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a,*
Department of Chemical Engineering, Korea University, 1, 5-ka, Anam-dong, Sungbuk-ku, Seoul 136-701, South Korea
b
Department of Environmental Engineering, Kyonggi University, 94 San, Iui-dong, Paldal-ku, Suwon-si,
Konggi-do 442-760, South Korea
Received 25 February 2001; received in revised form 19 February 2002; accepted 19 February 2002
Abstract
In the present work, photocatalytic degradation of volatile organic compounds including gas-phase trichloroethylene (TCE), acetone, methanol and toluene over illuminated TiO2 was closely examined in a batch photoreactor as a
function of water vapor, molecular oxygen and reaction temperature. Water vapor enhanced the photocatalytic degradation rate of toluene, but was inhibitive for acetone, and, there was an optimum water vapor concentration in the
TCE and methanol removal. In a nitrogen atmosphere, it showed lower photocatalytic degradation rate than in air and
pure oxygen. Thus, it could be concluded that oxygen is an essential component in photocatalytic reactions by trapping
photogenerated electrons on the semiconductor surface and by decreasing the recombination of electrons and holes. As
for the inuence of reaction temperature, it was found that photocatalytic degradation was more eective at a moderate
temperature than at an elevated temperature for each compound. 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Photocatalytic degradation; TiO2 lm; Gas phase; Volatile organic compound; Batch photoreactor
1. Introduction
Volatile organic compounds (VOCs) are widely used
in industrial processes and domestic activities, leading
to water and air pollution, even indoor work-place air
pollution (EPA, 1987). Many VOCs are known to be
toxic and considered to be carcinogenic. The most signicant problem related to the emission of VOCs is
centered on the potential production of photochemical
oxides: for example, ozone and peroxyacetyl nitrate.
The TiO2 -sensitized photodegradation of organic
compounds has been proposed as an alternative advanced oxidation process (AOP) for the decontamination of water and air. The AOP is initiated from the
0045-6535/02/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 5 - 6 5 3 5 ( 0 2 ) 0 0 1 0 1 - 7
438
vapor was essential to maintain the photocatalytic catalyst activity for an extended period, but higher water
vapor levels were strongly inhibitory. Anderson et al.
(1993) studied the dependency of the TCE photocatalytic degradation rate on the light intensity, feed composition (TCE, O2 , H2 O) and temperature in a bed
reactor packed with TiO2 pellets. They showed that the
reaction rate was rst order with respect to the light
intensity, independent of the concentration in the range
of 37450 ppm, oxygen mole fraction 0.010.2 and
water vapor mole fraction 0.0010.028, and the temperature did not aect the reaction rate in the range of
2362 C.
Peral and Ollis (1992) reported that the water vapor
inhibited oxidation of acetone. On the contrary, some
researchers showed that water vapor could enhance the
photocatalytic oxidation of hydrocarbons such as formic acid (Muggli and Falconer, 1999). Ibusuki and
Takeuchi (1986) investigated the photooxidation with
toluene (80 ppm) in air over UV irradiated TiO2 at an
ambient temperature. They observed that the CO2 concentration with 10 min residence time in reactor increased linearly with the increase of relative humidity
over 060%. Obee and Brown (1995) studied the photooxidation of toluene and other organic pollutants by
using polycrystalline TiO2 photocatalyst. They focused
on the inuence of the competitive adsorption between
water and toluene vapors.
The purpose of this paper is to nd the optimum
condition for the removal of the hazardous and nondegradable VOCs including TCE, acetone, methanol
and toluene as a function of water vapor, oxygen, and
reaction temperature. A batch photoreactor was applied
prior to the acquisition of fundamental data for a scaledup photoreactor design and the application of continuous
process for the gassolid heterogeneous photocatalytic
reaction.
2. Experimental methods
2.1. Materials
All of the chemicals used in the work were reagentgrade. The liquid phase VOCs were purchased from
Aldrich (TCEanhydrous, 99%, acetoneACS reagent,
99.5%, methanolanhydrous, 99.8%, toluene anhydrous, 99%).
The photocatalyst was prepared with TiO2 suspension (STS-01, anatase, 7 nm in diameter, 300 m2 /g of
specic surface area, Ishihara Sangyo Co.), tetraethyl
orthosilicate (TEOS, 98%, Aldrich), dimethoxy dimethyl
silane (DMDMS, 95%, Aldrich), isopropyl alcohol
(IPA, anhydrous, 99.5%, Aldrich) and nitric acid (65
wt% solution in water, Aldrich).
439
Fig. 2. SEM photographs of (a) top and (b) cross-sectional views of the TiO2 lm on the Pyrex glass tube.
440
Table 1
The photocatalytic degradation rate of each VOC according to water vapor contents
Water vapor contents
(mol m3 (vol%))
None
0.191 (0.5)
0.383 (1.0)
0.766 (2.0)
1.149 (3.0)
1.532 (4.0)
1.914 (5.0)
Acetone
Methanol
Toluene
1.22 0.01
1.88 0.02
7.13 0.10
4.14 0.02
3.92 0.02
1.86 0.02
1.08 0.02
0.561 0.008
1.57 0.02
1.72 0.01
1.81 0.01
1.20 0.02
0.963 0.008
0.154 0.005
0.254 0.005
0.325 0.007
0.456 0.004
Initial concentration of each compound: TCE 1:206 102 mol m3 , acetone 1:208 102 mol m3 , methanol 1:151 102
mol m3 , and toluene 3:835 103 mol m3 UV source: germicidal (254 nm) lamp, light intensity 2:1 103 W cm2 , temperature:
45 C.
441
TiO2 hm ! TiO2 e
cb hvb
h
vb OH ! OH
O2
e
cb
O
2
If water vapor takes part in the gassolid photocatalysis, the super-oxide radical can react with water
molecules, eventually forming the hydroxyl radicals as
shown in Eq. (4). Thus, the photocatalytic degradation
of VOCs can be increased due to the formation of hydroxyl radicals (Fox et al., 1990).
2O
2 2H2 O ! 2OH OH O2
442
Fig. 4. The eect of molecular oxygen on the photocatalytic degradation rate of each VOC. (a) TCE (CO 1:206 102 mol m3 ,
CH2 O 0:383 mol m3 ), (b) Acetone (CO 1:208 102 mol m3 , CH2 O 0:0 mol m3 ), (c) Methanol (CO 1:151 102 mol m3 ,
CH2 O 0:383 mol m3 ), (d) Toluene (CO 3:835 103 mol m3 , CH2 O 0:766 mol m3 ); UV source: germicidal (254 nm) lamp, light
intensity: 2:1 103 W cm2 ; temperature: 45 C.
4. Conclusions
443
Fig. 6. The eect of temperature on the photocatalytic degradation rate of each VOC. (a) TCE (CO 1:206 102 mol m3 ,
CH2 O 0:383 mol m3 ), (b) Acetone (CO 1:208 102 mol m3 , CH2 O 0:0 mol m3 ), (c) Methanol (CO 1:151 102 mol m3 ,
CH2 O 0:383 mol m3 ), (d) Toluene (CO 3:835 103 mol m3 , CH2 O 0:766 mol m3 ); UV source: germicidal (254 nm) lamp, light
intensity: 2:1 103 W cm2 .
For the eect of oxygen on the photocatalytic degradation of VOCs, molecular oxygen is an essential
component in photocatalytic reactions because it traps
photogenerated electrons on the semiconductor surfaces
and decreases the recombination of electrons and holes.
As for the eect of reaction temperature on the
photocatalytic degradation of VOCs, it can be seen that
the photocatalytic degradation was more eective at a
moderate temperature than at an elevated temperature
for each compound because the adsorption of reactants
from the photocatalyst surface was dicult at a higher
temperature range (75 C).
Acknowledgements
The authors thank the Korea Institute of Industrial
TechnologyNational Center for Cleaner Production
and MAGREEN INC. for support of this work.
References
Alberici, R.M., Jardim, W.F., 1997. Photocatalytic destruction
of VOCs in the gas-phase using titanium dioxide. Appl.
Catal. B: Environ. 14, 5568.
Anderson, M.A., Yamazakinishida, S., Salvador, C.M., 1993.
Photodegradation of TCE in the gas phase using TiO2
444
Ibusuki, T., Takeuchi, K., 1986. Toluene oxidation on UVirradiated titanium dioxide with and without O2 , NO2 ,
or H2 O at ambient temperature. Atmos. Environ. 20 (9),
17111715.
Levenspiel, O., 1972. In: Chemical Reaction Engineering, second ed. John Wiley & Sons Inc., New York, pp. 6971.
Luo, Y., Ollis, D.F., 1996. Heterogeneous photocatalytic oxidation of trichloroethylene and toluene mixtures in air:
Kinetic promotion and inhibition, time-dependent catalyst
activity. J. Catal. 163, 111.
Mark, R.N., William, A.J., Danial, M.B., Thomas, A.M., 1993.
Detection of intermediates from the gas phase photocatalytic oxidation of TCE. In: Photocatalytic purication and
treatment of water and air. Elsevier Science Publisher,
Amsterdam, pp. 387391.
Miller, R., Fox, R., 1993. In: The rst international conference
on TiO2 photocatalytic purication and treatment of water
and air. Elsevier, London, Ontario, Amsterdam, New York,
p. 573.
Muggli, D.S., Falconer, J.L., 1999. Parallel pathways for
photocatalytic decomposition of acetic acid on TiO2 . J.
Catal. 187, 230237.
Munuera, G., Rives-Arnau, V., Saucedo, A., 1979. Photoadsorption and photo-desorption of oxygen on highly
hydroxylated TiO2 surface: Part 1role of hydroxyl groups
in photo-adsorption. J. Chem. Soc., Faraday Trans. 175,
736.
Obee, T.N., Brown, R.T., 1995. TiO2 photocatalysis for indoor
air applications: Eect of humidity and trace contaminant