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q Institution of Chemical Engineers
Trans IChemE, Vol 79, Part B, March 2001

PARTIAL OXIDATION OF HYDROLYSED AND
UNHYDROLYSED TEXTILE AZO DYES BY OZONE
AND THE EFFECT ON BIODEGRADABILITY
A. B. C. ALVARES, C. DIAPER and S. A. PARSONS
School of Water Sciences, Cran®eld University, Cran®eld, UK

T

his work involved a series of batch tests where Acid Yellow 17, and unhydrolysed
and hydrolysed Reactive Black 5 textile dyes were ozonated to assess the ef®cacy of
partial oxidation and associated decolourization, and parent compound degradation.
Absorbance readings and a decrease in the chemical oxygen demand/total organic carbon
(COD/TOC) con®rmed that partial oxidation was the predominant degradation mechanism. An
applied dose of 0.6 g l 1 caused 100% colour removal through dye chromophore cleavage
whilst higher doses resulted in further degradation. Biodegradability improvement in ozonated
hydrolysed Reactive Black 5 was tracked through biological oxygen demand (BOD5) increase
and BOD/COD and BOD/TOC ratios. Partial oxidation improved the biodegradability of
hydrolysed Reactive Black 5 and the optimal applied dose requirement for maximum
biodegradability improvement was 1.8 g l 1 , which increased the BOD/TOC and BOD/COD
ratios from 0 to 0.58 and 0.27, respectively. This suggested that for maximum biodegradability
improvement, partial oxidation must proceed beyond decolourization.
Keywords: partial oxidation; ozone pretreatment; textile dye wastewater; biodegradability.

INTRODUCTION

increasing percentage of oxygen in the form of hydroxyl,
carboxyl or aldehyde function groups. Partial oxidation
products include aldehydes, ketones and organic acids,
which are biodegradable6 .
Whilst the cost of ozonation for complete mineralization of recalcitrant organics may be prohibitive except
for low pollutant concentrations, ozone pretreatment in a
combined chemical-biological treatment is more economically desirable due to a combination of the following:

Whilst aerobic biological treatment processes are conventionally employed to treat both domestic and industrial
wastewaters, it has been shown that they cannot successfully
treat all xenobiotic organic compounds. These compounds,
due to their complex nature, emerge from the treatment
process unchanged before discharge into the environment
via ef¯uents and sewage sludges1 .
Textile dyes are designed to resist fading and are thus
recalcitrant, resisting biodegradation and imparting colour
to receiving waters2 . There is currently no de®nitive
treatment for textile dyeing and ®nishing wastewater, and
increasingly stringent consents including those that limit
colour mean that water companies are passing treatment
costs back to the dyers3,4 . Acid and reactive dyes resist
aerobic biodegradation and are particularly problematic
because of their lower exhaustion rates and high solubility.
They are thus found in wastewater at higher concentrations than other dye classes and as they do not adsorb easily
to biomass cell walls5 , they will not be biodegraded or
removed from the wastestream adsorbed to settled sludge
(bioelimination).
The use of ozonation prior to aerobic biological treatment
is a potential solution to reduce both colour and `hard’ TOC
or COD entering receiving waters. Rather than complete
mineralization to form inorganic salts, carbon dioxide
and water, the purpose of ozone pretreatment is partial
oxidation. During this step-wise process, complex nonbiodegradable parent compounds are converted to simpler
by-products that contain in their chemical structure an

· less ozone is required than that needed for complete
mineralization
· biological processes, with operating costs up to a tenth of
chemical ones, complete the majority of mineralization7 .
A review of the literature 8 has shown that biodegradation
of wastewaters by downstream processes can be maximized
by pretreatment doses in the range 0.23 1.04 mg O3 /mg
COD. Combined treatment of a strong textile wastewater
(3000 mg l 1 COD) with pre-ozonation increased COD
removal through the activated sludge process from 70%
to 96%9 . A pilot-scale biological trickling ®lter was able
to remove 80% COD from ozonated textile wastewater
compared to 45% without ozone pretreatment10 .
This work focused on CI Reactive Black 5 (hydrolysed
and unhydrolysed) and CI Acid Yellow 17 textile azo
dyes (Figure 1), both of which are untreatable by activated
sludge11,12 . The ®rst stage examined the ef®cacy of partial
oxidation and associated colour removal and parent compound degradation. Further investigation then followed
to assess the effect of partial oxidation on HRB5
biodegradability.
103

The Blue Book Method14 was used to determine BOD5. This indicated that although there was some mineralization. A decrease in the COD/TOC ratio was. The reduction in absorbance with increasing ozonation is shown for HRB5 in Figures 2 (a) and (b). followed by boiling at above 908 C for 5 hours to maximize hydrolysis. RB5 and AY17 showed a major peak both in the visible and ultra-violet regions of the electromagnetic spectrum. much of the organic material was degraded by conversion to other organic molecules10. Chemical structure of textile dyes used. 55±57% of the initial COD was removed and TOC was reduced by 26±27% (Figure 4). (a) CI Acid Yellow 17. The continued detection of COD and TOC after the point of 100% colour removal showed that parent compound degradation was predominantly due to partial oxidation rather than complete mineralization. and an ozone concentration of 15 mg l 1 . A reduction in absorbance at the VISlmax indicated decolourization through the cleavage of dye chromophores which in azo dyes are characterized by an N N bond (Figure 1). COD and TOC removal for all three dyes showed similar removal ef®ciencies at the same applied dose. Ozonation was carried out at uncontrolled pH using a glass stirred batch reactor and a Prominent Ozon Lab 0. and (b) CI Reactive Black 5. March 2001 . an increase in the COD/TOC ratio would have resulted due to similar degradation rates for both COD and TOC. indicating the progressive Trans IChemE. observed with increasing ozone dose (Figure 5). Were total mineralization the predominant oxidation mechanism. suggesting that colour removal was the ®rst step of partial oxidation. MATERIALS AND METHODS RESULTS AND DISCUSSION Commercial grade CI Acid Yellow (100% Sandolen Yellow E-2GL) and CI Reactive Black 5 (100% Drimarene Black K3B) were obtained from Clariant. and TOC was measured using a Shimadzu TOC-500A Total Carbon Analyser. HRB5 was investigated for biodegradability improvement by batch ozonating one litre samples for 60±240 minutes under the same conditions. unhydrolysed CI Reactive Black 5 (RB5) and CI Acid Yellow 17 (AY17).6 g l 1 (Figure 3). Vol 79.ALVARES et al.15. Working solutions of 500 mg l 1 in deionized water were prepared from hydrolysed CI Reactive Black 5 (HRB5). Ozonation progressively reduced absorbance in all cases and no new peaks were formed.5 using sulphuric acid and sodium hydroxide. At the maximum ozone dose. A stock solution of 50 g l 1 CI Reactive Black 5 was hydrolysed by adjusting to pH 11 using sodium hydroxide. the carbonaceous biological oxygen demand (BOD5) of each sample of ozonated and unozonated HRB5 was determined using three different dilutions. 99±100% transformation of the parent dye compounds through chromophore destruction was achieved at an applied dose of 0. Tertiary ef¯uent from Cran®eld University STW was used as seed.5±7. Partial Oxidation Parent compound degradation was traced in terms of absorbance reduction at the maximum UV-VIS wavelengths (lmax ). during which subsamples were removed via a sampling port and analysed to track partial oxidation in terms of chemical oxygen demand (COD). however. After this initial exploration. One litre of sample was ozonated for 180 minutes. This lagged behind chromophore destruction. Degradation of the parent compound aromatic rings was suggested by reduced absorbance at the UV-lmax . absorbance scans of unozonated and ozonated samples were obtained using a Jenway 6505 UV/VIS spectrophotometer. In addition to the tests above. Initial absorbance scans for HRB5. 104 Figure 1.5/50A ozone generator using dried air as feed gas. respectively. For all three dyes. A comparison of colour.16. Part B. determined iodometrically13 . The alkaline pH of unozonated HRB5 and acidic pH of ozonated batches were adjusted to pH 6. total organic carbon (TOC) and absorbance.7 l min 1 .17 . a ¯owrate of 0. COD was measured using Hach vials.

An optimal ozonation period for partial oxidation for biodegradability improvement would be one that did not excessively remove COD or TOC. as non-biodegradable carbonaceous material is converted to simpler. Such a decline in COD/TOC ratio due to ozone pretreatment has also been noted by other authors18. A higher BOD after ozonation is indicative of a greater availability of organic substrate for aerobic microbial degradation. reaction time and COD vs. (b) corresponding reduction in absorbance at UV and VIS-maximum wavelengths.15. A review of the literature 8 has shown that for maximum biodegradability improvement >90% parent compound elimination Figure 3. Degradation of parent dye compound (measured as VIS-lmax ) by ozonation. incorporation of oxygen into the ozonation by-products through partial oxidation. Trans IChemE. Figure 4. In the current work.20 . The ®rst order rate constants for all three dyes were calculated from the relative change in VIS-lmax vs. Part B.19. with some incidental mineralization of organic carbon. HRB5 was investigated further for biodegradability improvement due to the commercial importance of reactive dyes. Biodegradability Improvement Figure 2. their comparatively low exhaustion rates and because the majority of the un®xed dye present in dyebath ef¯uent is present in a hydrolysed form. Peak at 380±392 nm is an artefact of the spectrophotometer. reaction time.16 . The results discussed earlier con®rmed that partial oxidation had occurred. Vol 79. Effect of applied ozone dose on degradation of HRB5. and resulted in an increased BOD5. (a) absorbance scans showing reduction in absorbance at selected ozone doses. Removal of COD and TOC from dye solutions by ozonation. The rate of colour removal was 9±13 times faster than that of COD removal during the same time period (Table 1). more bioamenable compounds14. March 2001 . RB5 and HRB5 show a near linear dependence between the decrease in both colour and COD and the reaction time (Figures 6 (a) and (b)). semi-log plots for AY17. demonstrating that colour removal was not due to mineralization of the parent molecule but due to its conversion to other organic molecules by partial oxidation.PARTIAL OXIDATION OF HYDROLYSED AND UNHYDROLYSED TEXTILE AZO DYES 105 Kinetics Previous work on the ozonation of azo dyes suggests that the degradation of the parent compound and COD follow pseudo ®rst-order kinetics21 .

(a) colour removal. Effect of ozone dose on HRB5 BOD5.97 0. by which time most of the parent compound has been eliminated19 · inhibition of biomass activity in the case of toxic parent compounds so that any remaining parent compound prevents the biodegradation of oxidation by-products19 . Decrease on COD/TOC ratio by ozonation.22. ozonation at doses above the optimum can be inef®cient due to minimal additional partial oxidation or parent compound degradation24 . The BOD5/TOC ratio matched the BOD5 trend discussed earlier.073 0. possible due to the complete mineralization of biodegradable ozonation by-products24 or their conversion into recalcitrant ones. possibly due to: · initial ozonation by-product recalcitrance that requires further oxidation.28 .99 0. Ozonation of HRB5 increased BOD5 (Figure 7). with a maximum increase occurring on the application of 1. Pseudo-®rst order rate constants for the ozonation of HRB5. As in the preliminary exploration.ALVARES et al. The ozonation conditions of this experiment increased the BOD5/COD ratio and BOD5/TOC (Figure 8). Part B.006 0.81 g l 1 gave maximum biodegradability improvement. Trans IChemE. is required. based on the preliminary ozonation results. March 2001 . Thus. 106 Figure 5. Figure 6. higher doses above the optimum can diminish biodegradability. which indicated an augmentation of the biodegradable proportion of the COD and TOC content. This implies that the HRB5 ozonation by-products generated in this work could be treatable at a downstream WWTW without the need for acclimatization. Pseudo-®rst order of decay of HRB5. Further partial oxidation after initial decolourization was therefore required for maximum biodegradable by-product formation. the ozone doses for investigating HRB5 biodegradability improvement were selected in anticipation of 100% VISlmax and >90% UV-lmax absorbance reduction. Whilst lower doses may not promote adequate partial oxidation for maximum biodegradability improvement. This was re¯ected by the <90% UV absorbance reduction that coincided with the maximum BOD5/TOC ratio. RB5 and AY17.064 0. biodegradability parameters when examined as a function of ozone dosage have similarly revealed an optimum dose for maximum biodegradability improvement19.23 .99 Figure 7. An applied dose of 1. showing the continued Table 1. the COD/TOC ratio declined. The use of such an unacclimatized seed provided a robust indication of the general ease of sample biodegradability because biodegradation occurred without the development of specialized enzyme pathways through previous acclimatization.99 0. con®rming that ozonated samples contained by-products that the domestic WWTW inoculum was able to utilize.26. equivalent to 22 mg O3/mg initial TOC.81 g l 1 ozone dose. RB5 and AY17.27.053 0.006 0. In many cases.005 0. raising the BOD from 0 to 35 mg l 1 (Figure 7). represented by BOD5. and (b) COD removal. HRB5 RB5 AY17 kCOLOUR R2 kCOD R2 0. where a value of 0 indicates nonbiodegradability and an increase in the ratio re¯ects biodegradability improvement.99 0. The BOD5/COD and BOD5/TOC ratios are commonlyused indicators of biodegradability improvement25.99 0. Furthermore. Vol 79. This optimum ozone dose for biodegradability improvement was double that required for complete chromophore destruction.

C. Once determined. the optimum ozone dose for biodegradability improvement can be employed in a laboratoryscale chemical-biological system for assessment of actual process feasibility. C. 5. in economic terms the minimal additional reduction in the COD/TOC ratio would not merit the use of a higher dose. Perkowski. March 2001 This work has shown that ozone pretreatment decolourized AY17. 1995. Wat Res. Tahnli. Potential treatment cost savings The Mogden formula is the UK charging scheme for ef¯uent discharging to sewer. Cooper. Huber.and VIS-lmax provides information regarding process ef®cacy. The calculations. and Dostal. D. A. I. A. BOD/TOC. G.. J. Effect of ozone on potential treatment charges and HRB5 biodegradability. H.29.. J. Jones. C. and Ledakowicz. Thus toxic samples with a high dilution factor will give a high BOD5 value because of diluted toxicity effects. and Reed. Ozone for dye waste colour removal: Four years operation as Leek STW. Hitz. performance and optimisation. 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