalytic reactor for the reaction time ranging from 0 to 60 minutes while measuring
the residual concentration of Orange G, which has initial concentration of Orange G of 10
mg/L. The pH level ranging from 3 to 11 was examined to investigate the influence of solution pH level on the photocatalytic decomposition of Orange G. The pH level at which the
Orange G has the fastest degradation rate was selected as the tested pH level for the rest of
the experiments. Five different TiO2 dosages ranging from 300 to 2000 mg/L were examined in the investigation. Four different illuminated light intensities ranging from 200 to
600 W/cm2 were tested in the study. Finally, the pseudo-first order degradation reaction
kinetic was applied to simulate the photocatalytic decomposition of Orange G in each reaction condition and the corresponding reaction rate constants were also calculated.
Results and discussion

314

Two comparison experiments were conducted to investigate the role of TiO2 and near-UV
light on the photocatalytic reaction. One experiment was to measure the residual concentrations of Orange G in the presence of TiO2 only and no light energy provided. The experimental results showed that less than 5% of initial Orange G could be absorbed by TiO2 after
a 60-minute reaction period while TiO2 concentration was 1000 mg/L and no near-UV light
energy was provided. Another experiment was to measure the residual concentrations of
Orange G under the illumination of near-UV light only in the absence of TiO2. The experimental results showed that less than 1% of Orange G can be directly photolyzed by
near-UV light. On the other hand, the maximum conversion ratio of more than 80% of
Orange G was observed in the presence of both TiO2 and near-UV light (see Figure 1). It is

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concluded that the fast decomposition of Orange G only takes place in the presence of both
TiO2 and near-UV light.
Several major experimental results concluded in this study for the photocatalysis of
Orange G were tabulated in Table 1. The corresponding pseudo-first order reaction constants for each reaction condition were also summarized in the Table. The initial concentrations of Orange G in each experiments were 10 mg/L. These experimental results showed
that the degradation rate constants ranged from 0.015 to 0.076 min1 and the assumed first
order reaction could predict the degradation of Orange G azo dye very well. A degradation
rate expression of Orange G as a function of dye concentrations, TiO2 content, and illuminated light intensity is proposed as Equation (1). It is concluded that the photocatalytic
decomposition of Orange G in the TiO2-powder-suspended reactor followed the first-order
reaction, basically.
Table 1 The ratio of residual concentrations to initial concentrations of Orange G and respective reaction
rates constants for different reaction conditions
TiO2

st
1 -order Correlation

Illumination pH

[Orange G] t/[Orange G]o

Dosage

Light

at different reaction period (mins)a

(mg/L)

Intensity
(W/cm2)

1000
1000
1000
1000
1000
300
500
1500
2000
1000
1000
1000

586 11
586 9
586 7
586 5
586 3
586 3
586 3
586 3
586 3
468 3
341 3
215 3

rateb

Coeff. R2

constant
0

10

15

20

30

60

(1/min1)

1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00

0.97
0.98
0.99
0.99
0.93
0.98
0.96
0.94
0.95
0.95
0.99
0.99

0.94
0.96
0.95
0.92
0.87
0.93
0.90
0.87
0.86
0.91
0.97
0.97

0.90
0.88
0.94
0.89
0.83
0.90
0.86
0.80
0.81
0.87
0.95
0.96

0.85
0.85
0.93
0.87
0.75
0.83
0.82
0.73
0.72
0.85
0.90
0.93

0.81
0.77
0.91
0.83
0.69
0.80
0.78
0.69
0.64
0.82
0.84
0.87

0.78
0.75
0.90
0.70
0.65
0.71
0.68
0.54
0.45
0.72
0.78
0.81

0.70
0.72
0.84
0.60
0.54
0.65
0.60
0.43
0.30
0.61
0.66
0.73

0.54
0.55
0.69
0.41
0.38
0.50
0.43
0.24
0.06
0.40
0.44
0.65

0.28
0.29
0.39
0.20
0.15
0.34
0.16
0.01
0.01
0.17
0.22
0.39

0.02061
0.02022
0.01401
0.02676
0.03172
0.01946
0.02935
0.06620
0.07600
0.02869
0.02445
0.01521

0.994
0.992
0.946
0.989
0.997
0.975
0.993
0.927
0.962
0.987
0.974
0.990

a: The initial concentration of Orange G for the experiments is 10 mg/L.

b: The decomposition of Orange G is assumed to follow a first-order reaction.

d[Orange G]
0.7263
0.7338
= k [Orange G] [Catalyst ]
[ Light Intensity]
dt

(1)

Where:
[Orange G]: concentration of Orange G (mg/L),
[Catalyst]: concentration of TiO2 in solution (mg/L)
[Light Intensity]: illumination light intensity (W/cm2),
k: first-order degradation rate constant [= 2.50106 min1*(mg/L)0.7263*
2
(W/cm )0.7338]
pH effect

The concentration ratios of Orange G as a function of the solution pH = 3.0, 5.0, 7.0, and
9.0, respectively, were depicted in Figure 1. Figure 2 showed the influence of solution pH
level on the photocatalytic degradation of Orange G. The experiments were performed
under the experimental conditions of 1000-mg/L TiO2 and 586-W/cm2 light intensity. As
mentioned before, decomposition of Orange G basically followed the first order reaction.
The experimental results showed that the residual concentrations of Orange G decreased
with increasing reaction time. The experimental results also showed that Orange G

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Figure 1 The residual concentration ratios of Orange G as a function of different reaction time at various
solution pH levels (Experimental conditions: [TiO2]o = 1000 mg/L; light intensity = 586 W/cm2)

Figure 2 The residual concentration ratios and the corresponding degradation rate constants of Orange G
as a function of different solution pH levels (Experimental conditions: [TiO2]o = 1000 mg/L; light intensity =
586 W/cm2)

316

decomposed more quickly under more acid or base conditions and degraded more slowly
under neutral conditions. Consistent results of reaction rate constants calculated from
experiments can be observed in Figure 3, too. The degradation rates for Orange G in pH= 3
and 11 conditions were about 1.5 ~ 2.0 times greater than those of Orange G in pH= 7
condition.
The formation of hydroxyl radicals (OH) on the surfaces of photocatalyst (e.g.TiO2)
irradiated with suitable light energy as an important reaction mechanism for the photocatalytic reactions of many organic compounds has been reported (Ollis, 1985). These highly

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reactive radicals can react with many organic species and, meanwhile, organic pollutants
can be removed. The formation of OH during decomposition of organic compounds is also
observed in many similar advanced oxidation processes, such as the Fenton process, ozonation, UV/O3, UV/H2O2. It is interesting to find that the optimal pH level for Fenton reactions, which has the fastest reaction rates, is also in acid conditions. The Fenton process has
greater reaction rates when the solution pH levels are in the range between 2 to 3. It may be
the same reason that Orange G degraded faster when the pH level of solution was at 3 in our
reaction systems. On the other hand, more OH present in the solution may result in more
formation of OH radicals. This may be the reason Orange G had greater degradation rates
and a solution pH level greater than 9 in our investigation. The slowest detected degradation rate of Orange G was in neutral conditions.
TiO2 dosage effect

The residual ratios of Orange G as a function of reaction time for different amounts of TiO2
powder present in the photocatalytic reactor is illustrated in Figure 3. The corresponding
reaction rate constants for different amount of TiO2 are compared in Figure 4. The experiments were examined under the experimental conditions of solution pH equal to 3.0, light
intensity equal to 586 W/cm2, and TiO2 concentrations ranging from 300 to 2000 mg/L. A
typical catalytic reaction for the decomposition of Orange G was observed. That is, the
more catalyst involved in the reactions, the greater reaction rates for photocatalysis of
Orange G were detected. As mentioned previously, the degradation rates of Orange G were
proportional to the TiO2 concentrations with the power order about 0.7. The reaction rate of
2000 mg/L TiO2 was nearly four times faster than that of 300 mg/L TiO2 in the reactor.
More than 94% of Orange G could be degraded in 30-minute reaction time while TiO2 concentration was equal to 2000 mg/L. The experimental results have shown the potential
practical application of this process for dyeing wastewater control.
Irradiated light intensity effect

Figure 5 depicts the effect of irradiated light intensity on the photocatalytic degradation of
azo dye as a function of various reaction times. The corresponding reaction rate constants
for different irradiated light intensity are shown in Figure 6. The tests were conducted
under the experimental conditions of pH = 3.0, TiO2 concentrations equal to 1000 mg/L,
and light intensity ranging from 200 to 600 W/cm2. The higher the light intensity, the

Figure 3 The residual concentration ratios of Orange G as a function of reaction time for various TiO2
dosage (Experimental conditions: pH = 3.0; light intensity = 586 W/cm2)

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greater reaction rates for photocatalysis of Orange G were observed. As shown in the
Equation (1), the degradation rates of Orange G were proportional to the light intensity with
the power order about 0.73. The literature investigations indicated that the recombination
of electron and electron-hole pairs on photocatalysis is the rate controling step of the reaction mechanisms with the reaction proportional to the light intensity with half power order
(Peterson et al., 1991). Thus, the recombination of electron-hole pairs may play an important role for the photocatalytic degradation of Orange G. Reducing the recombination rates
of electron-hole pairs by modifying the photocatalyst may enable us to enhance the degradation rates of Orange G.
Conclusions

The investigations of photocatalytic oxidation of Orange G (C16H10N2Na2O7S2) with

TiO2suspended solution as the photocatalyst in a batch photocatalytic reactor were conducted in this research. Orange G is a typical azo dye which is generally applied in textile
industries. The experimental variables for the study included reaction time, solution pH
level, concentrations of TiO2, and illumination light intensity. The experimental results
concluded that fast degradation of Orange G only occurred in the presence of both TiO2 and
suitable light energy. The fastest decomposition rate of Orange G was detected for the solution pH level equal to 3.0, while relatively slower degradation reaction of Orange G was
detected at the solution pH level equal to 7.0.
Both higher TiO2 concentration and irradiated light intensity could enhance the degradation rates of Orange G. More than 94 % of conversion ratio of Orange G in 30-minute
reaction time was observed in the experimental conditions of 2000 mg/L TiO2 in the
solution, illuminated light intensity equal to 586 W/cm2, and solution pH = 3.0. This
investigation has demonstrated the practical potential of applying photocatalytic oxidation
to textile wastewater for color removal.

318

Figure 4 The residual concentration ratios and degradation rate constants of Orange G as a function of
TiO2 concentrations (Experimental conditions: pH = 3.0; light intensity = 586 W/cm2)

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Figure 5 The residual concentration ratios of Orange G as a function of reaction time at various illuminated
light intensities (Experimental conditions: [TiO2]o = 1000 mg/L; pH = 3.0)

Figure 6 The residual concentration ratios and degradation rate constants of Orange G as a function of
illuminated light intensities (Experimental conditions: [TiO2]o = 1000 mg/L; pH = 3.0)

Acknowledgement

This study was performed under the auspices of the National Science Council, Republic of
China, under contract number NSC-88-2211-E-242-005. The authors are grateful to the
Industrial Development Bureau of The Ministry of Economic Affairs, Republic of China
and Foo Yin Institute of Technology for their financial support.
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