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Performance and modeling of a moving bed biolm

process: nickel and chromium heavy metal removal
Cite this: RSC Adv., 2016, 6, 113737
from industrial wastewater
Sepideh AghaBeiki,a Ali Shokuhi Rad*b and Ali Shokrolahzadeha

Received 29th September 2016
Accepted 25th November 2016
DOI: 10.1039/c6ra24259f
www.rsc.org/advances
The process of a lab-scale moving bed biolm reactor (MBBR) using simulated sugar-manufacturing
wastewater as feed was investigated. The concentration of the metals used in the present study were 10,
30, 50 and 100 milligrams per liter with a chemical oxygen demand (COD) of 800 mg L
1. After
activation of the reactor at adapted circumstances of microorganism, chromium and nickel as heavy
metals were added to the system during a specied time interval with concentrations of 10 to 100
milligrams per liter. The results showed that the COD removal eciency of the system was 1.87% at the
time of the microorganisms' adaptation. The maximum removal of chromium at the concentration of
50 mg L
1 and time of 20 h was 93.52% and this percentage was 82.41% for nickel at the concentration
of 30 mg L
1 and time of 20 h. Then, for the biological modeling process, three models including rst-
order, second-order (Grau) and StoverKincannon model were used. Finally, according to the kinetic
analysis of chromium and nickel removal, the StoverKincannon model was selected as the appropriate
model for modeling the MBBR process.

Cu, Ni and Zn using dierent absorption surfaces were inves-

1. Introduction
The increasing awareness about the irreparable dangers of
environmental pollution caused by discharging euents and
pollutants to nature has caused the environment protection
laws to become very strict in the past two decades.1,2 One of the
best options is to use a low-cost bioreactor capable of
enhancing the euent quality.3 Therefore, various methods
such as modeling,4 articial neural network,5 response surface
methodology,6 kinetic study,7 etc. have been used to investigate
the usefulness of these reactors. A Moving Bed Biolm Reactor
(MBBR) was supplied by a Norwegian company, in collabora-
tion with SINTEF research center in 1987 to exploit the
advantages of both suspended growth and attached growth
systems. This type of treatment benets from the growth of
microorganisms as biolms and is a promising option for
wastewater treatment.8,9 MBBR technology has been success-
fully applied to many types of wastewater including paper mill
wastewater,10 pharmaceutical industry wastewater,11 municipal
wastewater,12 and sh farm wastewater.13 Su et al.14 used MBBR
system to remove nitrate and Mn(II). Saien and Azizi searched
on chromium and nickle photocatalytic treatment eciencies
using this system.15 In another study, the removal of As, Cd, Cr,
a
Young Researchers and Elites Club, Tehran North Branch, Islamic Azad University,
Tehran, Iran
b
Department of Chemical Engineering, Qaemshahr Branch, Islamic Azad University,
Qaemshahr, Iran. E-mail: a.shokuhi@gmail.com; a.shokuhi@qaemiau.ac.ir; Fax:
+98-32367735; Tel: +98-9112134588
tigated by this system.16
MBBR is a combination of suspended and attached
biomasses. In such a reactor, the biomass grows as a biolm
on small carrier elements that move around in the reactor
maintaining the biomass per unit volume at a high level. In
aerobic processes, the biolm carrier movement is eected by
blowers. Therefore, the MBBR process has the advantages of
attached and suspended growth systems.17 A key characteristic
of MBBR reactors is not only the increase in the eective
carrier area that thereby directly contributes to a larger biolm
but also that it allows good conditions for the transport of
substrates into the biolm.18 Because of the extremely
compact high-rate process, the hydraulic retention time (HRT)
in the MBBR is low.8
Low operating costs as well as high system eciency and
performance, small coherent system and ecient treatment of
sewage, lack of eclipse, low hydraulic losses, process depen-
dence on the activated sludge systems and attached systems,
lack of necessity for reverse wash and lack of sludge are the
most important factors in the progression of the reactor in
wastewater treatment.13,19
The aim of this study is to evaluate the performance of
MBBR system in heavy metals removal from the wastewater. To
analyze the kinetics of the biological reactions, the rst-order,
second-order (Grau) and StoverKincannon models have used.
The reactor volume as well as the output pollutant concentra-
tion are predicted in proportion to the most appropriate
kinetic model.

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RSC Advances
2. Materials and methods
2.1. Reactor
The rectangular cube reactor with a capacity of 32 L is made of
Plexiglas. In this reactor, the original Kaldnes carrier was made
of high-density polyethylene (k1 type) produced by Pakan Gha-
treh Company with a density of 70%. The specications of the
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Kaldnes are presented in Table 1. At the bottom of the reactor,
an air stone, which is embedded, is connected to the air
compressor (Hailea-Model: ACO-318) with a capacity of 60 L
min
1 by a hose which provides the required amount of oxygen
and rotates the Kaldnes in the reactor.13 Furthermore, in the
reactor output, a net is embedded to keep the Kaldnes. To take
samples from the reactor, 4 valves are installed at a distance of
20 cm from each other on the reactor. To feed the reactor,
a 500 L tank was connected by a hose to the reactor and the feed
input to the reactor was adjusted by a dosing pump with the
known ow rate (see Fig. 1).
2.2. MBBR start-up
Aer piloting, to ensure the health and seal the system, the
reactors were lled with water for two days and the air
compressor was installed and the Kaldnes were put inside the
reactor to adjust the amount of the air required for completing
the Kaldnes rotation. The aim of activating the bioreactors is
to create the microbial videos inside the Kaldnes and eventu-
ally to obtain the stability state. Due to the use of the synthetic
wastewater, the stage of the micro-organisms adaptation is of
great importance. To prepare the synthetic wastewater,
molasses obtained from the sugar mill has been used as the
source of carbon and potassium dihydrogen phosphate
(KH2PO4) has been used as the source of phosphorus and urea
has been used as the source of nitrogen.20 To activate the
reactors, seeding operation was used. To seed the reactors, the
return line path sludge was used. During the activation time,
the organic load of the synthetic wastewater with the adjusted
ratio of C/N/P which is equal to 100 : 5 : 1 was added gradually
for the growth of the micro-organisms and the formation of
the biolms on the Kaldnes (see Table 2).21,22 An appropriate
biolm was formed on the Kaldnes aer the bioreactor activity
for 88 days. Aer the biolm growth and the micro-organisms
adaptation to the existing micro-organisms, dierent
concentrations (10, 30, 50 and 100 mg L
1) of chromium and
nickel heavy metal salts (Cr(NO3)3$9H2O 0.78 g L
1, NiN2-
O6$6H2O 0.5 g L
1) have been added to the synthetic
wastewater.
Table 1 Data for Kaldnes biolm carriers
Type of Kaldnes biolm carrier k1
Nominal diameter (mm) 9.1
Nominal length (mm) 7.2
Special biolm surface area (in bulk) (m2 m
3) 500
Special biolm surface area at 70% ll (m2 m
3) 350
Average weight of Kaldnes (g) 0.48
Average weight of Kaldnes with biolm (g) 2.46
113738 | RSC Adv., 2016, 6, 113737113744
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Paper
Fig. 1 (a) Activated reactor before (left) and after Kaldnes input and
biolm formation (right), and (b) biolm layer formation on Kaldnes
surface.
2.3. Sampling and analysis
During the period of test operation, dissolved COD, mixed
liquor suspended solids (MLSS), and dissolved oxygen (DO)
were measured at the inuent and euent from the reactors.
Analytical procedures followed in this study for COD, MLSS, and
DO determinations were those outlined in standard methods
for the examination of water and wastewater.23 The DO was
measured by a membrane covered amperometric electrode, and
nally CRISON pH meter was used to measure pH. To measure
metal concentration, inductively coupled plasma mass spec-
trometry (ICP-MS) device was used. ICP-MS is a category of mass
spectrometry that is capable of identifying metals and dierent
non-metals at concentrations as low as one part in 1015 (part per
quadrillion, ppq) on non-interfered low-background isotopes.24
2.4. Kinetics of biological reactions
The biological models are used to determine the relationship
between the variables (wastewater concentration (S0), output
concentration (Se), volume and hydraulic retention time (HRT)),
and these associations help to evaluate the empirical designs
and results.25 These models are also used to control and predict
the performance of the treatment and optimize the units built
in laboratory scale. In this study, to analyze the kinetic biolog-
ical reactions of chromium and nickel removal, three models of
rst-order, second-order (Grau) and StoverKincannon models
have been used.
2.4.1. First-order removal model. Assuming the rst-order
removal model, the rate of the pollutant concentration changes
in the reactor to remove the pollutants is presented as follows:26
Table 2 The composition of synthetic wastewater
Composition Amount (g/100 L)
Molasses 120
Nitrogen azote 3.77
Phosphate 1.82
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Fig. 2 (a) COD and MLSS output concentration changes during
reactor start-up, and (b) COD and MLSS removal eciency during
micro-organisms adaptation after 88 days.

dS/dt QS0/V
QSe/V
k1Se
where S0 and Se respectively represent the feed input and output
concentrations (mg L
1), k1 represents the rst-order kinetic
constant (h
1), Q represents the wastewater ow (L h
1) and V
Fig. 3 Removal eciency of chromium, nickel in concentrations of 10, 30, 50 and 100 mg L
1 and removal eciency of COD after the addition
of heavy metals.
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RSC Advances
represents the reactor volume (L). In the steady state of the
biological reactor, the removed pollutants concentration
change (dS/dt) is zero. Therefore, eqn (1) can be written as
follow:27
(S0
Se)/HRT k1Se (2)
where HRT represents the hydraulic retention time (h). More-
over, k1 can be obtained through plotting (S0
Se)/HRT against
Se (determine the concentration of ICP-MS method) and
according to eqn (2).
2.4.2. Second-order removal model (Grau). The equation
for the second-order model will be as follows:26,28
(S0  HRT)/(S0
Se) HRT + S0/k2X (3)
If the second part of the right side of eqn (3) is assumed to be
constant, the following equation is obtained:
(S0  HRT)/(S0
Se) a + bHRT (4)
where, a (S0/k2X) and b are xed. (S0
Se)/S0 represents the
pollutant removal eciency. The amount of X is equal to the
average concentration of the microbial mass in the reactor
(mg L
1) and k2 represents the pollutant removal rate constant
(h
1).
The reactor output concentration prediction equation is as
follows:27
(1) Se S0(1
HRT/(a + bHRT)) (5)
2.4.3. StoverKincannon removal model. One of the most
ecient and eective removal models for the expression of the
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biolm systems is StoverKincannon model. This model is 3. Results and discussion

presented as follows:29
3.1. Evaluation of bioreactors in adaptation stage
Umax QS0 =A
dS=dt (6) One of the most important steps in activating the biological
ks QS0 =A
systems is the adaptation of the micro-organisms to the envi-
ronmental conditions. As shown in Fig. 2, in the rst days of
Moreover, writing the mass balance around the system, the operation, the biological mass concentration and the COD
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following equation will be obtained:26,27 removal eciency percentage in the reactor were negligible.
However, at the time of the micro-organisms adaptation, the
dS/dt Q(S0
Se)/V (7) MLSS and COD removal eciency increased so that COD
removal eciency reaches to 85%. According to Fig. 2, aer the
Therefore, embedding the second sides of the equations in
micro-organisms adaptation (pH 68, DO 34 mg L
1, COD
equality, the following equation will be obtained:26,27
800 mg L
1 and retention time of 88 days), by increasing HRT,
Umax QS0 =A
dS=dt QS0
Se =V (8)
ks QS0 =A

Eqn (8) was used for the rst time for the rotating biological
contactors reactors assuming that the amount of the biological
or MLSS particles suspending in the system is negligible
compared to the attached biological solids. However, in MBBR,
the biological solids have a large share in the reactor and cannot
be neglected. Therefore, in eqn (8), instead of the parameter of
level (L), the parameter of volume (V) is used. Thus, we have:
Umax QS0 =V
dS=dt QS0
Se =V (9)
ks QS0 =V

Based on the studies by StoverKincannon30 and Henze and

Harremoes,31 the rate of COD removal and removal eciency
does not depend on the concentration of organic materials or
hydraulic load, but it depends on the organic load applied to the
system. With linearizing eqn (9), we will have:

V/Q(S0
Se) (k3V)/(UmaxQS0) + 1/Umax (10)

where Umax represents the maximum removal rate (mg L
1 h
1)
and k3 represents the saturation constant (mg L
1 h
1).
By plotting the reverse rate of the organic materials removal
V/Q(S0
Se) based on the reverse total organic load V/QS0, Umax
and k3 values can be calculated. By writing the mass balance for
the entire reactor, the volume and concentration of the output
organic material from the reactor can be calculated.
Substituting eqn (9) by eqn (7), we will have:
Umax S0
Se S0
(11)
ks QS0 =V

Moreover, volume of the reactor is given by following

equation:
QS0
V (12)
Umax S0 =S0
Se
ks

Eqn (11) and (12) show that StoverKincannon equation is an

appropriate equation for designing such reactors due to its
ability to calculate the volume and concentration of the output
Fig. 4 First-order removal model to remove chromium (a), nickel (b),
materials from the reactor. and COD (c) by MBBR.

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COD removal eciency also increases and this is due to the
high contact time for the enzymes secreted by the biolm and
the increase of the biolms biological usability of layers.29 Since
the metal concentrations were put gradually over a long time in
the system, the changes in MLSS were insignicant. Thus, the
biolm attached to the acne had insignicant losses which
caused an increase in the amount of microorganisms attached
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to the bed inside the reactor.
3.2. Chromium and nickel heavy metals removal
At a later stage, to evaluate the performance of the system in
removing the heavy metals, chromium and nickel solutions
containing the input concentrations of 10, 30, 50 and 100 mg
L
1 with the xed COD of 800 mg L
1 were added to the system
(see Fig. 3). The maximum eciency of chromium removal by
Fig. 5 Grau removal model to remove chromium (a), nickel (b), and
COD (c) by MBBR.
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the MBBR system was obtained 93.52%. Therefore, it can be
concluded that the biolm system used in this study has a high
eciency and is suitable for biological removal of chromium in
optimal conditions (with input chromium concentration of
50 mg L
1, COD 800 mg L
1 and hydraulic retention time of
20 h). For nickel, the removal eciency in optimal conditions
(with input nickel concentration of 30 mg L
1, COD 800 mg
L
1 and hydraulic retention time of 20 h) was obtained 82.41%.
The reason for the high eciency removal of nickel and chro-
mium polyphagia bacteria is attributed to the physical property
Fig. 6 StoverKincannon removal model to remove chromium (a),
nickel (b), and COD (c) by MBBR.
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Table 3 Equations to calculate reactor output concentration and concluded that the reactor does not follow this model and its
volume use is not recommended due to large errors.
Cr QS0 21:55S0
V Se S0
  3.4. Second-order pollutant removal model (Grau)
21:55S0 QS0

23:46 23:46
S0
Se V As the Fig. 5 shows, the coecient R2 of the second-order model
Ni QS0 6:18S0 is more adapted compared to the rst-order model. In Fig. 5,
V Se S0
 
6:18S0 QS0 a and b are calculated through plotting HRT/E against HRT and

9:64
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9:64
S0
Se
COD QS0
V Se S0

38:76S0

38:66 38:66
S0
Se
of Kaldnes. Moreover, the dierence in the removal amount of
chromium and nickel may be due to dierences in dimensions
and physical properties of their atoms.
Results showed that increase in chromium and nickel
concentration, the COD removal eciency decreases from 85%
to 44%. With increasing the concentrations of chromium and
nickel, the system would have a hydraulic shock due to the high
organic load. Chromium and nickel removal eciencies are
respectively 79.6% and 38.4% at the concentration of 100 mg
L
1. Furthermore, aer the shock, COD output concentration
increases to 870.56 mg L
1.
V displayed (see Table 4). An increase in each of the a and
38:76S0 b parameters has a direct negative eect on the eciency. The
 
QS0
value of Grau second-order constant (k2) depends on the
V
inuent substrate concentration (S0) and biomass concentra-
tion (X) in the reactor and increases with the increase of
substrate removal eciency.32
3.5. StoverKincannon pollutant removal model
According to Fig. 6, the Umax and k3 kinetic constants to remove
chromium and nickel, and COD are shown in Table 4. As the
gure shows, the coecient R2 indicates that the test results
follow the KincannonStover model. Aer calculating the Umax
and k3, their amounts were placed in the eqn (11) and the
reactor outlet concentration could be determined. By placing
the Umax and k3 values in eqn (12), the reactor volume required
for the concentration of the desired output can be achieved.
Accordingly, equations to calculate the volume and concentra-
tion of reactor output are also shown in Table 3.

3.3. First-order pollutant removal model

As Fig. 4 shows, k1 can be calculated from the slope of the
plotted line. Accordingly, the rst-order kinetic constant (k1) for
removal of COD and heavy metals like chromium and nickel is
provided in Table 4. Considering the low value of R2, it can be
4. Conclusions
The results obtained from samples with dierent concentra-
tions of metals as input into the MBBR system show that this
system has been successful in terms of COD and metals

Table 4 Parameters of rst-order, second-order (Grau) and StoverKincannon kinetic models on the absorption of chromium, nickel and COD

Kinetic model
Concentration
Type of pollutant (mg L
1) First-order Grau second-order StoverKinconnon

Cr 10 k1 0.2407 h
1, R2 0.8011 a 4.5755 h, b 0.9673, k2 Umax 7.44 mg L
1 h
1, k3

0.044 h
1, R2 0.9832 7.18 mg L
1 h
1, R2 0.9917
30 k1 0.2784 h
1, R2 0.8633 a 1.405 h, b 1.1188, k2 Umax 2.18 mg L
1 h
1, k3
0.427 h
1, R2 0.9589 2.1 mg L
1 h
1, R2 0.9828
50 k1 0.4082 h
1, R2 0.9391 a 2.6124 h, b 0.9668, k2 Umax 19.12 mg L
1 h
1, k3
0.382 h
1, R2 0.994 18.05 mg L
1 h
1, R2
0.9939
100 k1 0.6781 h
1, R2 0.9666 a 1.7178 h, b 1.1605, k2 Umax 57.47 mg L
1 h
1, k3
1.164 h
1, R2 0.999 66.52 mg L
1 h
1, R2
0.999
Ni 10 k1 0.352 h
1, R2 0.8553 a 3.9571 h, b 1.2362, k2 Umax 2.52 mg L
1 h
1, k3
0.056 h
1, R2 0.9941 3.11 mg L
1 h
1, R2 0.9941
30 k1 0.3066 h
1, R2 0.9494 a 4.319 h, b 1.0343, k2 Umax 7.83 mg L
1 h
1, k3
0.14 h
1, R2 0.9872 8.28 mg L
1 h
1, R2 0.9931
50 k1 0.1473 h
1, R2 0.6451 a 8.1838 h, b 1.3591, k2 Umax 6.08 mg L
1 h
1, k3
0.122 h
1, R2 0.8802 8.25 mg L
1 h
1, R2 0.8798
100 k1 0.1806 h
1, R2 0.4894 a 12.019 h, b 2.2881, k2 Umax 8.29 mg L
1 h
1, k3
0.166 h
1, R2 0.8955 18.92 mg L
1 h
1, R2
0.8943
COD 800 k1 0.0507 h
1, R2 0.926 a 20.38 h, b 1.0017, k2 Umax 38.76 mg L
1 h
1, k3
0.25 h
1, R2 0.9972 38.66 mg L
1 h
1, R2
0.9973

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removal. The maximum removal eciency of chromium
(93.52%) is achieved at the concentration of 50 mg L
1 and at
the time of 20 h and the maximum removal eciency of nickel
(82.41%) is achieved at the concentration of 30 mg L
1 and at
the time of 20 h. COD removal eciency also reached the
constant amount of 79.1% aer 72 h which only increased to
87.1% aer 144 h. The obtained results from the kinetic anal-
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ysis of the reactor at dierent stages indicated the proper
compliance of the obtained data with the StoverKincannon
model which is obvious in the determination coecients (R2).
As a result, using MBBR process and following the conditions to
exploit the biological processes, proper models can be designed
to remove the non-biodegradable compounds from wastewater.
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This journal is The Royal Society of Chemistry 2016