Adsorption and Bioadsorption of Granular Activated Carbon (GAC) For Dissolved Organic Carbon (DOC) Removal in Wastewater
Adsorption and Bioadsorption of Granular Activated Carbon (GAC) For Dissolved Organic Carbon (DOC) Removal in Wastewater
Abstract
In this study, the performances of GAC adsorption and GAC bioadsorption in terms of
dissolved organic carbon (DOC) removal were investigated with synthetic biologically
treated sewage effluent (BTSE), synthetic primary treated sewage effluent (PTSE), real
BTSE and real PTSE. The main aims of this study are to verify and compare the
efficiency of DOC removal by GAC (adsorption) and acclimatized GAC
(bioadsorption). The results indicated that the performance of bioadsorption was
significantly better than that of adsorption in all cases, showing the practical use of
biological granular activated carbon (BGAC) in filtration process. The most
significance was observed at a real PTSE with a GAC dose of 5 g/L, having 54% and
96% of DOC removal by adsorption and bioadsorption, respectively. In addition, it was
found that GAC adsorption equilibrium was successfully predicted by a hybrid
Langmuir - Freundlich model whilst integrated linear driving force approximation
(LDFA) + hybrid isotherm model could describe well the adsorption kinetics. Both
adsorption isotherm and kinetic coefficients determined by these models will be useful
to model the adsorption/bioadsorption process in DOC removal of BGAC filtration
system.
1. Introduction
The domestic wastewater typically contains pathogens, suspended solids, nutrients
(nitrogen and phosphorus) and other organic pollutants. For curtailing the
environmental and health hazards, these pollutants need to be removed to permissible
limits for safe disposal of wastewater (Devi and Dahiya, 2008). Consequently, removal
of the organic contaminants and pathogens from wastewater is very important for its
reuse in different activities.
Activated carbon adsorption has been widely applied in removing organic matters from
wastewater as it has a strong affinity for attaching organic substances even at low
concentration. Having large surface area for adsorption, granular activated carbon
(GAC) is one of the best adsorbents for removing various organic contaminants
(Nishijima et al, 1997). The GAC adsorption systems are therefore considered to apply
for producing the effluent of high quality from sewage treatment plant which can be
reused for various purposes. However, even though it has high adsorption capacity,
GAC can only maintain its adsorption for a short time after its available adsorption site
becomes exhausted with adsorbed organic pollutants (Aktas and Cecen, 2007). It is
well known that GAC is also a good support media for microbial growth. Thus,
biological GAC (BGAC) with attached biomass can effectively remove organic
contaminants both by adsorption and biodegradation (Nishijima et al, 1997; Carvalho
et al, 2007). The concept of bioadsorption is that adsorption is more dominant before
GAC is in full adsorption capacity and the biodegradation play major role after that
(Hoang, 2005; Aktas and Cecen, 2007). The GAC bioadsorption is usually applied in
the bioreactors either fixed bed or fluidized bed configurations (Aktas and Cecen,
2007). The previous studies showed that GAC bioadsorption systems were very
efficient (Zhao et al., 1999; Maloney et al, 2002; Loh and Ranganath, 2005; Persson et
al., 2005; Hoa et al., 2008) due to their simultaneous adsorption of non-biodegradable
matter and oxidation of biodegradable contaminants in a single reactor.
The main objectives of this study are: (i) to compare the adsorption and bioadsorption
capacity of GAC in terms of dissolved organic carbon (DOC) removal from different
wastewaters; and (ii) to develop the suitable adsorption isotherm and kinetic models
which can be used for a column model to predict DOC removal in the BGAC filtration
system.
2. Experimental
2.1 Materials
2.1.1 Wastewaters used
A. Synthetic wastewaters
1. Primary treated sewage effluent (PTSE)
The compositions of synthetic wastewater used in this study are presented in Table 1. It
represents the wastewater after primary treatment. The average DOC concentration of
this synthetic PTSE is around 120 mg/L.
B. Real wastewaters
1. Real PTSE
The sewage was collected from the SOPA (Sydney Olympic Park Authority)
Wastewater Treatment Plant. The average DOC of real PTSE is around 55mg/L.
2. Real BTSE
The real BTSE was also derived from the SOPA Wastewater Treatment Plant. It is the
effluent from the sequencing batch bioreactor (SBR) process and the DOC is around
10mg/L.
2.1.2 GAC used
The coal based GAC (ACTICARB GS1300, Activated Carbon Technologies Pty Ltd,
Australia) was used in this study. This coal based GAC has a surface area of > 1100
BET m2/g, an iodine number of > 1100 mg/ (g.min) and maximum ash and moisture
contents of 10% and 3% respectively. Prior to use in experiments, the GAC was rinsed
with distilled water to remove fines and dried at 105oC in the oven.
2.2 Experiments
2.2.1 GAC adsorption isotherm and kinetics
Equilibrium adsorption experiments were conducted at room temperature (25oC) with
synthetic BTSE, synthetic PTSE, real BTSE and real PTSE, respectively. Sodium
hydrogen chloride (NaOCl) was added into wastewater to prevent microorganism
growth. Different doses of GAC were distributed into 250 ml flask containing 100 ml
wastewater. To avoid the influence of the light, all flasks were covered by aluminum
foil. All samples were shaken continuously for 90 hours on a shaking table at speed
130 rpm. After 90 hours shaking, samples of wastewater were taken from all flasks and
filtered through 0.45m filter prior to DOC analysis. The adsorbed amount (q) from
equilibrium experimental data was calculated by the following equation:
q=
V (C i C e )
M
(Eq.1)
Where q is the adsorbed amount (mg/g), V is the volume (L) of solution, Ci is the
initial DOC concentration of wastewater (mg/L), Ce is the equilibrium DOC
concentration (mg/L), M is the amount of adsorbents (g)
In the experiment of kinetics adsorption, GAC was distributed into 2 liters beaker filled
with wastewater at three different concentrations. The solutions with GAC were mixed
using mechanical stirrer at speed of 110 rpm for 6 hours and 72hours, respectively.
5
During the kinetic experiment, samples were taken from these three beakers at
different period of time and filtered through 0.45m filter before analyzing DOC. The
performance of GAC adsorption was evaluated in terms of DOC removal efficiency
(%), which is estimated by the following equation:
RE =
(C
Ct )
Ci
100
(Eq.2)
3. Theoretical approach
3.1 Adsorption isotherm
6
In general, the three or more -parameter models fitted the experimental data better than
the two-parameter models. Thus, a four-parameter hybrid Langmuir-Freundlich
isotherm model was employed to describe the adsorption equilibrium in this study.
This hybrid isotherm model is based on Langmuir and Freundlich equations. It is
expressed by Equation 3:
q=
qm b C
+ k C 1/ n
1+ b C
(Eq. 3)
dC
M dq
=
dt
V dt
(Eq.4)
The mass transfer rate between liquid and solid phase represented by LDFA model
(Equation 5):
dq 3 k f
(ci c s )
=
dt R p
(Eq.5)
predict the kinetic experimental data. Regardless of the amount of the adsorbents,
kinetic constants had the same value with same concentration and temperature (Lee et
al., 2007).
4. Results and discussion
In the GAC adsorption kinetics experiments, DOC in four different wastewaters were
quickly adsorbed within the first 90 minutes and remained consistent after that. In the
other words, during the first 90 minutes, the available sites in the coal based GAC
surface for adsorption were abundant. When all the adsorption sites were occupied and
the rates of adsorption and desorption were balanced, DOC removals by adsorption
were constant.
10
11
12
It was found that BGAC bioadsorption with wastewaters required longer equilibrium
time for all the dosages investigated. Dissolved organics were removed from wastewater
quickly within the first 6 hours, and then the removal rates increased gradually during
the next 66 hours. It can be explained that at beginning the adsorption of GAC was
more predominant and after the available sites were occupied, the organic matters were
biodegraded by the activity of microorganisms which colonized the external surface and
macro-pores of the GAC.
5. Conclusions
BGAC bioadsorption could lower the GAC dose and prolong the life time of
GAC,
Acknowledgements
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This research was funded by ARC linkage project (LP 0775149). The authors are also
grateful to the supports of Sydney Olympic Park Authority (SOPA) and Activated
Carbon Technologies Pty Ltd.
References
Dahiya, R.P., 2008. COD and BOD removal from domestic wastewater
14
Hoang, T.T.L., 2005. Granular activated carbon (GAC) biofilter in water and
wastewater treatment, M.E.thesis, University of Technology, Sydney.
Lee, J.W., Yang, T.H., Shim, W.G., Kwon, T.O., Moon, I.S., 2007.
Equilibria and
15
16
Compound
Concentration (mg/L)
BTSE
PTSE
Glucose
230
NH4HCO3
19.8
(NH4)2SO4
7.1
71
K2HPO4
KH2PO4
Peptone
Humic acid
Tannic acid
(Sodium) lignin sulfonate
Sodium lauryle sulphate
Acacia gum powder
Arabic acid (polysaccharide)
2.7
4.2
4.2
2.4
0.94
4.7
5
13.2
2.7
4.2
4.2
2.4
0.94
4.7
5
Trace nutrient
MgSO4.7H2O
0.71
5.07
CaCl2.2H2O
0.0184
0.368
MnCl2.4H2O
0.01375
0.275
ZnSO4.7H2O
0.022
0.44
FeCl3
0.0725
1.45
CuSO4.5H2O
0.01995
0.391
CoCl2.6H2O
0.021
0.42
Na2MoO4.2H2O
0.063
1.26
Beef extract
1.8
Yeast extract
20
17
Wastewater Type
Synthetic BTSE
Synthetic PTSE
Real BTSE
Real PTSE
Dose
(g/L)
0.25
0.5
1
2.5
5
2.5
5
10
25
50
0.1
0.25
0.5
0.75
1
2.5
5
10
25
40
q (mg/g)
13.88
8.52
5.10
2.47
1.58
9.82
7.26
5.37
3.21
1.89
45.80
25.84
16.52
11.60
9.02
10.12
5.60
3.16
1.51
1.07
DOC removal
efficiency (%)
40.63
49.88
59.72
72.25
92.85
21.67
32.05
47.40
70.80
83.57
50.78
71.62
91.60
96.46
99.89
48.65
53.85
60.75
72.40
82.16
18
GAC
adsorption
Synthetic BTSE
Synthetic PTSE
Real BTSE
Real PTSE
qm
1.472
9.06
1.25
2.96E-03
4.884E+05
1.60E-02
2.37E+08
1.22E-06
5.492E-02
2.77E-11
3.21
8.43E-05
2.97E-01
1.72E-01
6.39E-01
2.80E-01
0.975
0.988
0.912
0.963
n
R
19
Wastewater Type
Synthetic BTSE
Synthetic PTSE
Real BTSE
Real PTSE
Dose
(g/L)
0.1
0.25
0.5
1
2
0.1
0.5
1
2
3
0.05
0.1
0.25
0.5
0.75
0.5
1
2
3
5
q (mg/g)
16.1
9.8
7.12
4.24
2.69
27.2
15.12
10.08
5.89
4.11
46
33.6
20.64
12.57
9.16
19.58
13.73
8.27
6.05
3.92
20
1.2
1.2
GAC = 1 g/L
GAC = 2 g/L
GAC = 3 g/L
LDFA
isotherm
LDFA++hybrid
Dual isotherm
0.8
C/Co
0.8
C/Co
GAC = 10 g/L
GAC = 20 g/L
GAC = 30 g/L
LDFA
LDFA+ +hybrid
Dual isotherm
isotherm
0.6
0.6
0.4
0.4
0.2
0.2
0
0
60
120
180
240
Time (min)
300
360
60
120
(a)
300
360
(b)
1.2
1.2
GAC=0.50 g/L
GAC=0.75 g/L
GAC=1.0 g/L
LDFA
+ hybrid isotherm
LDFA+Dual
isotherm
GAC=10 g/L
GAC=20 g/L
GAC=30 g/L
LDFA
LDFA+ hybrid
+ Dualisotherm
isotherm
1
0.8
C/Co
0.8
C/Co
180
240
Time (min)
0.6
0.6
0.4
0.4
0.2
0.2
0
0
60
120
180
Time (min)
(c)
240
300
360
60
120
180
240
Time (min)
300
360
(d)
Figure 1 GAC adsorption kinetics with LDFA + hybrid isotherm model ((a) synthetic
BTSE; (b) synthetic PTSE; (c) real BTSE; (d) real sewage)
21
DO concentration (%)
100
90
80
1st day
5th day
10th day
20th day
70
3rd day
7th day
15 th day
25th day
60
0
10
15
20
25
30
Time (min)
Figure 2 SOUR of biomass on GAC
22
GAC adsorption
GAC bioadsorption
100
90
80
70
60
50
40
30
20
10
0
Synthetic BTSE
(dose : 2g/L)
Real BTSE
(dose: 0.75g/L)
Synthetic PTSE
(dose 2.5g/L)
Real PTSE
(dose: 5g/L)
23