Journal of Chemical Technology and Biotechnology

J Chem Technol Biotechnol 78:6–14 (online: 2002)
DOI: 10.1002/jctb.713

Effect of stream segregation on ozonation for
the removal of significant COD fractions from
textile wastewater
Serdar Dogˇruel,* Fatos¸ Germirli-Babuna, Is¸ık Kabdas¸lı, Gu¨c¸lu¨ Insel and Derin Orhon
Environmental Engineering Department, Istanbul Technical University, I˙.T.U¨. I˙ns¸aat Faku¨ltesi, 80626 Maslak, Istanbul, Turkey

Abstract: Ozonation was tested on selected streams of cotton finishing textile plant wastewater for
optimizing chemical oxygen demand (COD) removal. For this purpose, significant COD fractions in
the wastewater were experimentally identified and the effect of ozone on these fractions was
investigated. Ozonation experiments were performed with a 1 dm3 sample volume. Ozone treatment of
batches of raw wastewater provided, at a rate of 62 mg min1 and a gas feeding time of 15 min, achieved
complete colour removal but only 21% COD reduction. Increasing the feeding time to 30 min slightly
increased the COD removal to 32%. At this feeding time, removal of the readily biodegradable COD
was 60%, but soluble inert COD reduction remained at 16%, indicating selective preference of ozone
for simpler compounds. At low concentrations, ozone was mainly influential on soluble COD compounds. Longer feeding times also affected particulate compounds, resulting in the solubilization of
the COD fractions. Pre-ozonation of the dye-house wastewater, as a segregated stream, proved much
more effective in the breakdown of refractory organic compounds, rendering the overall plant effluent
more amenable to biological treatment.
# 2002 Society of Chemical Industry

Keywords: ozonation; textile wastewater; cotton finishing; chemical oxygen demand fractionation; stream
segregation; reactive dyes.

NOTATION

F/M
OUR
SH
SI
SS
SS
ST
VSS
XT
YH

Food/microorganism ratio (g COD (g
VSS)1)
Oxygen uptake rate (mg O2 dm3 s1)
Rapidly hydrolysable COD
(mg COD dm3)
Soluble inert COD (mg COD dm3)
Readily biodegradable COD
(mg COD dm3)
Suspended solids (mg SS dm3)
Total soluble COD (mg COD dm3)
Volatile suspended solids (mg VSS dm3)
Total particulate COD (mg COD dm3)
Heterotrophic yield coefficient (g COD (g
cell COD)1)

1 INTRODUCTION

The dyeing process in cotton finishing textile plants,
such as that investigated in this study, mostly involves
reactive dyes. From an environmental impact standpoint, reactive dyes are much more soluble than
others, imparting to the wastewater a strong colour1,2

and organic residues with a significant non-biodegradable fraction, persisting through chemical precipitation and biological treatment.3,4 In fact, chemical
precipitation, although effective for the removal of
colour due to dyes with limited solubility, such as
disperse dyes, remains relatively inefficient for soluble
dyes.5 Regardless of the removal efficiency potential
provided, sludge generation, which requires additional
and costly handling and disposal, is a major drawback
for chemical treatment.5,6 Biological treatment inherently increases the non-biodegradable organic matter,
initially present in the wastewater, through the
generation of soluble residual microbial products.7
Chemical oxidation with ozone, however, is one of the
most suitable chemical oxidation processes for effective colour removal from textile effluents, with
simultaneous interaction and breakdown of refractory
organic matter resistant to biodegradation, without
leading to sludge production.6,8
Ozonation, despite its distinct technical advantages,
may prove costly when applied to the entire wastewater volume. Cotton finishing, however, like other
major textile operations, involves a sequence of welldefined batch operations in terms of chemicals used

¨ . ˙Ins¸aat Faku¨ltesi, 80626
* Correspondence to: Serdar Dogˇruel, Environmental Engineering Department, Istanbul Technical University, ˙I.T.U
Maslak, Istanbul, Turkey
Contract/grant sponsor: Environmental Biotechnology Center of the Scientific and Research Council of Turkey
Contract/grant sponsor: Volkswagen Stiftung
Contract/grant sponsor: Research and Development Fund of Istanbul Technical University
(Received 14 March 2002; revised version received 3 July 2002; accepted 28 July 2002)

# 2002 Society of Chemical Industry. J Chem Technol Biotechnol 0268–2575/2003/$30.00

6

It must be kept in mind that in the typical textile plants some processes are realized only once in a while.0 105. The plant used in the survey reflects a typical example of the knit fabric finishing sub-category.0 91.7 10. mercerized cotton knit fabric Total Average daily production (kg fabric day1) 5300 1700 700 Unit wastewater generation m3 (t fabric)1 82.2 9.7 5.7 22. Ozonation of this stream.3 68. Changes induced by ozonation on soluble COD components and specifically on the fate of soluble inert COD fraction were also evaluated under different operating conditions.7 13.3 10.8 42 62 43 82 11 11 750 0. polyester–viscose rayon blend knit fabrics.7 3.3 36.9 27.0 77.95 5. a new concept for treatability-oriented wastewater characterization.Stream segmentation in ozonation removal of COD from textile wastewater 2 MATERIALS AND METHODS 2.0 136.0 110. an effluent of dye-house operation. the objective of this study may primarily be defined as the investigation of the effect of partial ozonation of selected wastewater streams on the removal of COD and colour. and for the reduction of soluble non-biodegradable COD fraction.5 40.4 44.3 5. as a technically effective and economically feasible means of treatment.4 m3 day1 437 68 6. Plant characteristics Process Cotton knit fabric Optical brightening 60 °C reactive (Remazol1) dyeing with kiering Dyeing 1st rinse 2nd rinse Others 95 °C reactive (Procion2) dyeing with bleaching Dyeing 1st rinse Others Other finishing operations Mercerized cotton knit fabric Viscose rayon knit fabric 95 °C reactive (Procion2) dyeing Dyeing 1st rinse Others Other finishing operations Polyester þ viscose rayon knit blend Polyester knit fabric Cotton þ polyester knit blend Polyamide knit fabric Sugar bleached. such a selection is an important step in planning the experimental study.7 110. etc. cotton knit fabric 95 °C Procion2 dyeing with bleaching and viscose rayon knit fabric 95 °C Procion2 dyeing.85 0. The selected processes are cotton knit fabric optical brightening.8 2300 600 100 900 500 400 800 1700 1200 300 100 10 400 Sample % A 58.2      7. The experimental survey is conducted Table 1. polyamide knit fabrics and cotton–polyester.9–11 It is therefore possible to apply ozonation to a selected portion of the raw wastewater. for the optimum use of the chemical oxidation potential provided.2 Experimental approach Four processes among a total of 20 were selected for experimental investigation to represent the plant effluent as they are all routinely performed on a regular basis. which is consistent with the literature.7 50.9 167.1 7.9 1.85 0.85 5. J Chem Technol Biotechnol 78:6–14 (online: 2002) 7 .5 25.13. typical pollutants for textile effluents.1  0.95 0.4 6.5 1. bleaching. it lends itself easily to the segregation of wastewater streams.95 B        C  97.5 100        Investigated processes.14 2. was evaluated in terms of COD fractionation.0 114. both for the overall chemical oxygen demand (COD) and colour removal.1 42.1 Description of the textile plant and quality/quantity of polluted effluents generated. polyester. cotton knit fabric 60 °C Remazol 1 dyeing with kiering. involving batchwise operations such as dyeing. Therefore.4 6.9 0.6 8. In this framework. was the selected segregated stream as the major source of colour and nonbiodegradable COD in the overall plant effluent. Table 1 outlines the main production processes together with the daily production and related wastewater generation.2 82 5 99 3. Stream segregation is often practiced for wastewater recovery and re-use. applied to cotton. often a major problem in meeting the stringent effluent quality restrictions.12 According to the values given in this table. For this purpose. They also affect the effluent quality to a great extent and contribute approximately 55% to the daily total wastewater generation. when required.0 72 27. the investigated plant has a total volumetric wastewater load of 72 m3 (1 t fabric)1. involving dye-bath and rinsing discharges. viscose rayon. Consequently.

45 kPa) pressure by a feed gas flow-rate of 1.09 7. etc.67 g COD (g cell COD)1 in accordance with the data reported in the literature. analytical errors associated with COD measurements were also investigated. The pH of the biological reactors was kept in the range 7. 15 The method consists of running two aerated batch reactors of the same volume.13.77 Total COD Soluble COD (mg dm3) (mg dm3) 955 865 985 675 550 710 Colour (Pt–Co unit) TSS (mg dm3) 540 1580 275 105 190 80 J Chem Technol Biotechnol 78:6–14 (online: 2002) .42 dm3 min1 using a bubbling vessel with a total height of 120 cm.3 Experimental and analytical methods Ozone was produced from dry air by a PCI GL1 laboratory ozone generator. This evaluation indicated that the results depicted and discussed in the paper related to COD differences were significantly higher than what could be attributed to analytical errors. Two gas washing bottles containing 2% (w/w) potassium iodide solution were connected to the reactor in series in order to determine the output ozone gas passing through the reactor. ozone on different COD fractions. results obtained in a laboratory-scale system such as that used in the study. one fed with the filtered wastewater and the other with glucose. All pieces in contact with ozone were stainless steel. Experimental studies related to biological treatability involved the identification of significant soluble COD fractions. 7 mg dm3 (2. SS. The contributing wastewater streams to Samples A. Aliquots removed periodically from the mixed liquor were analysed for soluble COD.1%) for 30 mg dm3. glass or Teflon1 and stable in the presence of ozone. may affect the effectiveness of the ozonation reaction. although providing a relative evaluation on process parameters. namely the readily biodegradable COD (SS).68 10.17 OUR measurements were performed in a Manotherm RA-1000 continuous respirometer connected to a PC. 300 and 600 mg dm3. was assumed to be 0. This was a necessary experimental step of the evaluation of the impact of Wastewater volume Sample Table 2. an inner diameter of 4. As the experimental procedures in this study involve a sequence of differences in measured COD values. Conventional wastewater characterization 8 A B C m3 day1 % pH 412 89 323 100 22 78 9.0–8.5 dm3 as an ozone reactor. SI. B and C can also be seen in Table 1. In this respect. diluted to concentrations of 30. The soluble inert COD fraction. The reactors were seeded with the biomass obtained from fill and draw reactors acclimatized to wastewater.5 cm and a volume of 1. The heterotrophic yield coefficient. three different sets of COD experiments were carried out with the raw wastewater (Sample A) used in the study. The standard deviation was 1 mg dm3 (3. SI in the filtered wastewater reactor could be calculated by taking in the account the accumulation of soluble residual metabolic products in the glucose reactor. Ozonation experiments were conducted at 15 psi (103. vessel height. each measured on 30 samples. Experiments were continued until the observation of a stable threshold COD level coupled with no measurable biomass activity.S Dogˇruel et al on four different flow proportional composite samples (where batch wastewater discharges are mixed in proportion to their respective volumes to form the sample) originating from the above-mentioned processes: Sample A represents raw wastewater from the respective processes. the rapidly hydrolysable COD (SH) and the soluble inert COD (SI). Table 2 summarizes the results of conventional wastewater characterization for Samples A. may not be directly indicative of industrial practice of ozone–water contact. was performed respirometrically as defined in the method proposed by Ekama et al. B and C. Ozone gas was supplied at the bottom of the reactor through a sintered-glass plate diffuser. Sample C is defined as the remaining portion of wastewaters after the segregation of dye-baths and subsequent rinsings.6 g COD (g VSS)1. and Sample D is the flow proportional mixture of the pre-ozonated dye-baths and subsequent rinsing streams with the rest of the wastewater streams (ozonated Sample B þ Sample C). was measured according to the method proposed by Orhon et al. It should be noted that physical constraints such as bypassing of gas. and a semi-batch bubbled gas washing bottle reactor with an effective depth of 23 cm. The seed was obtained from a laboratory-scale fill and draw aerobic reactor operated at steady state with a feed composed of a glucose– wastewater mixture with equal COD contributions. The rated concentration of ozone was 2% by weight on air. Both reactors were started with the same initial COD concentration and seeded to secure an initial biomass concentration of around 40 mg VSS dm3. For this purpose.2%) for 600 mg dm3. 16 The oxygen uptake rate (OUR) measurements were conducted in samples periodically taken from 2 dm3 aerobic batch reactors where the initial food to microorganism ratio (F/M) was adjusted to 0. Sample B is composed of the dye-baths and subsequent rinsing streams.3%) for 300 mg dm3 and 13 mg dm3 (2. Wastewater samples of 1 dm3 volume were used in the ozonation experiments.0 and continuous aeration was supplied to 2. operated at a sludge age of 10 days. Determination of the readily biodegradable COD fraction. YH.

Stream segmentation in ozonation removal of COD from textile wastewater maintain a dissolved oxygen concentration of above 6 mg dm3. J Chem Technol Biotechnol 78:6–14 (online: 2002) 9 . the feeding time was set as 5 min for a wide range of ozone flow-rates ranging from 7 to 68 mg min1. Whatman GF/C glass-fibre filter-papers having a pore size of approximately 1.60 9. namely rapidly hydrolysable COD (SH). the raw wastewater sample (Sample A) and the sample representing the dye-baths and subsequent rinsing streams (Sample B) were subjected to ozonation experiments in two consecutive steps. a gradual improvement in colour removal was observed.2 mm were used for suspended solids (SS) and volatile suspended solids (VSS) measurements.52 9.06 10. A similar trend was also observed for the dye-baths and subsequent rinsing streams with an almost total colour removal and a limited COD reduction of 19%. with a parallel increase in colour reduction from 83 to 94%. namely ozone flow-rate (mg O3 min1). For Sample A. contact/feeding time (min) and utilized ozone (mg O3).47 9. The remaining soluble COD fraction. 10. as shown in Table 3.20 The colour measurements were performed by the platinum–cobalt method after filtering the samples through a 0. Following the preliminary experiments.45 mm membrane filter-paper.49 9.50 9. 3 RESULTS AND DISCUSSION 3. All have a significant impact on the efficiency of chemical oxidation. with a much narrower but higher colour removal range of 94–96%.19 All other analyses for conventional characterization were conducted in accordance with the APHA.94 Total COD Total COD Soluble COD Colour Colour (mg dm3) removal (%) (mg dm3) (Pt–Co unit) removal (%) 955 920 915 915 910 905 905 905 900 845 830 825 865 820 815 805 795 – 4 4 4 5 5 5 5 6 12 13 14 – 5 6 7 8 675 700 685 620 720 710 645 615 600 605 565 555 550 560 585 615 640 540 405 340 270 200 150 130 115 100 90 80 75 1580 100 90 80 70 – 25 37 50 63 72 76 79 81 83 85 86 – 94 94 95 96 Ozonation experiments were performed with a 1 dm3 sample volume. Samples A and B were ozonated for four different feeding periods of 5. In this way. The corresponding COD reduction was almost negligible for the majority of tests. In this part of the study. Soluble fractions were defined as filtrates of the samples subjected to vacuum filtration using also 0. with a single significant increase from 6 to 12% for 62 mg O3 min1.46 9.44 9.09 10.53 9. the selected O3 value provides a means of comparison for the two samples tested. but also in view of the fact that it corresponds to the same level of ozone utilization of around 125 mg for both samples.04 10. The results obtained could be characterized. Conventional characterization yields the total COD (CT) of the selected sample. SS was calculated from the area under the OUR curve as described by the proposed method. Results of preliminary ozonation experiments Sample a A B a Utilized Ozone flow-rate Ozone feeding time (min) ozone (mg) (mg min1) – 7 14 18 29 38 44 48 57 62 65 68 – 56 61 67 70 – 5 5 5 5 5 5 5 5 5 5 5 – 5 5 5 5 – 30 55 60 75 85 100 105 115 125 130 145 – 120 125 145 155 pH 9. coupled with a lower COD removal efficiency of 5–8%.39 10. was calculated from the following mass balance equation:18 SH ¼ ST  SS  SI ð1Þ COD measurements were performed as defined in ISO 6060. Experiments on the dye-baths and subsequent rinsing streams were conducted for a limited ozone flow-rate range of 56–70 mg min1.45 mm membrane filters. The results obtained are outlined in Table 3. mainly based on results associated with the raw wastewater. on the basis of equal ozone utilization values. In the first step.40 9.1 Ozonation experiments Ozonation involves at least three major process parameters. COD removal remained limited to 14% at 68 mg O3 min1. Each data point in the study was calculated as the mean of three replicate measurements. The results obtained are given in Table 4. As shown. It should be noted that raw wastewater and the dye-baths with subse- Table 3. the COD reduction efficiency was improved to 32% for the raw wastewater.68 9. 15 and 30 min at the selected optimum ozone flow-rate.45 9. The total soluble COD (ST) was the measured COD in the filtrate. starting from 25% at 7 mg O3 min1 and reaching 86% at 68 mg O3 min1.00 9. A value of around 60–62 mg O3 min1 was selected as the optimum ozone flow-rate.

Results of ozonation experiments at optimum ozone flow-rate Sample a A B a Utilized Ozone flow-rate Ozone feeding time (min) ozone (mg) (mg min1) – 62 62 62 62 – 62 62 62 62 – 5 10 15 30 – 5 10 15 30 – 130 235 465 1385 – 130 250 440 1360 Total COD Total COD Soluble COD Colour Colour (mg dm3) removal (%) (mg dm3) (Pt–Co unit) removal (%) pH 9. as previously explained. is perhaps the most significant COD fraction.83 9.21–23 This difference may be explained by the fact that Sample A was prepared to emphasize Table 5.85 8.35 8. using three feeding periods of 5. 3. 10 and 30 min and an ozone flow-rate of 60–61 mg O3 min1. The soluble inert COD.S Dogˇruel et al Table 4.14. Sample A represents raw wastewater and Sample D is a flow proportional mixture of the pre-ozonated dye-baths and subsequent rinsing streams with the rest of the wastewater streams. the merit of chemical oxidation by ozone may best be evaluated through its impact on SI. together with corresponding total soluble COD (ST) and colour levels are outlined in Table 5. The SI values determined experimentally for samples A and D. Review and evaluation of results in Tables 4 and 5 indicate the following. This observation may be justified on the basis of substrate (organic matter) selectivity of ozone. corresponding to 47% of the total soluble COD (ST) and to 34% of the total COD (CT). Results of inert COD experiments and colour levels at optimum ozone flow-rate Sample a A D a Ozone flow-rate (mg min1) Ozone feeding time (min) Utilized ozone (mg) ST (mg dm3) SI (mg dm3) SI removal (%) Colour (Pt–Co unit) Colour removal (%) – 61 61 61 – 60 60 60 – 5 10 30 – 5 10 30 – 130 245 1395 – 125 245 1320 675 580 545 480 675 680 685 690 320 300 295 270 320 285 275 240 – 6 8 16 – 11 14 25 540 90 45 30 540 235 225 220 – 83 92 94 – 56 58 59 Ozonation experiments were performed with a 1 dm3 sample volume. Therefore.13.2 Effect of ozonation on soluble inert COD fraction Figure 1. 10 J Chem Technol Biotechnol 78:6–14 (online: 2002) . SI.05 9. Relationship between utilized ozone and soluble inert COD removal for an ozone flow-rate of 60 mg min1 (1 dm3 sample volume). not often encountered in practice. quent rinsing streams have practically the same total COD content of around 900 mg dm3 and yet they respond differently to chemical oxidation. the effect of ozonation on soluble inert COD was investigated on samples A and D. as it by-passes biological treatment and accounts for the majority of the effluent COD. The results also indicated that changing the ozone contact time from 10 to 15 min did not appreciably affect the efficiency of chemical oxidation.90 9. It was tested in this study as an upper threshold value. SI in the raw wastewater sample was 320 mg dm3. in terms of the respective COD and colour removals achieved. as illustrated in Fig 1.72 955 850 775 750 650 865 815 790 760 700 – 11 19 21 32 – 6 9 12 19 675 580 545 525 480 550 580 605 610 625 540 90 45 35 30 1580 80 50 40 20 – 83 92 94 94 – 95 97 97 99 Ozonation experiments were performed with a 1 dm3 sample volume.68 9. In this context. For the soluble inert COD fraction (SI) experiments.09 10. A contact time of 30 min is an extreme level.18.69 8. a level significantly higher than the soluble inert COD content experimentally ascertained for similar textile effluents. mainly to evaluate its impact on COD fractions and especially on the soluble inert COD fraction.08 10.

stream segregation also proves attractive from an economical standpoint. the breakdown of the particulate compounds becomes more pronounced. as shown in Fig 1 and Table 5. from the rest of the wastewater streams. soluble COD compounds. When the latter was extended to 30 min. introduced and experimentally defined as part of the new modeling concepts. the same argument may also be put forward on the basis of Table 6. inspection of the data for Sample A shows that a 5 min contact time induced a total COD reduction of 11%. The total soluble COD level. 3. the rapidly hydrolysable (SH) and inert (SI) fractions of the soluble COD fraction. such as COD. due to a 14% decrease in the soluble fraction but only 4% in the particulate fraction. If colour removal is desired. the readily biodegradable (SS). presumably composed of dye residues. stream segregation is effective.Stream segmentation in ozonation removal of COD from textile wastewater the impact of dyeing and finishing most frequently used in the plant and therefore may not provide an accurate indication of the expected quality. J Chem Technol Biotechnol 78:6–14 (online: 2002) 11 . as preozonation of the most polluted stream renders the wastewater more amenable to subsequent biological treatment. in providing scientific explanations on the fate of organics after ozonation. remained practically unchanged at around 675–690 mg dm3 and the colour removal efficiency below 60% owing to addition of the untreated wastewater streams after pre-ozonation. Furthermore. COD fractionation. the selected dye-house effluent is only 22% of the total wastewater volume. involving only 22% of the ozone applied at the same ozone flow-rate and contact time. In fact. however. These results should be evaluated based on specific effluent requirements. if any. The effect of ozone is mainly observed on soluble components at low contact times. The effect of ozonation on the fate of different COD fractions was investigated for experimental set-ups previously used in the study. Pre-ozonation of the dye-baths and subsequent rinsing streams proved much more effective for the breakdown of these complex organics at source. If COD removal is the prime concern. Removal efficiencies obtained for individual COD fractions are given in Table 6 and the relative magnitudes of these fractions as percentage of the total COD after each ozonation experiment in Table 7. potential competition of chemical oxidation with biological treatment for biodegradable COD. It was used in this study to identify. At higher contact times. lowering ST to 480 mg dm3. corresponding to a reduction efficiency of 16%. however. Individual removal rates of COD fractions after ozonation experiments Ozone Utilized CT XT ST SS SH SI feeding ozone CT Removal XT Removal ST Removal SS Removal SH Removal SI Removal Sample a time (min) (mg) (mg dm3) (%) (mg dm3) (%) (mg dm3) (%) (mg dm3) (%) (mg dm3) (%) (mg dm3) (%) A D a b – 5 10 30 – 5 10 30 – 130 245 1395 – 125 245 1320 955 850 775 650 955 950 945 925 – 11 19 32 – <1 1 3 280 270 230 170 280 270 260 235 – 4 18 39 – 4 7 16 675 580 545 480 675 680 685 690 – 14 19 29 – 1b 1b 2b 110 40 50 45 110 75 65 100 – 64 55 59 – 32 41 9 245 240 200 165 245 320 345 350 – 2 18 33 – 31b 41b 43b 320 300 295 270 320 285 275 240 – 6 8 16 – 11 14 25 Ozonation experiments were performed with a 1 dm3 sample volume. the particulate COD reduction was significantly increased to 39%. yet providing a lower SI level.7. Therefore. with a final SI of 240 mg dm3 and a corresponding SI/ST ratio of 0. however. The same ozonation set-up was observed to provide an almost twice-higher removal efficiency for the total soluble COD. however. with little contribution.24 is a suitable tool for this purpose. Ozonation induced an SI reduction of only 8% with a contact time of 10 min. stream segregation does not appear suitable. compared with ozonation of the entire wastewater. The experimental data related to Sample D identified the dye-baths and subsequent rinsing streams as the major source of the soluble inert COD fraction. It underlines.3 Effect of ozonation on different COD fractions The experimental observations so far outlined give a clear indication of the limitations associated with overall substrate parameters. however. Increase. Review of the results obtained primarily underlines the significant impact of ozone contact time on the fate of COD fractions. At a contact time of 30 min. the crucial importance of the SI fraction and the need for optimizing the efficiency of chemical oxidation in meeting stringent effluent limitations. Evaluation of the experimental data can best be made first on the overall particulate and soluble COD components. aside from total soluble (ST) and particulate (XT) COD components. as 78% of the plant effluent is not subjected to ozonation. It should be noted that colour removal from textile effluents is not a requirement in most countries. For the same sample. resulting in the breakdown of particulate COD into smaller sized.35. together with a colour removal of 94%. This observation reflects the selective preference of ozone for simpler organics and in this respect. SI was brought down to 270 mg dm3. with a lower reduction of 29% for the soluble counterpart and averaging 32% for the total COD. lowering SI in sample D from 320 to 240 mg dm3.

The relative magnitude of different COD fractions provided the same overall picture. which indicate for Samples A and D. Prolonged ozone application for 30 min increased the oxidized total COD concentration to 305 mg dm3. which always remained the least vulnerable soluble COD component to ozone oxidation. only 10 mg dm3 from the particulate and 95 mg dm3 from the soluble portions. this time in favour of the soluble COD fraction reaching 74%. where ozone basically lowered the SS fraction. Effect of ozonation on COD ratios Sample a A D a Ozone ST SS SH SI XT feeding Utilized CT XT ST SS SH SI time (min) ozone (mg) (mg dm3) (mg dm3) CT (mg dm3) CT (mg dm3) CT (mg dm3) CT (mg dm3) CT – 5 10 30 – 5 10 30 – 130 245 1395 – 125 245 1320 955 850 775 650 955 950 945 925 280 270 230 170 280 270 260 235 29 32 30 26 29 28 28 25 675 580 545 480 675 680 685 690 71 68 70 74 71 72 72 75 110 40 50 45 110 75 65 100 11 5 6 7 11 8 7 11 245 240 200 165 245 320 345 350 26 28 26 25 26 34 36 38 320 300 295 270 320 285 275 240 34 35 38 42 34 30 29 26 Ozonation experiments were performed with a 1 dm3 sample volume. maintained the SH fraction at the same level and increased the SI fraction. with a much more significant contribution of 110 mg dm3 from the particulate COD fraction. at higher contact times. For a short contact time. It should be noted that the relative impact of ozone on particulate and soluble COD components was observed to depend on the nature of the wastewater. the SS removal was observed to remain at practically the same level because of the generation/ Figure 2. on the basis of biodegradability. as presented in Table 7. continued ozonation for 30 min reversed the ratio. indicating that ST generation through particulate COD breakdown apparently exceeded ST removal by total oxidation when ozone was applied for 30 min. however. Ozonation for 5 min was observed to change this ratio to 32:68%. presumably owing to the lack of available simpler organics. together with only a 16% decrease in SI concentration. the last mainly due to 70 mg dm3 SS removal. respectively. a level 3% higher than the initial value associated with the untreated wastewater. J Chem Technol Biotechnol 78:6–14 (online: 2002) . The sample was initially composed of 29% particulate COD and 71% soluble COD. XT and ST and (b) removal of SS. SH and SI (1 dm3 sample volume). The same observation is illustrated in Figs 2 and 3. where readily biodegradable COD (SS). the soluble COD concentration (Sample B) increased from its initial value of 550 to 625 mg dm3. A contact time of 30 min. compared with 2% for SH and 6% for SI. mainly composed of complex and non-biodegradable organics. A similar trend of oxidation was also observed for soluble COD fractions. Review of the data for Sample A in Table 6 reveals that a 5 min contact time was found to inflict an SS reduction of 64%. rapidly hydrolysable COD (SH) and inert COD (SI) are conveniently used to differentiate and group organics from simpler to more complex compounds. ozone was mainly effective on the partial oxidation of the particulate COD fraction. leveled SS and SH reductions at around 59 and 33%. through a gradual breakdown of the more 12 complex organics prior to total oxidation of the simple compounds. respectively. As clearly visualized by the data presented in Table 4. ozone preferentially attacks SS. fairly typical of textile wastewater. Removal of COD fractions of sample A by ozonation: (a) removal of CT.S Dogˇruel et al Table 7. Ozonation for 5 min was found to oxidize a total COD concentration of 105 mg dm3. a gradual increase occurs in SH and SI removal levels and a balance is established between SS generation through SH and SI breakdown and direct SS oxidation. For the dye-baths and subsequent rinsing streams. incremental concentration changes in mg dm3 for each COD fraction induced by different ozone feeding times. COD fractionation displayed in Table 7.

Istanbul (1982). emphasizing the need for optimizing the efficiency of chemical oxidation by ozone in meeting stringent effluent limitations. remained practically unchanged and the colour removal efficiency below 60%. 4 CONCLUSIONS The effluent of a knit fabric textile plant using reactive dyes was studied by means of a composite sample representing the most frequently used processes in the plant. the breakdown of particulate compounds became more pronounced. REFERENCES 1 Jedele K. Deutsch– Tu¨rkisches Umweltschutz-Seminar. even for extended contact times. a level of around 60 mg min1 was determined as the optimum ozone flow-rate. as potential sources of SS generation through chemical oxidation. soluble inert COD fraction due to complex dye residues. Oxidative Behandlung von farbigen. The total soluble COD level. Dr Thesis. If colour removal is the prime concern. especially at limited contact times. however. The concept of COD fractionation was introduced and experimentally tested to understand better and evaluate the impact of ozonation on different COD fractions. refrakta¨ren Abwa¨ssern der Textilveredelungsindustrie mit Kombination von H2O2. presumably owing to the lack of available simpler organics. the major source of the J Chem Technol Biotechnol 78:6–14 (online: 2002) ACKNOWLEDGEMENTS This study was conducted as part of the sponsored research activities of the Environmental Biotechnology Center of the Scientific and Research Council of Turkey. biologisch besser abbaubarer Reaktionsprodukte. It was also jointly supported by the Volkswagen Stiftung Fund and the Research and Development Fund of Istanbul Technical University. O3 und UV mit dem Ziel nichttoxischer. as 78% of the plant effluent is not ozonated. oxidation balance previously mentioned and the relative magnitude of SH and SI removals increased. however. stream segregation also proved attractive from an economical standpoint. Since the selected dye-house effluent constituted only 22% of the total wastewater volume. Entfa¨rbung von Textilabwa¨ssern. Pre-ozonation of the dye-house effluent. yet providing a lower SI. For the raw wastewater. prior to mixing with the rest of the wastewater flow. 2 Grau P. Textile industry wastewaters treatment. involving only 22% of the ozone applied at the same ozone flow-rate and contact time. could not be improved beyond 32%. Removal of the soluble inert COD fraction was found to remain at a much lower level of 16%. was selected as the segregated wastewater stream for chemical oxidation. however. For the dye-house effluent mainly composed of complex and non-biodegradable organics. as shown in Table 6. yielding smaller sized. soluble organic compounds. Water Sci Technol 24:97–103 (1991). The results indicated a selective preference of ozone for simpler organic compounds. SH and SI (1 dm3 sample volume). 4 Wagner V. high levels of colour and soluble inert COD. Removal of COD fractions of sample D by ozonation: (a) removal of CT. Institut fu¨r ¨ kologische Chemie der GSF Mu¨nchen und Solvey (1995). ozone was mainly influential on soluble components at low contact times. as expected. O 13 . owing to addition of the untreated wastewater streams after preozonation. if the objective of chemical oxidation by ozone is to render the wastewater more amenable to biological treatment. stream segregation does not appear suitable. Melliand Textilber 74:153– 157 (1993). with the combined effect of pre-ozonation of the segregated dye-house effluent and dilution due to mixing with the remaining wastewater volume. A more pronounced solubility could be associated with Sample D. The wastewater was found to contain. The fate of soluble biodegradable COD compounds was observed to depend on the complex balance between generation through particulate COD breakdown and removal by total oxidation. providing almost complete colour removal. Behandlung von reaktivfarbigen Abwa¨ssern mit Wasserstoffperoxid/Eisen(II) Sulfat. proved much more effective for the breakdown of these complex organics at source. At higher contact times however. Referat 10: 4. achieving an SI removal of 25%. ozone was mainly effective on the partial oxidation of the particulate COD fraction. 3 Sewekow U. Total COD reduction. Ozonation efficiency was tested both in terms of ozone flow-rate and contact time. XT and ST and (b) removal of SS. The dye-house effluent.Stream segmentation in ozonation removal of COD from textile wastewater Figure 3.

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