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(2014): Carbonaceous organics removal kinetics in an upflow anaerobic sludge blanket (UASB) reactor treating physico-
chemically pre-treated textile wastewater, Desalination and Water Treatment, DOI: 10.1080/19443994.2014.888687
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Desalination and Water Treatment (2014) 1–12
www.deswater.com
doi: 10.1080/19443994.2014.888687
ABSTRACT
techniques like sonochemical or advanced oxidation treating physico-chemically pre-treated synthetic tex-
processes are normally used for treating the textile tile wastewater containing different classes of textile
wastewater [4]. However, each of them has some limi- dyes. In this connection, Verma et al. [18] has reported
tations and drawbacks in their applications. Hence, the supremacy of magnesium chloride (MC) for de-
there is no single economically and technically viable colourisation of textile wastewater containing various
method to solve this problem and usually two or three classes of dyes. Further, the effectiveness of a novel
methods have to be combined together in order to aluminium based coagulant as aluminium chlorohy-
achieve adequate level of colour removal [5,6]. One of drate (ACH) has also been reported for decolourisa-
the effective combinations for the treatment of textile tion of synthetic as well as real textile effluents [6].
wastewaters is the use of physico-chemical coagula- However, the reported dosage of MC was very high
tion followed by biological treatment [7]. This inte- to achieve the desired (>99%) degree of colour
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grated process has an advantage to remove most of removal. Therefore, in the present study a composite
the dyes through physico-chemical coagulation and coagulant, i.e. mixture of MC and ACH, was used for
also to reduce the carbonaceous organic matters in the the decolourisation of synthetic wastewater containing
form of COD of the wastewater significantly, while various classes of textile dyes such as reactive black 5,
biological process further reduce the remaining carbo- disperse blue 3 and congo red along with the other
naceous organics of the wastewater efficiently. chemical constituents that are normally used during
The traditional aerobic biological processes do not textile processing and found in the texile wastewater.
effectively decrease the colour of the textile The objective of the present study is to investigate the
wastewater [8] and also generate large quantity of effectiveness of composite coagulant (MC + ACH) for
active biological sludge which needs further treatment the pre-treatment of textile wastewater and to evaluate
before being discharged to the environment. The the kinetics of carbonaceous organics removal by the
anaerobic biological processes can be considered as an UASB reactor treating physico-chemically pre-treated
energy efficient technology as less energy is required synthetic textile wastewater using various mathemati-
for its operation, and biogas is produced as a cal models.
by-product. These processes were previously used for
the treatment of textile wastewaters [9,10], preferably
for textile azo dye reduction. However, the azo dye 2. Materials and methods
reduction under anaerobic conditions leads to the
2.1. Chemicals
formation of various types of aromatic amines, which
possess the potential toxicity and carcinogenicity Extra pure MC and industrial grade (purity 30%
[11,12]. USEPA [13] provides the evidence of different w/w) aluminium chlorohydrate (ACH) were used as
types of toxicity due to the monocyclic aromatic coagulants. 1.0 M H2SO4 and NaOH were used to
amines on the different test models, where 96-h LC50 adjust the desired pH. Lime was also used to adjust
for the fish was reported in the range from 16.4 to the optimum pH, since it is well established that lime
49.5 mg L−1. The carcinogenic effects of these aromatic can be used as a coagulant aid as well as to adjust the
amines were well explained by numerous researchers desired pH [16]. The other chemical additives used in
[14,15]. Production of these aromatic amines can be the preparation of the synthetic wastewater were of
avoided using the integrated process of physico- analytical grade.
chemical coagulation and anaerobic biological
treatments. The suitability of different chemical salts
as coagulants for the decolourisation of various types 2.2. Textile wastewater
of textile wastewaters has been investigated
Synthetic textile wastewater was prepared as per
previously [6,16–18].
the reported chemical constituents of real textile
Literature shows that studies pertaining to the
wastewater [19], with a total dye concentration of 200
anaerobic treatment of textile wastewaters are very
mg L−1. The synthetic textile wastewater was prepared
limited. Also, very limited studies are available on the
by mixing three commercial dyes namely, reactive
physico-chemical treatment of synthetic textile
black 5 (RB5), congo red (CR) and disperse blue 3
wastewater containing majority of chemical additives
(DB3) in tap water, in equal ratio along with the vari-
that are used in textile industries during various steps
ous chemical additives such as starch, acetic acid,
of textile processing. To the best of our knowledge, no
sucrose, sodium carbonate, sodium hydroxide, sulphu-
such study in the literature is reported for the
ric acid, detergent, and sodium chloride, which are
evaluation of the upflow anaerobic sludge blanket
used during textile processing in textile industries.
(UASB) reactor as anaerobic post-treatment phase,
A.K. Verma et al. / Desalination and Water Treatment 3
Dyes were procured from Sigma-Aldrich, Germany. 62.18 and 41.98 g L−1, respectively. Initially, the reac-
The characteristic wavelength of simulated dye waste- tor was operated with the synthetic feed with sucrose
water was determined by running a scan of the dye as the carbon source equivalent to 1,000 mg L−1 COD
solution on a UV–vis spectrophotometer and the maxi- along with the nutritional composition. After achiev-
mum absorbance wavelengths (λmax) for RB5, CR and ing 75% COD reduction with the synthetic feed con-
DB3 were found as 591, 502 and 638 nm, respectively. sisting of sucrose as the sole carbon source, the
The colour content of the wastewater containing mix- reactors were fed with physico-chemically pre-treated
ture of dyes was determined by taking the sum of the synthetic textile wastewater. The reactors were oper-
absorbencies measured at 591, 502 and 638 nm [17]. ated at room temperature, between 22 and 27 ˚C with
The synthetic textile wastewater was having COD = five different HRTs of 30.8, 20, 15, 12 and 8 h (reactor
1944 to 2007 mg L−1, pH = 10.4 to 10.6, Abs (mixture) = 1 was operated at 30.8, 15 and 8 h HRT, and the reac-
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Abs(591) + Abs(502) + Abs(638) = 2.3992. tor 2 was operated at the 20 and 12 h HRT) at differ-
The percentage decolourisation efficiency was ent organic loading rates (OLRs). The performance of
determined using the following Eq. (1): the reactors was monitored regularly till the steady
state was achieved.
ðAb At Þ
Decolourisation efficiency ð%Þ ¼ 100 (1)
Ab
2.5. Analyses
where Ab and At are the absorbencies of the solution Colour measurement was carried out after filtra-
before and after treatment of the textile wastewater, tion of supernatant, obtained after chemical coagula-
respectively. Tap water was used as a reference. tion, through filter papers. Subsequently, the pH of
supernatant sample was adjusted to neutral and then
the absorbance of the sample was measured using
2.3. Coagulation and flocculation test procedures UV-vis spectrophotometer. The biochemical oxygen
The optimum pH value and coagulant dosage demand (BOD5), total suspended solids (TSS) and
required for efficient colour removal were deter- total volatile solids (TVS) were measured according
mined by jar test method. One litre beakers contain- to the standard methods [21]. The COD was analysed
ing 500 mL of wastewater were used for the as per the closed reflux colorimetric method [21] after
coagulation experiments. About 1.0 M NaOH or 1.0 digestion of the samples in COD reactor (Model DRB
M H2SO4 was added to each beaker for pH adjust- 200, HACH, USA) and then absorbance measurement
ment. The composite coagulant was added and was carried out by COD spectrophotometer at 600 nm
mixed for 3 min under rapid mixing condition at 80 (Model DR 2,800, HACH, USA). Total gas and meth-
rpm. The solution was then mixed at slow floccula- ane gas measurements were carried out using water
tion at 30 rpm for 15 min and allowed to settle displacement method as suggested by Isik and Spon-
down for 20 min. The supernatant from the beaker za [9]. Bicarbonate alkalinity (B- alkalinity) and vola-
was taken for analysis. tile fatty acid (VFA) were measured using a
titrimetric method as proposed by Anderson and
Yang [22]. Aromatic amines were also monitored
2.4. Description and operation of UASB reactors colorimetrically as per the method suggested by Oren
et al. [23]. Total nitrogen in the UASB reactor
Two identical UASB reactors made of Plexiglas
effluents was measured using persulphate digestion
having an effective volume of 4.62 L, with the dimen-
method, proposed and used by Bachman and
sion of 80 × 75 × 770 mm were used in the study.
Canfield [24].
Physico-chemically pre-treated textile wastewater was
used as an influent for the UASB reactors. The nutri-
ents were added to influent as per the composition
suggested by Bhunia and Ghangrekar [20]. Matured 3. Kinetic model description in UASB reactor
cow dung slurry obtained from nearby cattle farm Mathematical models are in general used to opti-
was anaerobically digested by constantly feeding C mise the plant design, predict the operational perfor-
and N source for one month. The reactors were fed mance, and to evaluate the experimental results.
with this digested sludge after having achieved the Kinetic analysis is an accepted pathway for describing
desired VSS concentration. Mixed liquor suspended the performance of biological treatment systems and
solids (MLSS) and mixed liquor volatile suspended for predicting their performance. A number of models
solids (MLVSS) of the inoculum were found to be
4 A.K. Verma et al. / Desalination and Water Treatment
3.1. Modified Stover-Kincannon model From the linearised plot of Eq. (8), the constants
“a”, “b” and ks can be obtained. The coefficient “b” in
This model considers the substrate removal rate as Eq. (8) is close to one and generally reflects the
a function of OLR at steady state. The original Stover- impracticality of attaining a zero value of COD.
Kincannon model is expressed with the Eq. (2) [26].
dX Q Q
dS Q ¼ X0 Xe þl X Kd X (9)
¼ ðS0 Se Þ (3) dt Vb Vb
dt V
dS Q Q lX
linearisation of Eqs. (2) and (3) yields Eq. (4) ¼ S0 Se (10)
dt V b Vb Y
3.2. Grau second-order multi-component substrate removal Specific growth rate and the concentration of rate
model limiting substrate can be related by Monod equation
The general equation of the second-order kinetic as follows:
model is exemplified in Eq. (5) [27]:
lm Se
l¼ (12)
2 Ks þ Se
dS Se
¼ ks X (5)
dt S0 The concentration of the biomass in the influent X0
can be considered as negligible at steady-state condi-
Integrated and linearised form of Eq. (5) is represented tions, Therefore, at steady state, the following equation
as Eq. (6): can be obtained after substitution of Eq. (12) in Eq. (9),
S0 hH S0 QðS0 Se Þ 1 1 1
¼ hH (6) ¼ þ Kd (13)
S0 Se ks X Vb :X Y hc Y
0 Se Þ
Considering the second term of the right part of Eq. The plot of QðSVb X vs. h1c will be linear one and from
(6) as a constant, the Eq. (7) will be obtained [27]. this the kinetic constants Y and Kd can be determined.
A.K. Verma et al. / Desalination and Water Treatment 5
3.4. Contois kinetic model as 9 and 12, respectively, by Verma et al. [18]. In the
present study, the optimum pH for the composite
Contois model is a modification over the Monod
coagulant was determined as 12. Lime was applied to
model. In case of Contois model, cell mass growth rate
adjust the pH of the solution up to optimum pH for
depends upon the concentrations of both substrate
further treatments using composite coagulant, since
and cell mass, and growth rate is inhibited at high
lime possess the dual characteristics, i.e. act as a coag-
concentrations of the cell mass. According to the
ulant aid and also increases the pH [16]. The optimum
Contois kinetic model:
dosage of composite coagulant for efficient chemical
coagulation of textile wastewater was determined by
lm Se varying the coagulant dosage with two different ratios
l¼ (14)
bX þ Se of MC + ACH (1:1) and MC + ACH (1.5:1). During the
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¼ þ þ (17)
Q ðS0 Se Þ Ki k k k 80
60
where “k” represents the maximum specific substrate
utilisation rate. 40
[MC+ACH] (1:1)
20
4. Results and discussions [MC+ACH] (1.5:1)
800 mg L−1 combined dosage of MC + ACH (1.5:1), the methanogens, which are slow in biochemical reac-
which was far superior over the colour removal tion, would not be getting sufficient contact time at
(~ 91%) produced by MC + ACH (1:1) at the same dos- lower HRTs to convert the produced VFAs into meth-
age. Therefore, the combination MC + ACH (1.5:1) was ane completely and hence, resulted in the accumula-
considered as the best composite coagulant at the opti- tion of VFA. The variation of pH was not much
mum pH and a dosage of 12 and 800 mg L−1, respec- significant and pH remained within the optimal range
tively. The maximum COD reduction efficiency of for anaerobic conditions. This is due to the fact that all
55% was obtained at the optimised conditions. As the the reactors were operated with sufficient buffering
residual COD in the pre-treated wastewater is higher capacity, which is evident from the data of influent
than the recommended limits of different countries, and effluent B-Alkalinity presented in Table 1.
the wastewater must further be treated to meet the VFAs were produced as the precursors during
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Table 1
Steady-state experimental performance at different HRTs
HRTs (h)
Parameter 30.8 20 15 12 8
Influent pH 7.5 ± 0.1 7.5 ± 0.1 7.5 ± 0.1 7.5 ± 0.1 7.5 ± 0.1
Effluent pH 7.4 ± 0.1 7.4 ± 0.1 7.3 ± 0.1 7.3 ± 0.05 7.2 ± 0.1
Influent B-Alkalinity (mg L−1 as CaCO3) 1,150 ± 10 1,130 ± 10 1,150 ± 10 1,130 ± 10 1,130 ± 10
Effluent B-Alkalinity (mg L−1 as CaCO3) 1,145 ± 15 1,120 ± 15 1,080 ± 20 1,065 ± 15 1,025 ± 15
Effluent VFA (mg L−1 as CH3COOH) 50 ± 5 55 ± 10 60 ± 5 110 ± 10 140 ± 10
Influent COD (mg L−1) 770 ± 10 790 ± 10 770 ± 10 790 ± 10 790 ± 10
COD reduction (%) 97.5 ± 1.5 98 ± 1.0 88 ± 1.5 82 ± 1.0 71 ± 2
OLR (kg COD m−3 d−1) 0.60 0.95 1.23 1.57 2.36
Effluent BOD5 (mg L−1) 30 ± 5 25 ± 5 45 ± 5 55 ± 5 65 ± 5
Total Neffluent (mg L−1) 8.5 ± 0.3 7.9 ± 0.2 9.1 ± 0.2 13.2 ± 0.2 16.4 ± 0.5
Total aromatic amines (mg L−1) BDL BDL BDL BDL BDL
Total gas production rate (mL d−1) 1,550 ± 50 2,355 ± 60 2,890 ± 55 3,470 ± 70 4,680 ± 60
Methane gas production rate (mL d−1) 735 ± 25 1,020 ± 30 1,135 ± 30 1,320 ± 35 1,650 ± 25
Operation period to achieve steady state (d) 42 34 47 35 35
A.K. Verma et al. / Desalination and Water Treatment 7
V/Q·(S0-Se)
1.2
were 1,550 and 755 mL d−1, respectively, at the HRT
of 30.8 h; whereas at HRT of 8 h, these parameters 0.8
were increased to 4,680 and 1,550 mL d−1, respectively.
It can be seen that methane gas fraction in the total 0.4
gas decreased from 51.29 to 35.25% with the increase
in the OLR from 0.6 to 2.3 kg COD m−3 d−1. This indi- 0.0
0.0 0.5 1.0 1.5 2.0
cates the slight imbalance of the UASB process in V/Q·S0
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y = 31.175x + 0.0202
0.15 R² = 0.9412
The observed value of ks in the present study is les-
ser than the value of ks reported in previous studies
Vb.Se/Q.Y.(S0-Se)
0.12
by Isik and Sponza [4] and Ubay [32]. This can be
attributed to the fact that ks highly depends on the ini- 0.09
tial substrate and microorganism concentration [4].
0.06
The initial substrate concentration in those previous
studies was far greater than that of the present study 0.03
and thereby resulted in the smaller ks value.
0
0 0.001 0.002 0.003 0.004 0.005
4.3.3. Monod kinetic model Se/X
0.04
y = 2.6613x + 0.0118 3
0.035 R² = 0.9179 y = -40.709x2+ 21.099x + 0.088
2.5 R² = 0.9878
0.03
Vb·Se·X/Q·(S0-Se)
(S0-Se)/θH·X
0.025 2
0.02 1.5
0.015
1
0.01
0.5
0.005
0 0
0 0.002 0.004 0.006 0.008 0.01 0 0.05 0.1 0.15 0. 2 0.25
1/θc Se
Fig. 4. Determination of yield coefficient (Y) and death rate Fig. 6. Determination of kinetic coefficients for Haldane
constant (Kd) of Monod model. model.
Downloaded by [Indian Institute of Technology - Bhubaneswar] at 21:09 16 February 2014
Table 2
Comparison of kinetic coefficients as per the modified Stover Kincannon, Grau second-order, Monod, Contois and Haldane model
Kinetic parameters
OLR
HRT (kg COD Umax L−1 KB
Model Reactor type Wastewater type (h) m−3 d−1) d−1) L−1 d−1) References
Modified Hybrid batch fed Synthetic phenolic wastewater 1.0 1.4 [37]
Stover moving bed
Kincannon UASB Synthetic textile wastewater 6–100 1.01–16.86 7.5 8.2 [4]
UASB Municipal wastewater 5–24 11.78–0.57 1.996 1.536 [31]
Microaerophilic – Real textile wastewater 55.2– 16.4–2.6 212 22.89 [10]
aerobic hybrid 218.4
UAFB Formaldehyde-containing wastewater 10–24 0.18–3.61 3.4 4.6 [38]
UAF Fruit canning wastewater 12 19 109.9 53.5 [39]
BFFR Distillery spent wash 432– 5.0–20.0 2.0 1.69 [40]
480
UASB Physico-chemically pre-treated synthetic 8–30.8 0.62–2.4 4.84 4.27 Present
textile wastewater Study
Grau second- ks a b
order Hybrid batch fed Synthetic phenolic wastewater 2.39 1.114 [37]
moving bed
UASB Synthetic textile wastewater 6–100 1.01–16.86 0.337 0.562 1.095 [4]
Hybrid UASB Synthetic coal wastewater 18–36 0.5–1.0 1.72 0.078 0.964 [41]
UAFB Formaldehyde-containing wastewater 10–24 0.18–3.61 0.133 0.64 9.36 [38]
UASB Physico-chemically pre-treated synthetic 8–30.8 0.62–2.4 0.1 0.162 0.8786 Present
textile wastewater Study
Monod Y Kd
Anaerobic batch Synthetic textile wastewater 240 0.115 0.000125 [8]
reactor −3.174 −0.006
MSBR Dairy wastewater 0.228 0.138 [42]
UASB Physico-chemically pre-treated synthetic 8–30.8 0.62–2.4 0.375 0.0044 Present
A.K. Verma et al. / Desalination and Water Treatment
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U max — maximum substrate utilisation rate (g L−1 d−1) 1159–1164.
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T. Velayutham, S. Nagarajan, Bio-kinetic analysis on
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Ks — half saturation constant (g L−1)
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