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Chemical Engineering Science 60 (2005) 2845 2850

www.elsevier.com/locate/ces

Periodic operation of biolters. A concise model and

experimental validation
Klaudia Chmiela , Agnieszka Koniecznya , Micha Palicaa , A.B. Jarzebskia, b,
a Department of Chemical Engineering, Faculty of Chemistry, Silesian University of Technology, M. Strzody 7, Gliwice 44-100, Poland
b Institute of Chemical Engineering, Polish Academy of Sciences, Batycka 5, Gliwice, Poland

Received 4 February 2004; received in revised form 5 December 2004; accepted 28 December 2004

Abstract
Concise model of bioltration based on a linear driving force concept, that takes into account adsorption of pollutant in the support phase
and its biodegradation therein with the rate governed by a modied three-parameter Monod-type expression, was shown to be suitable to
portray the transient behavior of biolters arising from the periodic operation. Good agreement between simulations and experiments was
obtained for the biodegradation of methyl-ethyl-ketone or n-butanol on a pre-selected bark bed in a broad range of operating conditions.
2005 Elsevier Ltd. All rights reserved.
Keywords: Bioltration; Periodic operation; Bioreactors; Kinetics; Environment; Mathematical modelling

1. Introduction
Biotreatment of off-gases containing volatile organic
compounds (VOCs) is a reliable and cost-effective technology for VOCs removal and there are scores of papers addressing its application to specic problems. At rst glance
its principles are simple, but when the process is examined
in more detail it appears quite complex, as Ottengraf and
Van den Oever indicated in their pioneering work in 1983.
To obtain its deeper understanding and to hammer up tools
suitable for the scale-up, design and operation control, a
number of models of different complexity has been proposed (Devinny et al., 1999; Hodge and Devinny, 1995;
Amanullah et al., 1999; Zarook et al., 1997; Mohseni and
Allen, 2000; McNevin and Barford, 2000, and references
therein). In the most practical situations, the level of VOCs
emission varies slowly and hence the industrial biolters
are often subjected to steady-state or pseudo-steady-state
Corresponding author. Department of Chemical Engineering, Faculty
of Chemistry, Silesian University of Technology, M. Strzody 7, Gliwice
44-100, Poland. Tel.: +48 32 2371 461; fax:+48 32 237 1461.
E-mail address: a.jarzeb@iich.gliwice.pl (A.B. Jarzebski).

0009-2509/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2004.12.035

conditions. However, there is also a clear interest shown

by smaller enterprises in the operation of biolters under
periodic conditions, with devices being switched-on and
-off daily. Clearly, this implies a transient bioltration all
along. The dynamic operations of biolters have been more
recently analyzed with considerable success (Zarook et al.,
1997; Amanullah et al., 1999). However, the models proposed are quite complex. In brief, they assume that the
organic pollutant is mainly degraded in a biolm, covering
partially the support media. The biodegradation kinetics
is governed either by the Monod or Andrews expressions,
corrected by effectiveness factors and limited by oxygen
concentration. The models often assume that the uncovered
surface of the solid support, considered biologically inert,
remains in direct contact with the gas phase and adsorbs the
pollutant, whereas biolm is usually considered passive in
this respect. Diffusivities of VOCs and oxygen in the biolm
are assumed equal to diffusivities of the same compound
in water, corrected by a factor depending on the biolm
density, with the latter value assumed constant. The number
of parameters (over 20) involved in these models and great
uncertainty in quantifying the specic parameters pertaining to both biolm and packing (often natural and complex)

2846

K. Chmiel et al. / Chemical Engineering Science 60 (2005) 2845 2850

themselves speak about the scale of difculties encountered

in their practical application (Spigno et al., 2003). Thus, not
surprisingly perhaps, the less rigorous models of bioltrations, i.e., a linear driving force (LDF) model devised by
Hodge and Devinny (1995), and a plain single-phase approach have more recently been recommended (Amanullah
et al., 1999; McNevin and Barford, 2000) for the performance assessment and design purposes after extensive analysis of various models. The former may be used to portray
the non-steady-state situations whereas the latter is recommended for the assessment of steady-state cases. However,
both these models, and especially the single-phase one, tend
to appear accurate enough only in a narrow range of process
parameters (Chmiel, 2003). In light of the aforementioned,
we deem it necessary to look for a solution suitable for
practical applications in strongly transient situations generated by the periodic operation of biolters. The appropriate
model should be physically realistic and able to offer predictions accurate enough in a broad range of process variables,
while being concise and easy to use.
In this paper, we address this issue by proposing a modied LDF approach and comparing the modelling predictions
with experiments of the periodic bioltration of air polluted
with either methyl-ethyl-ketone (MEK) or n-butanol, using
the pre-selected pine tree bark as a natural packing populated by microorganisms. As the VOCs involved are easy-todegrade compounds, the more detailed presentation of experiments performed is out of scope.

where the factor q N1 , easily seen in numerator of Eq. (1),

indirectly represents the aforementioned positive (N > 1)
effect, and the remainder is the Monod expression. In transient situations the values of both factors vary in time over a
height of bed, depending on the actual concentration of pollutant/substrate available to microorganisms in a solid phase.
Apparently, Eq. (1) takes the form of the Monod equation
when N equals unity. Alternatively, the modied Andrewstype equation, with q N1 factor, may also be used, if appropriate (Zarook et al., 1997; Spigno et al., 2003). The mass
balance equations for both phases are the same in this approach as in LDF, i.e., for the gas phase

jCi
j2 C i
jCi
1
= DL
w

[kigads (qi qi )]
2
jt
jx
jx

(2)

with initial and boundary conditions

Ci (x, 0) = 0,


jCi


DL
= w(Ci |0 Ci |0+ ),
jx
x=0


jCi


= 0,
jx
x=H

(3)
(4)

(5)

and for the solid phase

jqi
= kigads (qi qi ) rs
jt

(6)

subject to initial condition

2. Mathematical model

qi (x, 0) = 0.

We believe that under periodic operation of biolter, the

biolm is less developed than under continuous regime, due
to temporal nutrient shortages. This and the use of a natural
support with considerable adsorptive capacity plus uncertainty regarding the values of specic parameters concerning both the biolm and support, justies departure from
the biolm concept and adaptation of a less rigorous LDF
model. Notwithstanding its simplicity, this approach is still
fairly realistic; it makes use of an axially dispersed plug-ow
model for the gas phase, a linear driving force to approximate the pollutant interphase transport, and allows for the
pollutant adsorption and biodegradation in the support/biotic
phase using the rst-order kinetics with no oxygen limitation of the latter. Its major disadvantage, in our opinion, is
that the LDF model does not allow for the effect of varying pollutant concentration on the amount of microorganisms involved in the biodegradation and hence additionally
affecting its rate, aside from the specic rate of assimilation
of substrate by microorganisms. As the biophase is not explicitly present in the model we propose to take this effect
indirectly, and imperfectly perhaps, into account by expressing the rate of biodegradation as
rs =

qiN
,
Km + q i

(1)

(7)

The adsorption of organic pollutants on the packing was

described by the linear isotherm (Amanullah et al., 1999;
Delhomenie et al., 2002):
qi =

Ci
.
m2

(8)

The model has seven parameters out of which three

(DL , , kigads ) are standard quantities encountered in models of gassolid phase contacting devices, and the remaining
four, related to the bioconversion kinetics and adsorption,
have to be estimated from experiments involving the specic packing, biophase and air pollutant. The set of dening
Eqs. (1)(8) can easily be solved simultaneously using a
commercial gPROMS code.

3. Experiments
Two identical lab-scale biolters were used. Each biolter
consisted of a jacketed glass column with the inner diameter of 0.175 m and a height of 0.5 m, the systems of odor
generation and air prehumidication equipped with the appropriate control devices as shown in Fig. 1. Columns were
lled with the pre-selected natural pine tree bark pieces of

K. Chmiel et al. / Chemical Engineering Science 60 (2005) 2845 2850

2847

day in a random manner, taking the values from the range

of 5100 mgVOC/m3 to 210 m3 /h. To check whether the
bed was regenerated over night (cf. Eq. (7)) and to make
sure that this indeed was the case, each run commenced
with a half hour purge of a biolter using pure air. No trace
of odorant presence in the efuent air was detected indicating that adsorbed pollutants were fully assimilated by
microorganisms.
The adsorption tests were carried out at room temperature similarly as described earlier (Delhomenie et al., 2002)
using a sterilized bed (120 C, 45 min in an autoclave) wetted prior to adsorption experiments with the aqueous solution of CuSO4 to eliminate any microbial activity. The inlet
concentration of the given VOC in air was set at the predetermined value and it was controlled throughout the experiment, with the exit concentration being measured at 15 min
periods until the bed was saturated.

Table 1
Operating parameters of the biolters
VOC

C1 (g/m)3

V (m3 /h)

n-butanol
MEK

0.0050.12
0.0050.10

47
210

size 0.603 mm, supported on the sieve plate to ensure a homogeneous distribution of gas ow over the cross section
of the lter bed. The organic pollutant was introduced into
the inowing air prehumidied to about 9496% of relative
humidity to avoid drying of the lter bed. The lter material
was irrigated daily with water pumped overhead to maintain
proper moisture of the support and weekly with an aqueous
solution containing NH4 NO3 , (NH4 )2 SO4 and KH2 PO4 in
order to supply the microorganisms with the additional nutrients.
MEK and n-butanol were analyzed by injecting grab samples into an HP 5890 GC equipped with capillary column
(Fused Silica) and FID detector.
Table 1 summarizes the operating parameters of the biolters.
After inoculation of beds using a diluted sludge of
microorganisms prevailed by Pseudomonas and Bacillus
species, the biolter was subjected to the run-up, aimed at
the formation of an active bed. This period took about 34
months during which the biolter was run for about 910 h
a day with an air stream loaded with organics, initially
1020 mg/m3 and later 20100 mg/m3 . During main experiments, the inlet pollutant concentration and air ow rate
were kept constant over a day, but they varied from day to

4. Results and discussion

The equilibrium adsorption isotherms of n-butanol and
MEK on the pine bark packing, extracted from the adsorption breakthrough experiments without biodegradation, are
shown in Fig. 2. Table 2 gives the values of gassolid partition coefcient m2 determined from the tting of Eq. (8) to
experimental data for n-butanol and MEK, respectively, and
the values of kigads , DL and used in computations. The
porosity of the packing was determined earlier as part of the
characterization of its hydrodynamic properties. The value
of DL taken was the same as in the earlier studies (Hodge
and Devinny, 1995), and well within the range of values
applied in earlier computations (Amanullah et al., 1999),

0.16
n-butanol
MEK
2
C1= 0.0004 q* R = 0.9653

C1= 0.002 q* R2= 0.9932

0.12

C1[g/m3]

Fig. 1. Experimental setup (1compressor, 2ow meters,

3humidier, 4odour sparger, 5mixer, 6inlet gas sampling,
7outlet gas sampling, 8biolter, 9valve, 10sprinkler).

0.08

0.04

0.00
0

100

200

300

q*[g/m3]

Fig. 2. Variation of MEK and butanol concentration in gas phase vs. odor
concentration in stationary phase C1 = f (q ).

2848

K. Chmiel et al. / Chemical Engineering Science 60 (2005) 2845 2850

Table 2
The parameters used in simulations

0.1
MEK

kigads (1/s)
N

(g2N /m3N s)
Km (g/m3 )
DL (m2 /s)
m2

0.001
1.5
1.25 103
0.555
5 105
4 104
0.65

0.003
1.35
0.4 103
0.025
5 105
2 103
0.58

and that of kigads was determined by tting the adsorption

breakthrough curves. With these parameters held constant
the parameters of reaction kinetics were estimated from regular runs to obtain the values (Table 2) affording the best
agreement with transient exit concentrations proles. Such
an approach was adopted for a number of practical reasons.
The response of exit pollutant concentration to changes in
gas velocity is usually linked with the residence time variation and not so much seen as resulting from the change in
interphase mass transfer or longitudinal dispersion (cf. Jorio
et al., 2000; McNevin and Barford, 2000). The effect of
longitudinal dispersion on biolter performance is usually
small, and totally negligible, if Peclet number (P e =wH/D)
is
1000 (in our case P e > 500). No doubt the value of
kigads varies with gas velocity. However, the assumption of
its constant value throughout was dictated by the need to explore the potentials of the LDF model together with Eq. (1).
The agreement between experiment and predictions from the
model appeared to be quite good for a broad range of operation parameters: inlet contaminant concentrations between
5 and 100 mgVOC/m3 and air ow rates up to 10 m3 /h (i.e.,
air supercial velocities up to about 0.03 m/s). It is noteworthy that the best estimates of parameter N appeared to be
about 1.5 and 1.35, for butanol and MEK, respectively, i.e.,
notably larger than the unity predicted by the Monod or rstorder expression. In our opinion this clearly corroborates the
use of Eq.(1) as more suitable to quantify the complex kinetics of bioconversion. Attempts to apply the Monod equation
(N = 1) instead of Eq. (1) failed to produce the predictions
valid in a broader range of process variables. These observations again highlight the importance of a proper expression of the bioconversion kinetics to obtain a fair portrayal
of transient bioltration.
The variation of exit pollutant concentrations with time
elapsed after start-up obtained from experiments and simulations is presented in Figs. 36. As can be seen, the
model proposed describes quite well the complex transient
characteristics of bioltration, including strongly variable
sigmoidal changes of the exit concentrations in time. The
initial part of these curves reects two highly unbalanced
processes: (i) intensive transport of the pollutant from the
gas phase into the stationary phase and its adsorption therein,
and (ii) slow conversion of the pollutant not catching up

0.08

100 [mg/m3] - model

experimental data
3
50 [mg/m ] - model
experimental data
10 [mg/m3] - model
experimental data

0.06
C2 [g/m3]

n-butanol

0.04

0.02

0
0

t [h]
Fig. 3. Variation of outlet concentration of BuOH in air vs. working time
for various inlet concentrations,  = 2.7 (s).

0.04

50 [mg/m3] k=3.6 [s] - model

exper.
20 [mg/m3] k=2.7 [s] - model
exper.
10 [mg/m3] k=2.2 [s] - model
exper.

0.03

C2 [g/m3]

Parameter

0.02

0.01

0
0

t [h]
Fig. 4. Variation of outlet concentration of BuOH in air vs. working time
for various inlet concentrations,  = 3.6 2.2 (s).

with the former. This leads to the increase in adsorbate

concentration in the stationary phase, resulting in the slowdown of interphase mass transport, and enhancement of
bioconversion kinetics (cf. Eq. (1)). Note that exit concentrations attained a pseudo-steady state in about 56 h after
beginning and this process was also quite well portrayed.
The steady-state values were also quite well predicted by
the model in a rather broad range of process parameters,
with better agreement between the model predictions and

K. Chmiel et al. / Chemical Engineering Science 60 (2005) 2845 2850

0.1

0.08

0.6

C2 [g/m3]

0.06

100 [mg/m3] - exper. MEK

100 [mg/m3] - model MEK
3
13 [mg/m ] - exper. MEK
3
13 [mg/m ] - model MEK
100 [mg/m3] - exper. BuOH
100 [mg/m3] - model BuOH
20 [mg/m3] - exper. BuOH
3
20 [mg/m ] - model BuOH

0.8

100 [mg/m3] - model

exper.
3]
40 [mg/m - model
exper.
3
13 [mg/m ] - model
exper.
3
5 [mg/m ] - model
exper.

0.04

0.4

0.02

0.2

0
0

12

16

20

k [s]

t [h]

Fig. 5. Variation of outlet concentration of MEK in air vs. working time

for various inlet concentrations,  = 5.4 (s).

0.04

Fig. 7. Bioltration efciency for BuOH and MEK vs. contact time for
steady-state operation.

5. Conclusions

0.03

C2 [g/m3]

2849

The concise model which accounts for the rst-order

effects of bioltration, i.e., a convective transport of the
pollutants in the gas phase, a liner driving force of mass
transfer between the gas phase and the unied support/biotic
phase, and the pollutants adsorption and biodegradation
therein, was shown to be very efcient in describing
transient behavior arising from the periodic operation of
biolter. The use of an appropriate expression for the
kinetics of biodegradation appeared to be an important
factor to obtain good agreement between model predictions and experimental data in a broad range of operating
parameters.

40 [mg/m3] k=10.8 [s] - model

exper.
13 [mg/m3] k=5.4 [s] - model
exper.
5 [mg/m3] k=3.1 [s] - model
exper.

0.02

0.01

0
0

2
t [h]

Fig. 6. Variation of outlet concentration of MEK in air vs. working time

for various inlet concentrations,  = 10.8 3.1 (s).

experiments obtained for MEK and shorter residence times

(Fig. 7 ).
These ndings are hardly surprising. The approach proposed is a straightforward extension of the LDF model more
recently recommended by Amanullah et al. (1999) for the
prediction of biolter performance in result of the extensive
comparative analysis of various models. The use of a somewhat more complex expression for the reaction kinetics
resulted in the improvement of prediction capabilities.

Notation
Ci
DL
H
kigads
Km
m2
N
qi
qi
rs

odor concentration in gas phase, g/m3

dispersion coefcient, m2 /s
bed height, m
overall mass transfer coefcient, 1/s
saturation constant in Eq. (1), g/m3
partition coefcient of odor between gas and solid
phase, dimensionless
power exponent in Eq. (1)
solid-phase concentration of contaminant in the
biolter, g/m3
equilibrium concentration of component in the
solid phase, g/m3
reaction rate, g/m3 s

2850

t
V
w
x

K. Chmiel et al. / Chemical Engineering Science 60 (2005) 2845 2850

working time, s
volumetric gas ow rate, m3 /h, m3 /s
gas velocity, m/s
distance, m

Greek letters

k

contact time, s
porosity of the bed, m3 /m3
rate constant of bioltration process, 1/h, 1/s

Subscripts
ads
i

Adsorbent
component i

Superscript
equilibrium
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simulation of a biolter. Industrial and Engineering Chemistry Research
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Chmiel, K., 2003. Transient and steady state characteristics of butanol

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