PII: S0043-1354(98)00295-4

Wat. Res. Vol. 33, No. 4, pp. 10801084, 1999 # 1999 Elsevier Science Ltd. All rights reserved Printed in Great Britain 0043-1354/99/$ - see front matter

``CRITICAL'' EFFECT OF HYDROGEN PEROXIDE IN PHOTOCHEMICAL DYE DEGRADATION

M NILSUN H. INCE**

Bog i University, Institute of Environmental Sciences, 80815 Bebek-Istanbul, Turkey azic (First received January 1997; accepted in revised form July 1998) AbstractTertiary or pretreatment of dyeing euents by advanced oxidation processes (AOP) catalyzed by a source of UV light and a powerful oxidant is a promising alternative for the eective removal of color and refractory organics from the euent. A crucial feature in designing such systems is the optimization of operating conditions (such as UV and oxidant dosages), which yield maximum removal at acceptable costs. The present study describes a modeling approach to keep the oxidant dosage at the most ``eective'' level to sustain maximum rate of dye removal at the selected experimental conditions. The method of study involved monitoring the rate of dye degradation in a synthetic azo dye solution of nearly constant concentration during irradiation by a medium pressure light source and varying H2O2 dosages, followed by predicting a mathematical relation between the pseudo-rst order rate constant and the ``eective H2O2 level'' in the photoreactor. It was found that this ``eective level'' can be set by controlling the initial mass ratio of H2O2 to dye, or the light fraction absorbed by hydrogen peroxide within the UV emission spectra of the light source. # 1999 Elsevier Science Ltd. All rights reserved Key wordsAOP, hydroxyl radical, mathematical model, hydrogen peroxide, azo dye, Remazol Black-B

INTRODUCTION

Dyeing and nishing of textile goods is a major concern to the environmentalist, due to the introduction of large quantities of color, chemical oxygen demand (COD), nonbiodegradable organics, and other hazardous chemicals into the process euents (Lin and Peng, 1996). The expanded use of azo dyes in textile dyeing mills is a further source of concern, since some of the precursors and the reaction products of such dyes are reported to be highly carcinogenic (Boeniger, 1980; Brown and De Vito, 1993). Biodegradability studies on dyestus have shown that azo dyes are rarely biodegradable under aerobic conditions, large quantities of the dye and its metabolites being sorbed by bioocs in the sludge (Pagga and Brown, 1986; Ganesh et al., 1994). Nevertheless, biotreatment of textile euents containing azo dyes and their hydrolysis products can be a cost-eective alternative when the euents are pretreated chemically prior to treatment in the biological unit (Lin and Peng, 1996). Previous studies have shown that bleaching of colored euents by AOP catalyzed by UV light and/ or Fenton's reagent and a powerful oxidant such as

hydrogen peroxide or ozone result in substantial reduction in chemical oxygen demand (COD), total organic carbon (TOC) and toxicity (Gregor, 1992; Shu et al., 1994; Ince et al., 1997). The mechanism of removal in AOP is based on the formation of very reactive radical species, specically the hydroxyl radical, which is remarkably higher in oxidative capacity than any other oxidants (Bolton and Cater, 1994). Furthermore, the UV/H2O2 process has an additional advantage in that there is no sludge formation during any stage of the treatment. In spite of all advantages, to render AOPs competitive with other physico-chemical processes such as occulation, adsorption and electrochemical coagulation, it is essential that they are cost-eective, as well. The purpose of this work was to establish a mathematical relation between the rate of dye removal in a UV/H2O2 system and the applied H2O2 dosage, as represented by either the fraction of UV light it absorbs, or the ratio of its initial concentration to that of the dye. Remazol Black-B was used as a surrogate chemical to represent azo dyes. It is a diazo type reactive dye, containing two vinyl sulfonate reactive groups as represented by the following chemical structure:

*[Tel.: +90-212-263-1500; Fax: +90-212-257-5033; Email: ince@boun.edu.tr]. 1080

Nilsun H. Ince

1081

Fig. 1. Degradation kinetics of 35 ppm Black-B, spiked with 938 mg l1 H2O2.

Typical reactions of all reactive azo dyes under alkaline conditions are the production of vinyl sulfone and hydrolysis intermediates at elevated temperatures, all of which appear in the washwater and ultimately in the waste stream.
MATERIALS AND METHODS

6 cm. The data were then used in a modied Beer's law expression (assuming that the sum of the fractions of light absorbed by each component a dyehydrogen peroxide mixture is unity), represented by equation 1, where E and c are the molar extinction coecient and molar concentration of H2O2, respectively and b is the optical path length. F 1 10cb 1

Experimental
Remazol Black-B (991.8 g mol1) was obtained from Hoechst, Germany in 73% purity. Hydrogen peroxide (BDH) was 30% analytical grade. Reagent grade ceric sulfate (0.1 N in H2SO4) was used to determine the concentration of H2O2 (Sutton, 1955). The irradiation tests were run in a 36 l Rayox1 Model CU01-1 reactor, containing a cylindrical photoreactor (6.5 l) housing a 1 kW Solarchem medium pressure Hg lamp, separated from the solution by a quartz jacket. At the start of each run, the fractions of light absorbed by the dye and hydrogen peroxide in the area of 200300 nm were determined spectrophotometrically, using a 6 cm quartz cell. The experiments consisted of feeding the reactor with a synthetic dye solution of nearly constant concentration (3537.5 mg l1) and systematically increased dosages of hydrogen peroxide (between 0 and 1312 mg l1) and monitoring the dye during a 20 min irradiation period, when the reaction mixture was circulated through the reactor at 110 l min1. The dye was analyzed spectrophotometrically at its maximum absorption wavelength of 596 nm, using a Hewlett Packard Model 8450 A diode array spectrophotometer. Modeling The relationship between the rate of dye degradation and the amount of H2O2 injected to the system was modeled by using nonlinear regression methods with two variables (SYSTAT, Inc., 1992). The dependent variable was dened as the pseudo-rst order color degradation rate constant estimated by linear regression from dye absorption (at 596 nm) vs time data. The independent variable called ``the eective H2O2'' was dened in two ways: 1. As the fraction of total UV ux of the lamp (in the 200300 nm UV range) absorbed by the quantity of H2O2 added to the dye solution at time zero. To calculate this fraction (F) for each of the dyeH2O2 test mixtures, the optical density of a pure dye and a pure H2O2 solution (each at the test concentration that made up the mixture in concern) was monitored in the dened UV range by using an optical path length of

2. As the relative concentration of H2O2 to that of the dye at time zero. The model was dened by a rational equation based on a modied kinetic expression of competitive inhibition as: k a bH 1 gH E 2

where, k is the rst order color degradation rate constant, (min1), H is the ``eective'' H2O2 dosage, E is an error function to account for the deviations between model predictions and observed values of k, and a, b and g are the model's parameters.
RESULTS AND DISCUSSION

The rate of color degradation for each set of dyeH2O2 combination was estimated by rst order kinetic assumption and from the slope of log (dye concentration) vs time data. Dye concentrations in
Table 1. Model input data H2O2/Dye at t=0 (mg l1/mg l1) 0 0.912 1.914 3.277 3.657 5.404 7.412 10.968 14.441 20.000 23.100 26.724 36.751 F, fraction of UV absorbed by H2O2 at t = 0 0.000 0.047 0.090 0.140 0.152 0.201 0.248 0.312 0.361 0.421 0.448 0.476 0.535 k, 1st order rate constant (min1) 0.023 0.218 0.454 0.589 0.623 0.749 0.849 0.897 0.937 0.918 0.851 0.845 0.801

1082

Eect of H2O2 in dye degradation

Fig. 2. First order degradation rate constant of Black-B as a function of light absorption capacity of H2O2 in the UV range. The solid line represents a nonlinear regression t to the data by use of equation 2, where a, b and w are 0.03, 4.03 and 1.13, respectively.

euent samples were determined by Beer's law, using the optical density (observed at 596 nm) and the molar extinction coecient of the dye (3.57 104 M1 cm1) and a path length of 1.00 cm. A typical rst order plot of color degradation with time during the rst 8 min of irradiation of a 35 ppm dye solution spiked with 938 ppm H2O2 is shown in Fig. 1. The plateau at the beginning of the run represents the warm-up time of the lamp (H45 s). The data used to model the relation between dye degradation and the ``eective H2O2'' by use of equation 2 is given in Table 1.

The t of experimental data to the assumed model for each scenario of ``eective H2O2'' described in the previous section are presented in Figs 2 and 3, respectively. Estimates of model parameters (at 95% condence level), the correlation coecient r2 and the error function E for each H are listed in Table 2. It is remarkable that the error (E) of the model for both cases of H, is approximated by a simple polynomial, dH2, where d is a case specic constant, whose magnitude reects the relative signicance of the polynomial to the accuracy of the model. The parameter a, or the intercept of equation 2 takes care of the photo-degradation of the dye in the

Fig. 3. First order degradation rate constant of Black-B as a function of the relative concentration of H2O2 to that of the dye. The solid line represents a nonlinear regression t to the data by use of equation 2, where a, b and w are 0.02, 0.30 and 0.19, respectively.

Nilsun H. Ince

1083

Table 2. Correlation coecients and model parameters to predict rst order degradation rate constant of Black-B by equation 2. (Figures in parentheses are 95% condence intervals) ``Eective H2O2'' H F(H2O2) (200300nm) (H2O2)0/(dye)0 (mg l1/mg l1) r2 0.999 0.995 a 0.031 (20.02) 0.015 (20.010) b 4.027 (20.49) 0.300 (20.02) w 1.143 (20.57) 0.193 (20.03) E dH2 d = 8.160 (20.49) dH2 d = 0.003 (20.00)

absence of light and H2O2 and the estimated values (for both denitions of H) within the reported condence intervals agree well with the observed value of k given in Table 1 (0.024 min1). It is evident from Figs 2 and 3 that the rate of dye degradation increases with increasing concentrations and/or photolysis rates (as expressed by the amount of UV absorption F) by H2O2 up to a threshold value, above which it declines, exhibiting typical inhibition. This is reasonable, since faster rates of degradation are expected as more and more hydroxyl radicals are produced upon the photo-dissociation of H2O2 as H O hv 42. OH 3
2 2

a polyrational equation, resembling those proposed for competitive inhibition k a bH , 1 cH dH 2 4

However, the absorption spectra of Remazol Black-B showed that, in addition to its high absorption capacity in the visible band, it also has a strong absorption in the near UV range (300 nm), where H2O2 has an absorption. Hence, when the relative quantity of H2O2 to that of the dye in the mixture is higher than the ``most eective level'' which yields maximum dye degradation, a competition for UV light is anticipated. Furthermore, hydrogen peroxide is known to be a scavenger of hydroxyl radicals at high concentrations (Yue and Legrini, 1992), inhibiting signicantly the radical uptake of the dye. Finally, it was found that dening the ``eective'' level as a fraction or a ratio rather than an absolute quantity (e.g. concentration), largely improved the sensitivity of the model, reecting as well the expected competition between the dye and hydrogen peroxide for light and hydroxyl radicals. The proposed model predicts a most ``eective'' level of approximately 14.0 and 0.33 for H2O2/dye ratio and F, respectively, at which dye degradation rate is maximum (Figs 2 and 3). These predictions are in good agreement with the experimental data of 14.44 (corresponding to 517 mg l1 H2O2 and 35.8 mg l1 Black-B, respectively) and 0.36, given in Table 1.

where, k is the rst order dye degradation rate constant (min1), H is the ``eective hydrogen peroxide'' (expressed as either the fraction of light it absorbs or the ratio of its concentration to that of the dye at time zero) and a, b, c and d are empirical constants. It is expected that the proposed model for Remazol Black-B is useful in estimating the right oxidant dosages in UV-enhanced chemical treatment of dyeing euents, to prevent excess dosing induced by the addition of the stoichiometric requirements. The constants of the model will naturally vary in ac\cordance with the operating conditions, such as the UV dose and the chemical characteristics (such as dye structure, radical scavengers, pH) of the euent tested.
Acknowledgements The study presented here is part of a research project supported by Bog i University azic Research Fund in Turkey through Grant No. 94H0067, and the Natural Science and Engineering Research Council of Canada through collaboration with Calgon Carbon Oxidation Technologies. The technical advice and discussions of Professor James R. Bolton in the Chemistry Department of the University of Western Ontario are highly appreciated.
REFERENCES

CONCLUSIONS

The impact of H2O2 in color removal kinetics of a reactive textile dye under UV light was investigated and modeled by use of a nonlinear regression technique. It was found that the rate of decolorization increases with increasing doses of ``eective hydrogen peroxide'' H, up to a ``critical'' value at which it is a maximum and beyond which it is inhibited. The correlation was modeled in terms of

Boeniger M. F. (1980) Carcinogenity of azo dyes derived from benzidine. Department of Health and Human Services (NIOSH), Publ. No. 80119, Cincinnati, OH. Bolton J. R. and Cater S. R. (1994) Homogenous photodegradation of pollutants. In Aquatic and Surface Photochemistry, ed. G. R. Helz, R. G. Zepp and D. G. Crosby, pp. 467490. CRC Press, FL. Brown M. A. and De Vito S. C. (1993) Predicting azo dye toxicity. Crit. Rev. Environ. Sci. Technol. 23, 249324. Ganesh R., Boardman G. G. and Michelsen D. (1994) Fate of azo dyes in sludges. Water Res. 28(6), 1367 1376. Gregor K. H. (1992) Oxidative decolorization of textile wastewater with AOP's. In Proc. of the 2nd Int. Symp. on Chemical Oxidation Technology for the Nineties, Feb. 1921, Nashville, TN. Ince N. H., Stephen M. I. and Bolton J. R. (1997) UV/ H2O2 degradation and toxicity reduction of textile azo dyes. J. Adv. Oxid. Technol. 2(3), 442448. Lin S. H. and Peng C. F. (1996) Continuos treatment of textile wastewaters by combined coagulation, electrochemical oxidation and activated sludge. Water Res. 30(3), 587593.

1084

Eect of H2O2 in dye degradation Sutton F. A. (1955) Systematic Handbook of Volumetric Analysis. Butterworths Scientic Publications, 13th edn, London. SYSTAT for Windows: Statistics, Version 5 edn, Evanston, IL. Yue P. L. and Legrini O. (1992) Photochemical Degradation of organics in water. Water Pollut. Res. J. Can. 27(1), 123137.

Pagga U. and Brown D. (1986) The degradation of dyestus in aerobic biodegradation tests. Chemosphere 15(4), 479491. Shu H. Y., Huang C. R. and Chang M. C. (1994) Decolorization of mono azo dyes in wastewater by advanced oxidation processes: a case study of Acid Red 1 and Acid Yellow 23. Chemosphere 29(12), 2597 2607.