Anaerobic Oxic

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Chemosphere, Vol. 33, No. 12, pp. 2533-2542.

1996
Copyright 0 1996 Elsevier Science Ltd
Printed in Great Britain. All fights resewed
PII: ?4045-6535(%)00349-0 W45-6535/96 $15.00+0.00

Biological Treatment of Dye Wastewaters Using an Anaerobic-Oxic System

Huren An*, Yi Qian’, Xiasheng Gu”, Walter 2. Tang*


*Dept of Civil & Environmental Engineering, Florida International University, Miami, FL 33 199, USA
“Department of Environmental Engineering, Tsinghua University, Beijing 100084, P.R.China

(Received in USA 8 April 1996; accepted 16 September 1996)

Abstract: Three dye solutions, namely, C.I. Acid Yellow 17, C.I. Basic Blue 3, and C.I. Basic Red 2, were
treated in an upflow anaerobic sludge blanket (UASB) reactor followed by a semi-continuous aerobic activated
sludge tank. When hydraulic retention time was about 12 hours, no significant color removal was observed in the
aerobic stage. In the anaerobic stage, Acid Yellow 17, Basic Blue 3, and Basic Red 2 were removed by 20%,
72%, and 78%, mqectively. To treat wastewater horn a dye manufacturing factory with COD concentration of
1200 rngfl and Color of 500 degree (dilution factor), an UASB reactor (4.5 liters) and an activated sludge tank
(5 liters, adjustable), COD and color were removed by more than 83% and 90% at a COD loading rate of 5.3 kg
COD/m’day in the anaerobic stage, and at the hydraulic retention time of 6- 10 hours for the anaerobic stage and
6.5 for the aerobic stage. The anaerobic stage of the A/O system removes both color and COD. In addition, it
also improves biodegradability of dyes for further aerobic treatment.
Copyright 0 1996 Elsevier Science Ltd

Keywords: Anaerobic-Oxic System; Dye Wastewater; Decolorization

Introduction
Dye wastewaters usually contain refractory dyes and other organic chemicals. Many studies
demonsuamd that traditional activated sludge systems were not effective in removing these chemical compounds
(1). Therefore, anaerobic processes become more and more popular because of their effectiveness in
treating many wastewaters containing synthetic organics such as organochlorine and phenol compounds which
are refractory under aerobic conditions (2,3). Biodegradability studies on various dyes showed that anaerobic
prcxxsses can also be used to decolorize dye wastewaters and improve the wastewater biodegradability for aerobic
treatment (4,5). To date, most anaerobic treatment studies investigate the treatment of azo dyes. For example.
Seshadri et al. reported that an anaerobic fluidized-bed reactor to accomplish the cleavage of azo bond, leading
to decolorizing azo dyes of Acid Orange 7, Acid Orange 8, Acid Orange 10, and Acid Red 14. Complete
cleavage of azo bond can be accomplished under hydraulic retention time of either 12 or 24 hours (6). The
potential decolorization of azo dyes by anaerobic microorganisms was also explored by Carliell et al. (7). The
degradation kinetics of azo dyes and limiting steps in the reaction were investigated. Harmer and Bishop reported
that 18%to 97% removal of Acid Orange 7 in a synthetic municipal wastewater could be achieved using lab-
scale, rotating drum biotilm reactors (8).
In order to investigate the biodegradability of different classes of dyes by anaerobic-oxic (A/O) system,
three dye solutions, namely, Acid Yellow 17, Basic Blue 3, and Basic Red 2, were studied. The efficiency in
removing color and COD and the improvement of biodegradability of the dyes for further aerobic treatment by

*To whom all the correspondences should be addressed.

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anaerobic stage were evaluated. In addition, the feasibility to use the A/O system to treat an dye-manufacturing
dye wastewater was also investigated.
Material and Methods

A laboratory scale anaerobic-oxic system as shown in Figure 1 was used in this study. An upflow
anaerobic sludge blanket (UASB) reactor was used at the anaerobic stage and an adjustable aeration tank with
a maximum volume of 5 liters and settling volume of 2.0 liter was used at the aerobic stage. The UASB reactor
has 3.5 liters of reaction volume, 7 cm in diameter and 90 cm in height, 1.O liter settling volume, 10 cm in
diameter, and 35 cm in height.

biogas

‘Xi-$!-

water
air

I G

r aeration-settling tank
1
influent pum r effluent

Figure 1. The A-O System

Each dye solution contained about 40 mgil of dye and 1000 mgIl of COD, which was contributed mainly

by glucose. The COD:N:P ratio of the solution was about 200:5: 1 and 600-900 mg/l (as CaCO,) of alkalinity
was added. In terms of chemical structure of the dyes studied, Acid Yellow 17 has a pyrazole ring attached to
a mono-azo bond. Basic Blue 3 is a phenoxazine dye and Basic Red 2 is an acridine dye. The dye concentration
was measured by a W-visible spectrophotometer (Shimadz) using the calibration curve established before
experiments, Color was measured using colormetric analysis after dilution, in which the dilution factor was
determined by comparing with the blank. The molecular structures of the three dyes are shown in Figure 2.

=-+=QcHI
cr+0sm.’

Acid Yellow 17 Basic Blue 3 Basic Red 2

Figure 2. The Molecular Structure of the Dyes


2.535

The industrial wastewater containing dyes contained about 1200 mg/l of average COD and 500
degree (d&ion factor) of average color. It was a mixture of neutralized discharge from a dye manufacturing mill
and glucose solution simulatmg municipal wastewater at a volume ratio of 3: 1. The average water quality of the
original wastewater from the dye manufacturing mili was: 55 mg!l SS, pH 7.0 - 7.2, 2500 mg/l COD, 5000
degree color dilution factor, 0 mg/l NH,-N, and 320 mg/l BOD,. The compositions of synthetic glucose solution
were: 500 mg/l glucose, 27 rngfl urea, 22 ms/l KH,PO,, and 1000 mg/l Na$O,.
The anaerobic seed sludge was obtained from an municipal anaerobic digester and used after
screening. The sludge had a VSS concentration of 27.6 g/l, with a VSWSS ratio of 0.38, a sludge loading rate
of 0.269 gCOD/gVSSday, and a SV of 95% with poor settleability. The aerobic seed sludge was obtained from
a wastewater treatment plant and was used after settling and incubation. The sludge had a VSS/SS ratio of 0.5 1
and a SVI of 34. Operational parameters used in anaerobic treatment of the three dye solutions were: average
HRT of 12 hours with maximum 20 hours and minimum 8 hours, 12 g/l MLSS, organic loading rate of 2-2.4
gCOD/m3-day, and an operation time about one month for each dye solution. Part of the anaerobic effluent of
each dye solution was treated by the semicontinuous activated sludge process in a shake flask with 2 g/l of MLSS
at a HRT of 23 hours and temperature of 25-30°C.

Results and Discussion


Anaerobic-oxic (A/O) treatment of dye solutions: Figure 3 presents the results after anaerobic
treatment of Basic Red 2 dye solution. The trend in terms of percentage removal of Basic Blue 3 is similar to
that of Basic Red 2. During the first ten days, both COD and dye removal rate declined from rather high value
at the beginning to very low removal rate. It appears that both the adsorption of dye onto anaerobic sludge and
degradation of dye by bacteria contribute to removal of dyes from the solution. In a continuous flow system,
adsorption may reach equilibrium in about ten days. If no degradation occurs, dye will be adsorbed to sludge
gradually until the equilibrium concentration was reached, the color removal rate will decrease along with the
decrease of the adsorption capacity. Therefore, it can be concluded that the high initial removal rates are mainly
due to the adsorption of dye to the sludge, while little dye degradation occurred in the first ten days. However,
after the adsorption equilibrium was reached, the steady-state color removal should be contributed through
biological degradation. As shown in Figure 3, COD &rd dye removal rates increased gradually after
ten days until the steady state was reached, indicating significant degradation occurred, which suggests the
acchmation of the bacteria to the dye. It implies that although the dyes can inhibit the anaerobic process at the
beginning, the bacteria were quickly acclimatedwithin ten days. Since aerobic bacteria could not digest dyes after
very long time acclimation, it can be concluded that the acclimation of the anaerobic bacteria to various dyes is
faster than that of aerobic bacteria. The acclimation of aerobic bacteria to dyes is a difficult process. For
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example, Shaul et al. reported that 15 out of 18 azo dyes passed through the activated sludge system substantially
untre&d even after more than 80 days of acclimation (9). Ganesh et al. concluded that dye removal in aerobic
process was mainly due to dye adsorbed or trapped by activated sludge iu stead of acclimation of bacteria to dyes
(10). The anaerobic process was very effective in removing color and COD. At steady state, color removal rates
were 20%, 72%, and 78% for Acid Yellow 17, Basic Blue 3, and Basic Red 2, respectively. The different
degradation efficiencies seemto be greatly influeaced by the molecular structure of the dye. For example, anionic
dyes are more degradable than other dyes under anaerobic conditions, the color removal rate of Basic Blue 3 and
Basic Red 2 are higher than tbat of Acid Yellow 17. No adaptation time of the anaerobic sludge to Acid Yellow
17 were observed. The removal rate was maintained at about 20% during the experimental period.

Figure 3. Anaerobic Degradation of Basic Red 2

Apparently, adsorption plays an important role in removing dyes in the aerobic process followed. The
e&ent from
theanaerobic reactor was fed to the aerobic reactor. Table 1 lists the COD and dye removal rates
after aerobic treatment of the effluents containing the three dyes, separately. It shows that dyes were removed
by sludge adsorption in the fn-stweek. However, no significant removal of dyes was observed aRerwards. Acid
Yellow 17 concentration was remained at high level, which indicates that the dye was not effectively removed
by the anaerobic process. The aerobic process did not further remove the dye except at the beginning due to
adsorption. Basic Blue 3 was removed at the first 8 days with declining removal rate, no color removal was
observed r&r 8 days, Therefore, the color removal during the 8 days should be contributed by adsorption.
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Table 1. Aerobic Treatment of Anaerobic Effluent

15 16 17
118 115
75 62
36.4 46.1
35.8 36.9 33.6 32.7 33.5
32.2 33.5 32.5 33.0
12.7 0 0 0
759 1065 203 255 198
156 556 117 90 67 85
79.4 47.8 55.7 73.7 57.1
16.6 18.8 13.9 2.9 3.2 3.2 4.6
13.2 10.1 2.9 2.8 3.2 4.6
29.8 27.3 0 12.5 0 0
869 684 117 126 119
70 32 52 31 35 31
91.9 95.3 73.5 72.2 73.9
__ __ __
__ I -- __

100 100 100

Anaerobic-oxic treatment of a dye manufacture waste water: The biodegradability of wastewater


from a dye manufacturing factory was also studied. Since the major organic compounds in the dye manufactory
wastewater were commercial dyes, they were refractory under aerobic conditions. In addition, other dyes and dye
precursors are also present. Therefore, feasibility of using anaerobic-oxic system to treat the wastewater
has to be experimentally studied.
Experiments were carried out in three stages, namely, start-up, acclimation, and operation. The start-up
stage was the first 27 days, the influent was the glucose solution only, with no dye wastewater added. The
purpose of this stage was to increase the sludge activity. The stage was completed after COD removal exceeded
80% and both the settleability of sludge and the sludge loading rate were improved. The acclimation stage was
tkrm the 27th to the 47th day. To acclimatethe bacteria to the dye wastewater, the dye wastewater was gradually
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added to the infhtent until the dye concentration was the same as the dye wastewater at volume ratio of 3 :1, Dye
concentrations were changed after the color removal rate become constant, The acclimation time of 20 days
appears to be the same as reported in previous study when anaerobic bacteria was acclimated to various dyes,
After the acclimation stage, the COD removal rate by the A/O system was about 85%. Treatability and
operational parameters were analyzed during the operation period from the 47th to 77th day. The aerobic reactor
was operated only on the second and the third stages at HRT of 6.5 h, 4 g/l MLSS, and 3 g/l DO.
The COD concentration and COD removal rates during the three stages are shown in Figures 4 and 5.
The figures indicate that COD removal rate reached 80% at the end of the start-up stage, and slightly decreased
when the dye wastewater was added during the acclimation period, after which the COD removal rate became
constant, COD removal rate by the anaerobic stage in operational period was above 60% at HRT of 8- 10 hours,
and the removal rate of the whole system was about 85%.

Figure 4. COD Changes During the Process


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Figure 5. COD Removal Rate During the Process

Figure 6 presents the eflluent COD and color removal rates during the operational stage at HRTs of
10, 8, 6, and 4 hours, respectively. It demonstrates that the removal rates decrease with decreasing HRT. In
addition, the removal rates were not significantly different when HRT was 10 h and 8 h, respectively. The
system has a low removal rate when the HRT was shorter than 6 hours. Therefore, the optima1 HRT appeared
to be about 8 hours. Figure 7 shows the effect of organic loading rate on the effluent COD. It suggests that when
the organic loading rate was below 5.3 gCOD/m’d, the effluent COD from the A/O system could be maintained
below 200 mg/l. Decreasing the organic loading rates did not significantly increase the removal rates due to the
constant amount of biomass. Therefore, the recommended organic loading rate is about 5.0 g COD/m’d.
L.ettinga(11) reported that treatment of wastewater containing refractory chemicals by UASB could reach high
efticient when organic loading was about 1-4 gCOD/m’d.
In this study, the dye wastewater was treated with glucose solution simulating the water quality of
municipal wastcwatcr. In engineering practice, the best approach is to treat dye wastewaters by combining with
municipal wastewaters, especially when dye wastewater contains less than one quarter of the total volume (12).
This is because municipal wastewaters supply nitrogen, phosphorus and the other nutrients which are essential
for bacteria growth. In addition, the fluctuations in pH. alkalinity, and temperature of dye wastewater could be
reduced by combining with municipal wastewaters.
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2 3 4 5 6 7 8
Ckga~cLnadingRate (k&IUD/m d)
0
the A-OSy&n
o the Anaaobic Ructor

Figure 6. Effect of the HRT of Anaerobic Reactor Figure 7. EMuent COD vs Organic
on Treatment Efficiency Loading Rate

The role of the anaerobic process: The anaerobic process plays an essential role in removing color
and COD, and in improving the biodegradability of the wastewater under aerobic conditions. More than 60%
of COD was removed in the anaerobic reactor. Figure 8 demonstrates the color removal at different HRTs, which
indicates that anaerobic process is very important in decolorization. It contributes to more than 80% of color
removal when HRT was 8-10 hours. However, the color removal rate decreased at the HRT of 6 hours. The
color removal of the whole system is above 90%. On the other hand, the aerobic process removed only small
portion of the color, possibly by adsorption. Another important role which anaerobic process plays is to
improve biodegradability intermsof BODJCOD ratios. Generally, the wastewater is considered biodegradable
when BODJCOD ratio is above 0.25. Figure 9 shows the BOD,/COD before and after the anaerobic treatment.
When HRT was longer than 6 hours, BODJOD ratio increased from about 0.2 for the influent to more than 0.3
for the effluent, which indicates the improved treatability of wastewater under aerobic conditions. One of the
most reasonable explanation for this improvement is that anaerobic process apparently changed the molecular
structure of the dyes into different !Yagments,which was readily degradable under aerobic conditions.
56 60 65 70 75 80 /

Tie(d)
01
m mumt m Effluent of Amembic Reactor 4 5 8 10
El3luent of The A-O System HRTofthsAnmbicIfmctm(h)

0 b@lLm = pfnuent of the Anaerobic Rude

Figure 8. Color Removal at Different HRT Figure 9. BOD,/COD at Different HRT

Conclusion
Anaerobicprocessesareeffectiveforthe treatment of dye solutions, especially for decolorization. Three
dye solutions are decohnized anaerobically to different extents, while the aerobic process showed no significant
removal of the original dyes. When a dye wastewater with COD concentration of 1200 mg/l and color of 500
degree was treated by the A-O systun COD and color removal rates can be as high as more thau 83% and 90%,
respectively. The effluent COD less than 150 mgil and color less than 100 dilution factor were obtained. In the
A-O system, the anaerobic stage played an essential role in removing both color and COD, because it apparently
improves biodegradability of dyes for fnrther aerobic treatment. Therefore, it may be concluded that anaerobic-
oxic system is a better treatment system than anaerobic processes.

References
1. Lise, H.A., et al.,“Nonpriority Analysis of the Wastewater Streams of Four Dye Manufacturing
Facilities”, JWPCF, 62,665-669, (1990)

2. Vochten, P., et al., “Aerobic and Anaerobic Wastewater Treatment”, Proceedings 5th International
Svmvosium on Anaerobic Digestion, 69, (1988)

3. Young, L.Y., “Anaerobic Degradation of Aromatic Compounds”, In Microbial Degradation of Orcanic


Comvounds, (1984)

4. Brown,D., et al., “The Degradation of Dyestuffs, Part I- Primary Biodegradation under Anaerobic
2542

Conditions”, Chemosuhere., & 397, (1983)

5. Hum, A., Yi, Q.,aud Xashmg, G., “A Way for Water Polhuion Control in Dye Manufacturing Industry”
Proceedines of Purdue IndustliaJ waste conference, 49th, 771-775, (1994)

6. Seshadri, S., Bishop, P. L., and Agha, A. M., “Anaerobic/aerobic Treatment of Selected Azo Dyes in
Wastewater”, Waste Manaoement, j& 127-137, (1994).

7. Carliell, C. M., Barclay, S. J., Naidoo, N., Buckley, C. A., Mulhollaud, D.A., and Senior, E., ” Microbial
Water S.A. 2 1 61-69, (1995).
Decolourisation of a Reactive Azo Dye under Anaerobic Condition” 1~,.-..._.

8. Hatmer, C., and Bishop, P., “Transformationof Azo Dye AO-7 by Wastewater Biotilms”, Water Science
and Technolow, & 627-636, (1992).

9. Shaul, G. M., Dempsey, C. R., and Do&al, K. A., “Fate of Water Soluble Azo Dyes in the Activated
Shtdge Process” EPA/600/S2-88/30, Water Engineering Research Laboratory, Cincinnati, OH, (1988)

.lO. Ganesh, R, Boardman, G. D., and Michelsen, D., “Fate of Azo Dyes in Sludge”I->_)
Wat. Res. 28 1367-
1376, (1994).

11. Lettinga, G., “Anaerobic Tmatment of Sewage and Low Strength Wastewater”, Proceedines of the 2nd
lntemational Svmnosium on Anaerobic Dieestion, (198 1).

12. Gratt, P., “Textile Industq Wastewaters Treatment”, Water Science & Technology, 24_ 97-103, (1991).

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