Process Biochemistry 34 (1999) 429 – 439

Dyestuff wastewater treatment using chemical oxidation, physical

adsorption and fixed bed biofilm process
Dae-Hee Ahn a,*, Won-Seok Chang a,b, Tai-Il Yoon b
a
Water En6ironment Research Center, Korea Institute of Science and Technology, P.O. Box 131, Cheongryang, Seoul, 130 -650, South Korea
b
Department of En6ironmental Engineering, Inha Uni6ersity c 253, Yonghyun-dong, Namgu, Inchon, 402 -751, South Korea

Received 16 February 1998; received in revised form 7 July 1998; accepted 9 August 1998

Abstract

Fenton’s oxidation and activated carbon adsorption were examined as pretreatment processes for dyestuff wastewater having
high salinity, colour, and non-biodegradable organic concentrations. In this work, each wastewater stream produced by individual
production processes was classified as streams R1, R2, and R3. The stream having a value of BOD5/COD lower than 0.4 was
pretreated by Fenton’s oxidation or activated carbon adsorption to increase the ratio of BOD5/COD which indicates biodegrad-
ability. For Fenton’s oxidation with one stream having a value of BOD5/COD lower than 0.4, the optimal reaction pH was 3.0
and the minimum dosing concentration (mg l − 1) of H2O2:FeSO4·7H2O was 700:3500. Stream R3, which consisted mainly of
methanol was efficiently treated by activated carbon adsorption. The ratio of BOD5/COD was also increased to 0.432 and 0.31
from 0.06 in Fenton’s oxidation and activated carbon adsorption, respectively. A biological treatment system using a fixed bed
reactor was also investigated to enhance biological treatment efficiency at various hydraulic retention times, pretreatment
conditions by Fenton’s reagent and salt concentrations by dyestuff wastewater. In addition, the efficiency of Fenton’s oxidation
as a post-treatment system was also investigated to present a total treatment process of dyestuff wastewater. As the influent COD
and salinity were increased, the effluent SS and COD were consequently increased. However, as the microorganisms became
adapted to the changed influent condition, the treatment efficiency of the fixed bed reactor quickly recovered under the high COD
and salinity since the microorganisms were well adapted to toxic influent conditions. A wastewater treatment process consisting
of chemical oxidation, activated carbon adsorption, fixed bed biofilm process and Fenton’s oxidation as a post-treatment system
can be useful to treat dyestuff wastewater having high salinity, colour, and non-biodegradable organic concentration. © 1999
Elsevier Science Ltd. All rights reserved.

Keywords: Dyestuff wastewater; Fenton’s oxidation; Activated carbon adsorption; Optimal pretreatment condition; BOD5/COD; Fixed bed
biofilm process

1. Introduction At present, several methods have been developed to

In the textile industry, the main pollution source of
wastewater comes from the dyeing and finishing indus-
try. Major pollutants include high suspended solids
(SS), chemical oxygen demand (COD), biochemical
oxygen demand (BOD5), heat, colour, acidity, basicity
and other soluble substances.
Abbre6iations: BOD5, 5 day biochemical oxygen demand; COD,
chemical oxygen demand; FDS, fixed dissolved solids; PAC, powder
activated carbon; SS, suspended soils; TDS, total dissolved solids.
* Corresponding author. Tel.: + 82-2-9585837; fax: +82-2-
9585805.
E-mail address: dhahn@kistmail.kist.re.kr (D.-H. Ahn)
treat dye wastewater, but they cannot be used individu-
ally because dye wastewaters have high salinity, colour,
and non-biodegradable organics [1]. For example, in
the coagulation process, a large amount of sludge is
created, which may become a pollutant itself and in-
crease the treatment cost. In addition, the oxidation
process, such as ozonation effectively decolorizes al-
most all dyes except disperse dyes, but does not remove
COD effectively [2–5]. The effectiveness of decoloriza-
tion by the oxidation process will also be reduced by
impurities in the wastewater. These may increase the
amount of ozone used and the treatment cost. Thirdly,
activated carbon adsorption is not suitable for insoluble

0032-9592/99/$ - see front matter © 1999 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 3 2 - 9 5 9 2 ( 9 8 ) 0 0 1 1 1 - 3
430 D.-H. Ahn et al. / Process Biochemistry 34 (1999) 429–439

dyes [6,7]. Finally, conventional aerobic biological pro-
cesses do not treat dye wastewater effectively because
most commercial dyes are toxic to the organisms used in
the process and result in problems of sludge bulking,
rising sludge and pin point floc formation [8 – 11]. A
method of treating dye wastewater with a hydrogen
peroxide-ferrous ion system, known as Fenton’s reagent,
has been reported in many investigators [12 – 19]. Hydro-
gen peroxide and ferrous ions are usually more stable in
a strong acid. However, if hydrogen peroxide is added
to an aqueous system containing an organic substrate
and excess ferrous ions in a strong acid, a complex redox
reaction [20] as in Eqs. (1) – (4), will occur:
’ addition, the characteristics of each stream are variable
Fe2 + + H2O2 “Fe3 + +HO − +HO
’ ’
RH+ HO “H2O + R
’ Conventional biological process are not effective for
R + Fe 3+
“ R + Fe
+ 2+
R + +H2O “ ROH +H +
The hydroxyl radical generated would attack the
organic substrate RH such as the unsaturated dye
module used in this work and the chromophore or
chromogen of the dye molecule would be destroyed and
decolorized. The most likely side reactions [21] in the
redox system are Eqs. (5) and (6), as follows;
’ ’
HO +H2O2 “ H2O +HO2
’ ’
2R “ R −R
The dimerization, as Eq. (6), of such organic
molecules as dyes, will also aid decolorization. The
Fenton’s oxidation process not only possesses the advan-
tages of both oxidation and coagulation processes, but
can also increase the amount of oxygen in water [12].
Consequently, it is expected that the method could
effectively decolorize all dye wastewater and could be
ecologically safe. Hydrogen peroxide is also a commonly
used pretreatment reagent in dyeing processes, so this
method can be expected to be more economically effi-
cient in treating wastewater than others
However, it is essential to use a biological treatment
process for reduction of COD because the use of Fen-
ton’s reagent alone to treat whole dye wastewater can
increase treatment costs. Generally, dyestuff wastewater
is composed of a variety of streams produced by each
production process, for example, diazotization, cou-
pling, filtration, milling and final product process. In
(1)
in terms of SS, COD, BOD5, heat, colour, acidity,
(2) basicity and other soluble substances.
(3)
treating dyestuff wastewater because many commercial
(4) dyestuffs are toxic to the organisms being used and result
in the problems of sludge bulking, rising sludge and pin
point floc [1]. To decrease the toxicity of dyestuff
wastewater, pretreatment by Fenton’s reagent and by
activated carbon adsorption has been investigated
[16,18].
The use of Fenton’s reagent and carbon adsorption
process, according to the characteristics of each wastew-
(5) ater stream produced by individual production pro-
cesses, was found to be a useful pretreatment prior to
(6)
biological treatment.
Therefore, to enhance the treatment efficiency from
the view of economy, it is necessary that each wastewater
stream produced by individual production processes is
analyzed and classified. According to Symons [23], the
ratio of BOD5/COD of the wastewater should be

Table 1
Characteristics of dyestuff wastewater streams produced by the individual production process

Stream pH Volume (%) COD (mg l−1) BOD5 (mg l−1) TDS (g l−1) FDS (g l−1) (BOD5/COD) ratio

A 1.38 27.2 9960 6100 183.98 110.38 0.612

B 1.71 7.6 2860 30 109.28 5.08 0.010
C 1.36 5.4 8840 2340 18.42 5.48 0.265
D 1.59 16.3 5100 1240 84.10 9.58 0.243
E 1.40 9.78 13 520 140 136.03 70.63 0.010
F 1.45 0.87 2640 1200 26.48 11.76 0.455
G 9.84 6.52 81 200 9600 207.30 92.10 0.118
H 1.54 9.78 4080 1860 118.46 93.58 0.456
I 9.75 6.52 43 200 5760 98.71 49.12 0.133

Table 2
Characteristics of dyestuff wastewater streams classified for each experiment

Stream pH Volume (%) COD (mg l−1) BOD5 (mg l−1) TDS (g l−1) FDS (g l−1) (BOD5/COD) ratio

R1 ŽA, F, H 1.43 47.85 7200 3900 130.45 83.56 0.541

R2 ŽB, C, D, E 1.52 39.08 9200 600 98.38 32.47 0.065
R3 ŽG, I 9.80 13.04 73 000 8400 162.70 84.90 0.115
 D.-H. Ahn et al. / Process Biochemistry 34 (1999) 429–439
Fig. 1. Schematic diagram of fixed bed reactor and packing material used in this experiment.
\ 0.6 if the wastewater is to be treated easily using
biological treatment and 0.4 is the minimum value for
biological treatment. Therefore, in this work, to investi-
gate the optimal pretreatment conditions for dyestuff
wastewater by chemical oxidation and adsorption, each
wastewater stream produced by individual production
processes was classified and the stream having values of
BOD5/COD lower than that of 0.4 was pretreated by
Fenton’s oxidation or activated carbon adsorption to
increase the ratio of BOD5/COD [24].
Meanwhile, a biological treatment system using a
fixed bed reactor was also investigated to enhance
biological treatment efficiency of dyestuff wastewater in
the respect of maintaining biological activity. In addi-
tion, the efficiency of Fenton’s oxidation as post-treat-
ment system [22] was also investigated in this article to
present a total treatment process of dyestuff
wastewater.
2. Materials and methods
2.1. Preparation of dyestuff wastewater streams
A disperse dyestuff wastewater used in these experi-
ments was obtained from a commercial factory and
each stream produced by individual production pro-
cesses was classified (Table 1). Their major components
are sulphuric acid (H2SO4), hydrochloric acid (HCl),
sodium thiosulphate (Na2S2O3), sodium carbonate
(Na2CO3), acetic acid (CH3COOH), methanol
(CH3OH), n-hexane (CH3(CH2)4CH3), sodium chloride
(NaCl), phenol (C6H6O), aromatic compound (includ-
ing nitro compounds) and ethylamine (C2H5NH2, ani-
line derivatives).
Each stream was reclassified into one of categories,
431
R1, R2 and R3 (Table 2). The R1 stream which was
composed of streams A, F and H stream did not need
pretreatment by chemical oxidation or adsorption be-
cause the ratio of BOD5/COD was higher than 0.4. The
R2 stream was composed of streams B, C, D and E and
showed a value lower than 0.4 (BOD5/COD). Though
the R3 stream, which consisted of streams G and I, also
showed a value lower than 0.4, it was separately
classified from R2 because the major component of G
and I stream was methanol which is difficult to oxidize
chemically. Therefore, in this work, to investigate opti-
mal pretreatment condition, Fenton’s oxidation and
activated carbon adsorption were used with the R2 and
R3 streams.
2.2. Fenton’s oxidation experiment
The chemical oxidation of the R2 stream was done in
a jar test apparatus at a temperature of 25°C. The
optimum pH for Fenton’s reagent has been shown to
be 3–5 [14,16]. Therefore, in the tests to determine the
minimum concentration of hydrogen peroxide and fer-
rous sulphate, a pH of 3.5 was chosen, using 6N H2SO4
to adjust the pH. The effect of pH variation was then
examined over the range 1–10 with 6N H2SO4 and 6N
NaOH being used to adjust the pH. In both these sets
of tests 500 ml of the waste stream R2 were placed in a
beaker (1 l) together with Fenton’s reagent (2–4 ml),
the pH was set and the mixture stirred at 200 rpm for
60 min. Adjusting the pH to 8, an anionic polymeric
coagulant (1 ml, Yang Floc A701-P, Korea) was added
and the mixture stirred for 60 min (50 rpm). The solids
were allowed to settle for 30 min and the supernatant
removed for analysis. The same basic procedure was
followed when the effect of reaction time was being
evaluated.
432 D.-H. Ahn et al. / Process Biochemistry 34 (1999) 429–439

2.3. Acti6ated carbon adsorption experiment

Activated carbon adsorption using powder activated

carbon (100 mesh) was examined with the R3 stream.
The characteristics of the PAC (powder activated car-
bon, Union Carbon) used in this experiments were:
bulk density=300 g l − 1; specific surface area = 1000
m2 g − 1; dry weight content= 5%. In this experiment,
500 ml of R3 wastewater were taken into a beaker (1 l),
mixed with PAC at 150 rpm and filtered using a GF/C
filter before analysis.

2.4. Fixed bed reactor

The schematic diagram of the fixed bed reactor and

packing material is shown in Fig. 1. The fixed bed
reactor was composed of two separate sections, each
Fig. 4. Effect of pH on Fenton’s oxidation for R2 stream.

Fig. 2. Effect of Fenton’s reagent dosing amounts on Fenton’s

oxidation for R2 stream (I). Fig. 5. Effect of reaction time on Fenton’s oxidation for R2 stream.

with the same configuration in order to acquire a good

flow pattern. The dyestuff wastewater was fed into the
base of the first section so that the process was operated
as a 2-stage submerged upflow filter. The volumes of
fixed bed reactor used in this experiment was 37.35 l
(length: 58 cm; width: 28 cm; height: 30 cm). The
working volumes of two sections were 10.29 and 10.88
l, respectively. The air was supplied from the bottom of
reactor by an air diffuser. The temperature of the
reactor was maintained at 2595°C.

2.5. Characteristics of packing media

The characteristics of the plastic packing material

were, outer diameter: 25 mm; inner diameter: 22 mm;
height: 25 mm; void volume: 89.92%; specific surface
Fig. 3. Effect of Fenton’s reagent dosing amounts on Fenton’s area: 142.78 m2 m − 3; average weight per one packing
oxidation for R2 stream (II). media: 2.009 0.15 g.
 D.-H. Ahn et al. / Process Biochemistry 34 (1999) 429–439 433

2.6. Fixed bed reactor operation

The fixed bed reactor was initially loaded with 1 l of

an activated sludge seed obtained from the aeration
tank of an urban wastewater activated sludge treatment
plant (MLSS: 4000 mg l − 1). To increase attachment
efficiency, the biomass was initially operated during 10
days using synthetic wastewater containing glucose.
The composition and features of synthetic wastewater
were (mg l − 1): glucose, 1010; CH3COONH4, 330;
Sodium glutamate, 430; NH4Cl, 50; KH2PO4, 75;
K2HPO4, 100; MgSO47H2O, 40; MnSO4, 12.5; NaCl,
30; FeCl37H2O, 2; CaCl2, 25.
After 10 days, the biomass was acclimatized with a

Fig. 8. Acclimatization results of biomass in fixed bed reactor.

Fig. 6. Effect of Fenton’s reagent dosing amounts on Fenton’s Fig. 9. Effect of variations of hydraulic retention time (HRT) on
oxidation for R3 stream. treatment efficiency of fixed bed reactor.

dyestuff wastewater which had been pretreated with

Fig. 7. Effect of powder activated carbon dosing amounts for R3
stream.
Fenton’s reagent. In this acclimatizing period, the ratio
of pretreated dyestuff wastewater to synthetic wastewa-
ter was increased stepwise. As the dyestuff wastewater
was deficient in nitrogen and phosphorous, urea
(CO(NH2)2) and potassium biphosphate (KH2PO4)
were added to the wastewater to maintain 100:5:1 of
BOD:N:P ratio. As the biomass in the fixed bed reactor
was acclimatized with dyestuff wastewater, 100% of
dyestuff wastewater classified as R1, R2 and R3
streams were injected to the fixed bed reactor to investi-
gate the biological treatment efficiency under various
hydraulic retention time, pretreatment condition with
Fenton’s reagent and salt concentration of the dyestuff
wastewater.
434 D.-H. Ahn et al. / Process Biochemistry 34 (1999) 429–439

2.7. Analysis

COD, BOD5, total dissolved solids (TDS) and fixed

dissolved solids (FDS) measurements during Fenton’s
oxidation and the activated carbon adsorption tests
followed the procedures described in standard methods
[25]. Turbidity and absorbency were also measured
using a turbidimeter (Hack, 2100A) and a UV-visible
spectrophotometer (Shimadzu, UV-120-02), respec-
tively. pH measurements were carried out using a pH
meter (Orion, SA-720). Residual hydrogen peroxide
was measured using a iodimetric method. A typical
procedure for the iodimetric method consists of the
addition of a sample to 50 ml of a 1% KI solution,
acidified with 1 ml of 1:4 H2SO4 solution and warmed
to 40°C. After stirring and allowing to stand for 5 min,
the iodine liberated was titrated with thiosulphate solu-
Fig. 11. Effect of salt concentration on treatment efficiency of fixed
tion [26]. Microscopic examination of microorganisms bed reactor.
in the biofilm was followed by standard microscopic
examination procedures [27].

3. Results and discussion

3.1. Fenton’s oxidation with wastewater stream R2

3.1.1. Minimum dosing amounts of H2O2 /FeSO4 ·7H2O

Preliminary work has shown that the optimal dosing
ratio of H2O2/FeSO4·7H2O was 1/5, therefore, in this
work, the concentration (mg l − 1) range of
(H2O2:FeSO4·7H2O) was varied from (1000:5000) to
(4000:20 000) to determine the optimal dosing amounts
of Fenton’s reagent.

Fig. 12. Effect of Fenton’s oxidation as a post-treatment to treat

dyestuff wastewater.

The COD removal efficiency after Fenton’s oxidation

Fig. 10. Effect of Fenton’s oxidation pretreatment on treatment
efficiency of fixed bed reactor.
was 61.6–74.9% (initial, 9200 mg l − 1; final, 3760–2460
mg l − 1), and the BOD5 was increased from 600 to
2820–1820 mg l − 1 (Fig. 2). Thus, the ratio of BOD5/
COD was also increased from 0.06 to 0.75–0.72 which
is sufficient to allow the use of the wastewater as the
influent of a subsequent biological treatment process.
This result shows that the biodegradability of organic
compounds in the dyestuff wastewater can be enhanced
by Fenton’s oxidation. However, it is not essential to
increase the ratio of BOD5/COD to above the value of
0.6 because the cost of using Fenton’s reagent is high
and the ratio of 0.4 (BOD5/COD) is sufficient as a
minimum value for biological treatment.
 D.-H. Ahn et al. / Process Biochemistry 34 (1999) 429–439
Therefore, to investigate the minimum dosing
amounts of hydrogen peroxide and ferrous sulphate,
the concentration (mg l − 1) range of
(H2O2:FeSO4·7H2O) was varied from (200:1000) to
(800:4000). The COD removal efficiency was 52.8–
62.3% and the BOD5 was increased from 600 to 1380–
1550 mg l − 1 (Fig. 3). The final ratio of BOD5/COD
was increased from 0.06 to 0.47. Therefore, for the
purpose of using dyestuff wastewater stream R2 as an
influent to a biological treatment process, it is desirable
to maintain the minimal dosing concentration (mg l − 1)
of H2O2:FeSO4·7H2O in the Fenton’s oxidation as
700:3500.
3.2. pH effect
In this experiment, the dosing amounts of hydrogen
peroxide and ferrous sulphate were each fixed at 10 000
mg l − 1 to supply a sufficient amount of reagent for the
oxidation reaction. A pH at 3 gave the greatest COD
removal and biodegradability of the dyestuff wastewa-
ter (Fig. 4). Also, the lowest concentration of residual
hydrogen peroxide was obtained at pH 3. This result
may be due to the fact that the OH’ radical will not be
produced below pH 3 because hydrogen peroxide is
stabilized and the radical reaction will not be propa-
gated above pH 5 since hydroxide floc is simultaneously
formed by the injection of hydrogen peroxide and
ferrous sulphate above a pH 5 [17,18].
3.3. Reaction time effect
To investigate the effect of reaction time on treat-
ment efficiency of Fenton’s oxidation, the reaction time
Fig. 13. Schematic diagram of dyestuff wastewater treatment process proposed in this article.
435
of the oxidation was varied from 0.5 to 4 h. The
concentrations of hydrogen peroxide and ferrous sul-
phate fixed at 700 and 3500 mg l − 1. There were few
differences in the treatment efficiency at times \1 h
(Fig. 5). Therefore, the minimum reaction time for
Fenton’s oxidation was taken as 1 h.
3.4. Treatment of dyestuff wastewater stream R3
Stream R3 (G and I streams) consisted of 3–5%
methanol solution which is a dyestuff intermediate. It is
known that chemical oxidation of methanol is not easy
because methanol is nearly the last step in chemical
oxidation [18]. According to Walling [15] it is difficult
to oxidize methanol with Fenton’s reagent. In the
present tests of the oxidation of stream R3, the COD
removal efficiencies decreased to the range of 37.9–
49.3% and consequently the ratios of BOD5/COD were
the range of 0.24–0.27 (Fig. 6). In addition, the turbid-
ity of the wastewater increased and the settleability of
sludge after Fenton’s treatment decreased. The dosing
concentrations condition of Fenton’s reagent
(H2O2:FeSO4·7H2O) had been varied from 5000:10 000
to 25 000:10 000.
In the activated carbon adsorption experiment, al-
though the COD removal efficiency (31.4–52.6%) was
nearly same as the result obtained with Fenton’s oxida-
tion, the BOD5/COD ratio was increased to 0.31 and a
clear effluent was obtained (Fig. 7). This result indicates
that it is more desirable to use the activated carbon
adsorption process than Fenton’s reagent on a dyestuff
wastewater stream which is composed of methanol if
biodegradability and turbidity are being considered.
436 D.-H. Ahn et al. / Process Biochemistry 34 (1999) 429–439
Table 3
Treatment result of dyestuff wastewater using the process proposed in this article
Each process proposed in this article
(1)a
COD (mg l−1) 17 200
BOD5 (mg l−1) 3350
FDS (g l−1) 80.7
(BOD5/COD) 0.19
Absorbance 0.50
SS (mg l−1)
a
Total stream ŽA-I raw waste.
b
Effluent after pretretment.
c
Influent for biofilm reactor.
d
Effluent of biofilm reactor.
e
Effluent after post-treatment by Fenton’s oxidation ŽH2O2:500 mg l−1; FeSO4·7H2O:2500 mg l−1.
3.5. Acclimatization of biomass in fixed bed reactor
Fig. 8 shows the acclimatization results of biomass in
the fixed bed reactor as the ratio of dyestuff wastewater
to synthetic wastewater was increased stepwise. In this
acclimatizing period, the hydraulic retention time and
influent COD concentration were 0.48 day and 3600 mg
l − 1, respectively. When the dyestuff:wastewater ratio
was 3% in over the influent, the effluent COD concentra-
tion increased over 4 days. However, the biomass recov-
ered its activity after 5 days and effluent COD
concentration decreased to the concentration obtained
when the influent consisted only of synthetic wastewater.
When the dyestuff:wastewater ratio was increased to
10%, the effluent COD concentration increased and the
recovery speed of biomass activity was slower than that
noted previously. However, in contrast of this result,
shock loading effects such as turbid effluent or rising
sludge were not observed and treatment efficiency was
increased as the dyestuff:wastewater ratio was increased
to 20%. This result may be due to the fact that the
biomass was better acclimatized.
Although the value of the effluent COD concentration
was increased as the dyestuff:wastewater ratio was in-
creased stepwise to 100%, the biomass in the fixed bed
reactor recovered its activity quickly. This shows that
treatment efficiency of wastewater containing toxic
chemicals can be enhanced by the stepwise increasing of
organic loading rate since the biomass had sufficient time
for adaptation.
3.6. Effect of 6ariation of hydraulic retention time
After 48 days of operation, as the biomass of the fixed
bed reactor was acclimatized to the dyestuff wastewater,
the hydraulic retention time (HRT) was changed stepwise
from 0.48 to 0.96 day for the purpose of investigating the
treatment efficiency due to HRT variation (Fig. 9).
(2)b (3)c (4)d (5)e
8680 3800 580 82
4010 1450 120 38
84.9 29.7 19.0 18.2
0.46 0.42
0.26 0.09
210 8
With a HRT of 0.48 day, the effluent COD and SS
concentrations decreased continuously and a clear
effluent was obtained. When the HRT was increased to
0.64 day, the effluent SS concentration increased initially
as attached microorganisms were detached from the
media. This may be due to the fact that overgrowing
attached microorganisms were detached periodically
from the biofilm surface. However, as the microorgan-
isms were adapted to the changed HRT condition, the
effluent SS decreased and the treatment efficiency of the
fixed bed reactor was quickly recovered and the quantity
of the effluent were not affected by further increases of
HRT. This result may be due to the fact that microorgan-
isms attached to the media are maintaining adequate
biofilm thickness to fit the amounts of organic loading
[28–31].
3.7. Effect of Fenton’s oxidation pretreatment
The R2 stream had a BOD:COD ratio B0.4 and it had
been pretreated with Fenton’s oxidation to increase the
BOD5/COD ratio. The preliminary results show that it
was desirable to maintain the minimum concentration
(mg l − 1) of (H2O2:FeSO4·7H2O) in the Fenton’s reagent
as700:3500 However, this mixture was linked purely with
the ratio of BOD5/COD. Therefore, in this work, to
investigate the pretreatment effect influencing the actual
biological treatment system, the R2 stream which had
been pretreated with Fenton’s reagent with the concen-
tration (mg l − 1) range of (H2O2:FeSO4·7H2O) varied
successively from 5000:10 000 to 700:3500, was used as
influent.
The use of influents which had been pretreated with
the concentration (mg l − 1) range of (H2O2:FeSO4·7H2O)
of 5000:10 000 and 1500:7500, had little effect on biolog-
ical treatment efficiency (Fig. 10). However, as the
concentration (mg l − 1) range of (H2O2:FeSO4·7H2O)
was successively decreased from 1000:5000 to 700:3500,
the effluent SS and the effluent COD increased. This was
 D.-H. Ahn et al. / Process Biochemistry 34 (1999) 429–439
thought to be due to the biodegradability of the influent
decreasing or the toxicity of the influent being in-
creased.
As the microorganisms became adapted to the
changed influent condition, the effluent SS decreased
and the treatment efficiency of the reactor recovered
after 34 days of operation. This result shows that a
stable effluent can be obtained if the microorganisms
were well adapted to a toxic influent condition. Com-
paring the pretreatment conditions of using a
H2O2:FeSO4·7H2O ratio of 5000:10 000, with that of
700:3500 shows a saving of 7.14 times for hydrogen
peroxide and 2.85 times for ferrous sulphate.
3.8. Effect of salt concentration
While it is reported that the maximum salt concen-
tration in wastewater for biological treatment is 35 g
l − 1 [32–35] some reports show that it is possible to
achieve good operational efficiency at 50 g l − 1 salt
concentration if the microorganisms are acclimatized
gradually to wastewaters containing high salinity [36–
38]. The inorganic salts in dyestuff wastewaters are
sulphuric acid (H2SO4), hydrochloric acid (HCl),
sodium thiosulphate (Na2S2O3), sodium carbonate
(Na2CO3), sodium chloride (NaCl) and its concentra-
tion is too high (FDS =80.7 g l − 1) to be used directly
in biological treatment. Therefore, it is important to
know the extent of any salinity affect on the fixed bed
bioreactor.
This was examined by using a series of dilutions of
the original wastewater as the feedstock. Initially, a
dilution which give a FDS concentration of 26.4 g l − 1
was used. Fig. 11 shows the results of these salinity
changes on the fixed bed biofilm reactor. As the salt
concentration (mg l − 1) of the influent was successively
increased from 26.4 to 43.2, the effluent SS and COD
showed periodically shocking, recovery and stabiliza-
tion. However, this trend was disrupted when the influ-
ent containing 54.8 g l − 1 of salt concentration was
injected and resulted in foaming and rising of the
settled sludge.
In addition as the salinity of the influent was in-
creased, microorganisms in the biofilm were easily de-
tached from the media. This was thought to be because
high salinity decreased the flocculating force between
microorganisms [39,40]. These results indicate that it is
important to acclimatize microorganisms and maintain
salinity below 50 g l − 1 if the operational efficiency of a
fixed bed biofilm process is not to be impaired at high
concentrations of salt.
3.9. Characteristics of microorganisms
The most common microorganisms including proto-
zoa and higher life forms observed in the fixed bed
437
biofilm reactor were filamentous organisms, flagellates,
amoebae, free-swimming ciliates, attached ciliates, rot-
ifers, and a few other invertebrates. Filamentous bacte-
ria like Sphaerotilus natans and Nocardia were observed
as the basic microorganisms attached to the media
during experiments.
The predominant species of protozoa and higher life
forms observed in the biofilm changed as the influent
condition was changed. In the acclimatization period,
protozoa like Vorticella, Opercularia, Carchesium and
Aspidisca spp. mainly constituted the microorganisms
of the first stage, and higher life forms like Nematode,
Rotifer and Philodina were predominantly observed in
the second stage. The presence of higher life forms
predominantly in the second stage suggests that organ-
ics which were not completely degraded in the initial
stage and sludge detached from the biofilm acted as
substrates for higher life forms.
As the ratio of dyestuff wastewater to synthetic
wastewater was increased, the treatment efficiency
simultaneously decreased. Most of the ciliates disap-
peared and Colpoda, Colpidium, Bodo and Okimonas
were predominantly observed. As the microorganisms
were acclimatized to the increased organic loading con-
dition, the treatment efficiency recovered. The colour of
the biofilm changed from grey or black to brown and
the predominant microorganisms changed to Vorticella,
Opercularia, Carchesium, Rotifer, philodina spp.
3.10. Post-treatment by Fenton’s oxidation
The efficiency of Fenton’s oxidation as a post-treat-
ment system was also investigated to provide a total
treatment process of the dyestuff wastewater using a
dosing weight ratio of H2O2/FeSO4·7H2O fixed to 1/5.
The minimum dosing amounts of hydrogen peroxide
and ferrous sulphate were derived by varying
H2O2:FeSO4·7H2O ratio from 100:500 to 500:2500.
The COD and BOD5 removal efficiency increased as
the dosing amounts of Fenton’s reagent was increased
(Fig. 12). For the purpose of using Fenton’s reagent as
a post-treatment process, these results show the need to
maintain the H2O2:FeSO4·7H2O ratio at 200:1000 from
the view of economy.
4. Conclusions
Fenton’s oxidation and activated carbon adsorption
were examined as a pretreatment process for dyestuff
wastewater having high salinity, colour, and non-
biodegradable organics. In this work, to investigate
optimal pretreatment condition of dyestuff wastewater
by chemical oxidation and activated carbon adsorption,
each wastewater stream produced by individual produc-
tion process was classified and the stream having a
438 D.-H. Ahn et al. / Process Biochemistry 34 (1999) 429–439
value of BOD5/COD lower than 0.4 was pretreated by
Fenton’s oxidation or activated carbon adsorption to
increase the ratio of BOD5/COD which indicates
biodegradability. In Fenton’s oxidation with stream
R2, the optimal reaction pH was 3.0 and the minimum
dosing concentration (mg l − 1) of H2O2:FeSO4·7H2O
was 700:3500, respectively.
Meanwhile, stream R3, which consisted mainly of
methanol, was efficiently treated by activated carbon
adsorption. The ratio of BOD5/COD was also increased
to 0.27 and 0.31 from 0.06 by Fenton’s oxidation and
activated carbon adsorption, respectively. Therefore,
the adaptation of Fenton’s oxidation and a carbon
adsorption process, according to the characteristics of
each wastewater stream produced by individual produc-
tion processes, may be useful as a pretreatment process
prior to biological treatment with respect to biodegrad-
ability and economy.
Meanwhile, biological treatment using a fixed bed
reactor was also investigated and the effect of varying
the hydraulic retention time, the pretreatment condi-
tions by Fenton’s reagent and the salt concentration of
dyestuff wastewater noted. In addition, the efficiency of
Fenton’s oxidation as a post-treatment system was also
investigated to present a total treatment process of
dyestuff wastewater.
As the influent COD and salinity were increased, the
effluent SS and COD increased since the toxicity of
influent was increased. However, as the microorganisms
were adapted to the changed influent condition, effluent
SS decreased and the treatment efficiency of the fixed
bed reactor quickly recovered under the high organic
loading and salinity. This result shows that a stable
effluent can be obtained if the microorganisms were
well adapted to toxic influent condition. In addition,
the influent toxicity affecting the microorganisms of a
fixed bed reactor can be decreased by chemical oxida-
tion using Fenton’s reagent and carbon adsorption
process according to the characteristics of each wastew-
ater stream produce by individual production process.
Therefore, as shown in Fig. 13 and Table 3, the
wastewater treatment process consisting of chemical
oxidation, activated carbon adsorption, fixed bed bi-
ofilm process, Fenton’s oxidation as a post-treatment
system can be useful to treat dyestuff wastewater hav-
ing high salinity, colour, and non-biodegradable or-
ganic compounds.
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