Water 43.

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5:38 pm

Page 221

I.A. Balciog˘lu and ˙I. Arslan
Bog˘aziçi University, Institute of Environmental Sciences,80815 Bebek, I˙stanbul, Turkey
Abstract Ozonation and O3/H2O2 oxidation of reactive dyestuffs and simulated textile dye-bath were
investigated. Effects of reaction pH, initial dye concentration, H2O2 concentration and assisting chemicals
on treatment efficiency were examined. We found considerable improvement in COD and colour removal
rates at pH=11, that was almost the actual pH of the prepared textile wastewater, whereas in particular
increasing the initial dyestuff concentration had an adverse effect upon oxidation rates. Removal of colour,
COD and TOC were found to be fairly sensitive to the introduction of soda that is frequently applied as an
auxiliary chemical during the reactive dyeing process. The addition of H2O2 had negligible effect on COD
removal efficiency and decolorization rate compared to ozonation alone at different pH values. Accordingly it
can be inferred that the theoretically expected effect of OH˙ radical scavengers (e.g. carbonate, chloride)
present in the synthetic dye-bath as well as introduced radical formation promoters (e.g. H2O2, OH–) were
probably hidden due to the complexity of the synthetic wastewater matrix. Biodegradability of the ozonated
dye-bath was accelerated by a factor of three corresponding to a 233 % relative enhancement. The inhibition
of the oxygen uptake rate decreased from 91 % to 75 % within only 5 min treatment time.
Keywords Advanced oxidation processes; spent reactive dye-bath; ozonation; O3/H2O2 treatment; reactive
dyestuffs; textile wastewater

Introduction

Colour removal of effluent from the textile dyeing and finishing industry is becoming
important because of aesthetic as well as environmental concerns (Grau, 1991; Reife and
Freeman, 1996). Interest in water reuse and particularly stricter discharge standards
including remediation of industrial effluent to recreational water force textile manufacturers to treat their wastewater more thoroughly. Ultimately the concern is being driven by
public perception that coloured effluents are not environmentally acceptable. For the
treatment of textile industry wastewater ozone is applied especially for colour removal
since it reacts quickly with coloured compounds so that residual ozone is available to
reduce the remaining COD and TOC of the wastewater (Singer, 1990). However, full-scale
use of ozone is still rare due to the high (electrical energy) costs involved in its
formation, but it is increasingly used as a complementary process for the removal of
recalcitrant compounds in water and wastewater. Consequently colour free and partially
oxidized effluent can be achieved by ozonation together with minimum sludge formation
and associated disposal costs. It is also generally accepted that ozone transforms refractory,
poorly biodegradable impurities into by products that are of a smaller molecular size,
more oxygenated and polar thus enhancing a preceding activated sludge treatment
(Rice, 1981).
In our preliminary studies conducted with reactive dyestuffs and synthetic dyehouse
wastewater simulating typical effluents from the dyeing and rinsing stages, we have
demonstrated that compared with the Photo-Fenton, H2O2/UV and TiO2-mediated photocatalytic oxidation processes, ozonation provided a much quicker and more practical
decolorization (Gaehr et al., 1994; Arslan and Balcıog˘lu, 1999 a, b; Arslan et al., 1999).
Treatment of rinse water is less economic, because the industrial practice is to use 5–10

Water Science and Technology Vol 43 No2 pp 221–228 © IWA Publishing 2001

Partial oxidation of reactive dyestuffs and synthetic textile
dye-bath by the O3 and O3/H2O2 processes

221

From the practical point of view it is more feasible to treat the concentrated dye-bath. TOC. All chemicals employed for analysis were at least reagent grade.0 4. Composition of the concentrated dye-bath mixture is presented in Table 1. Balcıog˘lu and I˙. it was taken into account that practically 15 % of the dyestuffs in their fixed and/or hydrolyzed form and 100 % of the assisting chemicals always remain in the exhausted dye-bath. From Table 1 extraordinarily high concentrations of Cl– and CO32– known as effective radical scavengers are apparent (Buxton et al.076 0. Materials and methods Materials H2O2 (30% w/w) used in the ozonation experiments was obtained from Merck. The selected dyes were representative in their structure as well as their reactive groups.583 0. The recipes were obtained from a local integrated textile manufacturing plant. 1988). These are expected to inhibit treatment performance of the selected AOPs seriously. Six reactive dyestuffs purchased from Hoechst and Sandoz corporations and their corresponding assisting chemicals were used without further purification. Experimental procedure Ozonation experiments were carried out for one hour in a 1. The characteristics of effluents such as COD.8 to ensure complete hydrolysis. 1997).Water 43.084 0. With this in mind. In the preparation of dye-bath. Furthermore. The choice of textile wastewater is due to its recalcitrant and even toxic nature towards conventional biotreatment. the reactive dyestuffs were continuously stirred for 3 hours at a pH of 11.5 L-capacity (78 cm height. Distilled deionized water was used for the preparation of the analytical solutions. the possibility to integrate an ozonation step as a part of an effective treatment to increase its biodegradability was examined.167 0.0 *colour index number not known **contains 1.0 70. Remazol Red 3B (-)* ** Remazol Brilliant Yellow GL (Reactive Yellow 37) Drimarene Orange K-GL (-)* Drimarene Rubinol R/K-5BL (-)* Drimarene Blue K-2RL (-)* Urea NaCl Na2CO3 NaOH 222 Concentration in the spent reactive dye-bath (g/L) 0. reactive dyestuff and simulated dye-bath solutions.0 5. Arslan times the volume of the dye-bath during the proceeding washing-off stages.092 3. 6 cm diameter) semi-batch ozone bubble column made of glass. optical density in the UV and visible region (UV – vis spectrophotometry) were used to demonstrate the performance of the oxidation processes in treating dyestuffs as the target compounds in multi-component water matrices. During the preparation of synthetic dye-bath effluent.6 % w/w complexed copper . IOUR (relative inhibition of the oxygen uptake rate). BOD5.126 0.2 (B74) corr 3/2/01 5:38 pm Page 222 I. Ozone was produced from Table 1 Composition of the synthetic exhausted dye-bath liquor Chemical Remazol Black SB 133% (Reactive Black 5) . the present study focused on the treatment of simulated dye-baths by ozonation alone and combined with H2O2 within one hour treatment time..A. Preparation of the synthetic dye-bath effluent Synthetic dye-bath effluent was prepared as a mixture of four different recipes most widely used in the reactive cotton dyeing process (Akın Tekstil.

1989). The pH of the samples to be ozonated was adjusted to the desired value by the addition of either sulfuric acid or sodium hydroxide to the medium. mg/(L.h). OUR was measured for two hours aeration of the sample (t=0.min) Characterization of dye-bath effluents Table 2 summarizes selected process parameters to follow the treatment performance of the oxidation reactions.51 g/h (IOA. Procedure for respirometric measurements Acclimatized activated sludge from the treatment plant of a local integrated textile factory was mixed with 1:1 diluted and pH-adjusted 750 mL raw wastewater from the factory. 30. 10.0) immediately after sampling. Balcıog˘lu and I˙.. mg/(L. 1989). The residual H2O2 was decomposed by catalase enzyme (176. the indigo colorimetric method (Bader and Hoigné. The wavelength of maximum absorption. OUR values obtained for raw textile wastewater were taken as the control. O3 production rate: 5 g/h).A.Water 43. Ozone input rate was determined iodometrically as 3. 50 and 60 min in the same way. Results and discussion Effect of the initial pH value Reaction pH is an important operating parameter influencing treatment performance of the ozonation process significantly (Glaze et al. TOC was measured by a Carlo-Erba Model 480 TOC-analyzer (Fisons Instruments). Samples were taken at regular time intervals for 1 hour and kept for 30 min prior to analyses to quench residual ozone. O2 flow rate to the generator was maintained at 100 L/h and monitored with a rotameter incorporated into the ozone generator.340 U per ml. I. 20. For the detection of residual O3. beginning of aeration) at 15min time intervals as follows. Prior to the respirometric measurements the pH of the raw and ozonated samples was adjusted to 7.8. 1981) was employed. Then the bottle was aerated with two diffusers for 2 hours. Per cent relative inhibition of the respirometric activity was calculated by the equation presented below: IOUR (%) = where OURc − OURs × 100 OURc IOUR = relative inhibition of OUR.5 and 1⁄2 diluted with O2 saturated and nutrient-enriched distilled water prepared according to Standard Methods (AWWA. 40. of Reactive Black 5 shifts from 597 nm to 620 nm above pH>11. The absorbance measurements at 597 nm and 254nm were used to evaluate the colour and aromatic content of the effluents. 15. To demonstrate its effect on treatment 223 . 1987). BOD5 and COD measurements were conducted in accordance with Standard Methods (AWWA. The 1500 mL-mixture was introduced to a 2000 mL bottle with 50 mL pre-settled activated sludge. The ozone-oxygen mixture was introduced from the reactor bottom through a sintered glass plate diffuser at a rate of 2340 mg/(L. (%) OURc = OUR of control sample.0–7. The dynamic oxygen uptake rate (OUR) was determined with a WTW Oxi 3000 model respirometer equipped with a microprocessor.min) OURs = OUR of raw or ozonated sample. 1 U destroys µmoles of H2O2 at pH=7. OURs were measured for the untreated full recipe as well as the samples ozonated at alkaline pH for t=5. 1987). λmax.2 (B74) corr 3/2/01 5:38 pm Page 223 Analytical measurements Absorbance of dye-bath solutions in the UV-visible region was detected by a Shimadzu double beam spectrophotometer using a 1 cm quartz cuvette. Arslan dry and pure oxygen by a Fischer OZ 500 Model ozone generator (max.

2 (B74) corr 3/2/01 5:38 pm Page 224 Table 2 The characterization of Reactive Black 5. whereas COD removal increased to 86 % at an initial pH of 11.4 11. Balcıog˘lu and I˙. respectively. For the pH range 2–9 colour removal proceeded almost equally fast (average kd = 1 1/min). as a function of initial pH. 67 and 72 % was obtained. 7.3 5. For the pH values 2. 7 and 9. 5. 5.6 *could not be measured due to Cl– interference **absorbance at 597nm wavelength efficiency. Arslan 224 Dye dye + soda dye + NaCl dye + urea dye mixture full recipe COD (mg/L) TOC (mg/L) UV254nm (1/cm) A597nm** (1/cm) BOD5 (mg/L) 281.4 11. dyestuff + assisting chemical and the simulated dye-bath Dye-bath components I.4 –* 314. an overall COD removal of 65. Raising the pH to 11 increased the pseudo-first order decolourization rate constant by a factor of two.1 11. the pH of 500 mg/L hydrolyzed Reactive Black 5 being the major component of the exhausted dye-bath was adjusted to 2.4 11. kds.3 5. At all tried pH values complete decolorization was achieved in the first 10 min of ozonation. Figure 1 a and b shows COD reduction kinetics and pseudo-first order decolorization rate constants.5 13.6 – – – 15.6 19.7 16. Figure 1 Effect of initial pH on a) COD abatement and b) decolorization rate constant kd for 500 mg/L hydrolyzed Reactive Black 5 . This hypothesis is also supported by the evidence that no residual O3 was detected at pH=11 in the reaction medium. This observation is thought to be the consequence of enhanced O3 decomposition and shift towards a radical type reaction at alkaline pH values.Water 43.4 281.4 13.5 746 –* 99 – – – – 909 5. 9 and 11 and subjected to ozonation for one hour. From the Figure 1 b.3 5.A. 69. a sharp increase in colour removal rate constant at pH=11 is obvious.

Kd (1/min) = 129. Figure 2 implies that. Arslan To explore the effect of initial dyestuff concentration on treatment efficiency. Figure 3 b contains the mathematical relationship established between decolorization rate constant kd and Ci for ozonation at alkaline pH. 1989). relative overall COD removals for initial dye concentrations of 100.6426 Similarly. 750 and 1000 mg/L Reactive Black 5 ranged between 67 % and 83 %.08Ci (mg/L)–0.05Ci (mg/L) –0. Balcıog˘lu and I˙. Effect of added H2O2 Due to the fact that initiation of ozone decomposition by H2O2 is much more rapid than with the hydroxide ion (Glaze and Kang.Water 43. 500. The following kinetic relationship was established between pseudo-first order COD removal rate constant kCOD and initial dyestuff concentration Ci. experiments were conducted with 100–1000 mg/L Reactive Black 5 at pH=11 for one hour.7762 From these findings it is obvious that increasing the dyestuff concentration had a detrimental effect upon COD removal rates. I. respectively. the effect of H2O2 addition at millimolar Figure 2 Effect of initial dye concentration on COD abatement for hydrolysed Reactive Black 5 at pH = 11 Figure 3 Plot of a) lnkd-lnCi and b) lnkd-lnCi at various initial hydrolysed Reactive Black 5 concentrations varying between 100–1000 mg/L and pH = 11 225 . after ozonation. Figure 2 and Figure 3 a and b present COD removal kinetics and obtained kd values for COD and colour removal at pH=11 and various initial reactive dyestuff concentrations.A. 250.2 (B74) corr 3/2/01 5:38 pm Page 225 Effect of initial dyestuff concentration KCOD (1/min) = 4.

Effect of H2O2 addition at varying pH values and H2O2 concentrations on COD abatement rates and kd values is displayed in Figure 4 a and b. Balcıog˘lu and I˙. the COD and colour removal rates were only improved by increasing the initial pH of the medium. It was observed that applying H2O2 did not enhance the treatment efficiency in terms of both parameters at all.A.. 1999). For this purpose. 1 a). 5. separate ozonation experiments were performed with 500 mg/L Reactive Black 5 at the pH values of 2.5. Approximately 60 % TOC removal of 500 mg/L Reactive Black 5 was obtained for both H2O2/O3 at pH=7. The expected enhancement of reaction rates by the addition of H2O2 did not occur since the aromatic structure of dyestuffs can also be destroyed rapidly via direct molecular O3 attack. Effect of dye auxiliaries and recipe dye mixture Effect of reactive dyestuffs and assisting chemicals present in the recipe dye-bath mixture were separately investigated and shown in Figure 5. COD and UV254nm removal and decolorization rate constants kd for one hour O3/OH– treatment .. 1. 1996. Arslan Figure 4 Effect of initial a) pH and b) H2O2 dose on per cent COD removal and decolorization rate constants for one hour H2O2/O2 oxidation of 500 mg/L Reactive Black 5 concentrations was investigated.2 (B74) corr 3/2/01 5:38 pm Page 226 I. Addition of the assisting chemicals NaCl and soda resulted in a significant inhibition of the colour removal rates.8. This observation is in accordance with recent studies conducted with the H2O2/O3 combination for the treatment of industrial wastewater (Gulyas et al. 9 and 11 in the presence of 10 mM H2O2 and at initial H2O2 concentrations of 0.Water 43. 7.5 and O3/OH– oxidation at pH=11. Beltran et al. 10 and 50 mM (pH = 7) added at the beginning of the ozonation process. Even more pronounced was the negative effect of recipe dyestuff 226 Figure 5 Effect of assisting chemicals and dyestuffs on per cent overall TOC. As in the case of O3 alone (Fig.

complete decolorization could be achieved even for the concentrated dye-bath. A 233 % relative increase in BOD5 values and a fair improvement of oxygen uptake rates in the wastewater samples was achieved within five min ozonation at its actual alkaline pH. The O3/OH– treatment was sufficient to remove 15 % TOC. Urea addition did not affect removal rates of the selected process parameters at all. Arslan Changes in the biodegradability BOD5 and dynamic oxygen uptake rate OUR as a function of treatment time Conclusions The results of the present study have clearly revealed that ozonation at elevated pH values provides a promising technique for partial oxidation and rapid decolorization of concentrated exhausted dye-bath liquors. increasing ozonation time) might not be necessarily advantageous for the enhancement of biodegradability and very short contact times were already sufficient to achieve the specific biodegradability potential of the effluent. respectively. Similarly. 1983. 75 % COD and 100 % colour of the concentrated dye-bath at its natural alkaline pH (=12) in only 60 min. changes in BOD5 values and dynamic OURs were measured for concentrated reactive dyebaths at their natural pH (pH=12) as a function of ozonation time. per cent overall TOC removal decreased from 61 % for 583 mg/L Reactive Black 5 to 15 % for the concentrated dye-bath liquor. From these results it can be inferred that applying higher ozone doses (e. However.Water 43. The treatment efficiency was strongly affected by the pH medium and the initial dyestuff concentration. I. Generally speaking. BOD5 values increased from 15 to 52 mg/L within the first 5 min of ozonation and remained almost constant thereafter. 1987. Gilbert. per cent IOURs of the spent dye-bath effluent were improved from 91 % to 75 % within the same time interval. For this purpose.2 (B74) corr 3/2/01 5:38 pm Page 227 addition at concentrations indicated in Table 1. g. The H2O2/O3 combination had no advantage over the direct O3 application. 1994. The extent of degradation was negatively influenced by the complex background matrix of the spent dye-bath. As can be seen from the figure.. Takahashi et al. Figure 6 presents BOD5 values and calculated % IOUR values based on 15 min aeration time in activated sludge. the potential of integrating AOPs with conventional treatment processes has been extensively investigated in the past (Scott and Ollis. 1996). the major goal of applying advanced oxidation process (AOPs) and ozonation is to increase the biodegradability of refractory pollutants and wastewater (Medley and Stover. Removal of UV254nm decreased from 91 % for Reactive Black 5 solution to only 77 % and 51 % for dye + soda and the full recipe mixture. In view of these experimental results it can be Figure 6 Changes in per cent relative inhibition of OUR and BOD5 values during O3/OH– treatment of concentrated dye-bath effluent as a function of ozonation time 227 . In the present study.A. 1995).. Parallel to the enhancement of the biodegradability. Stockinger et al. Balcıog˘lu and I˙.

. (1989). D. Brussels. 21(10). Alvarez. Ozonation – an important technique to comply with new German laws for textile wastewater treatment. Ind. J. 489–494.. Rice. Advanced oxidation processes.2 (B74) corr 3/2/01 5:38 pm Page 228 concluded that ozonation might be more feasible for the enhancement of biological oxidation than other advanced oxidation methods.P. 98Y03) is gratefully acknowledged. and Hoigné. Beltran. and Heinzle. Gilbert. (1996).. Environ. Journal WPCF. hydrogen atoms and hydroxyl radicals (OH•/O–•) in aqueous solution. Treatment of industrial wastewaters with ozone/hydrogen peroxide.L. Gulyas. 15(1). and Ollis. Iodometric method for the determination of ozone in a process gas. APHA/AWWA/WPCF (1989). 17. L. E. Prog.. Scott.M. 39. A. Kut. Helman. I. Wat. Grau. 88–104. Biodegradability of ozonation products as a function of COD and DOC elimination by example substituted aromatic substances. Gaehr.. Advanced oxidation of synthetic dyehouse effluent by O3. 32(7).A. Washington DC. Tech. Glaze. 78–88. Arslan. IOA Standardisation Committee – Europe (1987). Wat. I.. Standard methods for the examination of water and wastewater. 449–456. Dyes and Pigments. Arslan 228 References Akın Tekstil (1997).. Sci.V. 28(11). Eng. T. (1999). Ref. 1573–1580. 20(9).. and Tuhkanen. G.. Canada. Bader. R. H2O2/O3.R. Wat. Res. Nakai. 14(2). Degradation of commercial reactive dyestuffs by heterogenous and homogenous advanced oxidation processes: a comparative study. I˙. (1981).. and Katoh. Wat. F. and Ross. 001/87 (F). Oxidative treatment of simulated dyehouse effluent by UV and near-UV light assisted Fenton’s reagent. I. Ozonation of wastewater containing n-methylmorpholine-n-oxide. (1996). I.. Res. and Chapin. (1995). 2767–2783. hydrogen peroxide and ultraviolet radiation. Res. 1273–1278. (1999b). 921–932. and Kang. D. E. Sci. J. Textile industry wastewaters treatment. The chemistry of water treatment processes involving ozone. (1994). F. Acknowledgement The financial support of Bog˘aziçi Research Fund (Project Nr. 1563–1570. I˙. Greenstock. W. 28(7). J. Garcia-Araya.. Chemosphere. and Hemmerling. J. Y. 77(209).. J. (1983). Wat. J. O.. H.. von Bismarck. Technol.. and Balcıog˘lu Akmehmet. W.Water 43. USA. and Stover. T. Wat. Ozone for the treatment of hazardous materials. Singer. 30(3). Chem. Balcıog˘lu. F. Technical Report. (1995). 79–93. 127–134. (1988). Eng.. Balcıog˘lu and I˙.H. Effects of single and combined ozonation with hydrogen peroxide or UV radiation on the chemical degradation and biodegradability of debittering olive industrial wastewaters. Technol. 33(3). Tech. P. W.Res.W. Arslan. G. Assessing ozonation research needs in water treatment.. C.B. (1994). 55(5). (1987).R. (1987). .. Res. Determination of ozone in water by the indigo method... Phys. Environmetal chemistry of dyes and pigments. 723–732. J. I˙. (1999a). Data. and Balcıog˘lu Akmehmet. (1991).A.. 43(2). E.. 255–263. W. Kang. H. A. Buxton.. 30(8). Takahashi.F. Frades. Chem. S. and Oppermann. 513–886.C. (1990). 189–195. Integration of chemical and biological oxidation processes for water treatment: review and recommendations. Environ.J. 17th edn. N.P. Y. and Gimeno. AICHE symposium series.H. Effects of ozone on the biodegradability of biorefractory pollutants. 24(1).H. and Freeman. Wat Sci. Critical review of rate constants for reaction of hydrated electrons. John Wiley and Sons Inc. Variation of biodegradability of nitrogenous compounds by ozonation.L. Research. Stockinger. Reife.F. Ö. (1999). and H2O2/UV processes. 97–103. H. Glaze. P.. Description of a kinetic model for the oxidation of hazardous materials in aqueous media with ozone and hydrogen peroxide in a semibatch reactor. Journal AWWA. 9. Satoh. D. 335–352.W. Medley. (1981). Wat. Hermanutz. Ozone Sci. 1745–1748. P. Arslan.