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Journal of Environmental Management 91 (2010) 1039–1054

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Journal of Environmental Management


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Review

Bioreactors for treatment of VOCs and odours – A review


Sandeep Mudliar*, Balendu Giri, Kiran Padoley, Dewanand Satpute, Rashmi Dixit,
Praveena Bhatt, Ram Pandey, Asha Juwarkar, Atul Vaidya
Environmental Biotechnology Division, National Environmental Engineering Research Institute (NEERI), Nehru Marg, Nagpur 440 020, India

a r t i c l e i n f o a b s t r a c t

Article history: Volatile organic compounds (VOCs) and odorous compounds discharged into the environment create
Received 25 August 2008 ecological and health hazards. In the recent past, biological waste air treatment processes using biore-
Received in revised form actors have gained popularity in control of VOCs and odour, since they offer a cost effective and envi-
12 December 2009
ronment friendly alternative to conventional air pollution control technologies. This review provides an
Accepted 3 January 2010
overview of the various bioreactors that are used in VOC and odour abatement, along with details on
Available online 23 February 2010
their configuration and design, mechanism of operation, insights into the microbial biodegradation
process and future R&D needs in this area.
Keywords:
VOC Ó 2010 Elsevier Ltd. All rights reserved.
Odour
Biological treatment
Bioreactor
Biofilter
Membrane bioreactor

1. Introduction design and configuration, as well as necessary parameters for their


operation will not only help in increasing the efficiency of the
Volatile organic compounds (VOCs) and odorous compounds treatment process but also give insights to develop newer, better
emitted from various industries pose problem to human and and robust treatment techniques. This review attempts to provide
environmental health. With increasing population, and new resi- an overview of the various bioreactors used for the control of VOCs
dential and industrial developments, the demand for VOC and and odours, their merits and demerits, their important operational
odour control systems to provide nuisance-free breathable air is parameters and future R&D needs in this area.
increasing. Stringent environmental legislations enforced by
government agencies, have led polluting industries to adopt
2. Bioreactors in VOC and odour control
effective air pollution treatment processes in order to comply with
these regulations. As a consequence, biological treatment tech-
Bioreactors play a very important role in the control of VOCs and
niques for VOC and odor control have gained tremendous popu-
odorous gases that are emitted by polluting industries. Although
larity in view of the several advantages they offer in comparison to
a number of different configurations exist, the main types of
traditional physical and chemical removal methods. Biological
conventional air phase biological reactors include biofilters, bio-
waste air treatment processes are not only cost effective as
trickling filters and bioscrubbers. Among the newly developed
compared to conventional techniques such as incineration or
reactors are the membrane reactors (Shareefdeen and Singh, 2005;
adsorption but are also environment friendly (Devinny et al., 1999;
Kumar et al., 2008a,b), which have been used for VOC and odour
Delhomenie and Heitz, 2005; Shareefdeen and Singh, 2005).
abatement. Although, the basic pollutant removal mechanisms of all
Biological waste air treatment technology makes use of several
the reactors are more or less similar, differences exist in the use of
types of bioreactors depending on the load and kind of pollutant to
microorganisms (may be either in suspended (in liquid) or immo-
be treated. The type of bioreactor used for abatement has a direct
bilized (biofilm) form), packing media, pollutant concentration etc.
consequence on the efficiency of the treatment process. An under-
standing of the bioreactors used for VOC and odour treatment, their
3. Biofilter

* Corresponding author. Tel.: þ91 712 2240097; fax: þ91 712 2249900/2249961. Biofilters (BFs) are reactors in which a humid polluted air stream
E-mail address: sn_mudliar@neeri.res.in (S. Mudliar). is passed through a porous packed bed on which a mixed culture of

0301-4797/$ – see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jenvman.2010.01.006
1040 S. Mudliar et al. / Journal of Environmental Management 91 (2010) 1039–1054

pollutant-degrading organisms is immobilized (Fig. 1). Generally,  The close design BFs, with either ascending or descending gas
the pollutant gases flow through the porous packing media, are flows, installed in closed rooms. These reactors require less
transported from the gaseous phase to the microbial biofilm space than the open configuration.
(through liquid phase or moisture) and the biological oxidation of
VOCs occurs.
3.1. Biofilter operation
BFs are used to treat a wide variety of organic and inorganic
pollutants in industrial and municipal exhaust streams. Although,
The operation of BFs involve a series of steps beginning with the
traditionally used for treatment of odorous gases from sewage
transfer of the pollutant from the air to the water phase, adsorption
treatment plants and composting facilities, BFs now find wide
to the medium or absorption into the biofilm, and finally biodegra-
application in treatment of several VOCs and odours. Among these
dation of the VOC/odorant within the biofilm (Devinny et al., 1999).
are odourants such as ammonia, hydrogen sulphide, mercaptan,
The most important physical, chemical and biological parameters
disulphides, etc., and VOCs like propane, butane, styrene, phenols,
influencing the biofiltration process are described below.
ethylene chloride, methanol, etc. Bench and pilot scale studies
have shown that 60 out of 189 hazardous air pollutants (HAPs) can
3.1.1. Transfer and partitioning of pollutant
be successfully treated with biofiltration (Devinny et al., 1999;
The first step in the biofiltration process is the transfer of
Shareefdeen and Singh, 2005). In Europe, more than 600 chemical
contaminants from the air to the water phase. This is generally not
processing industries use BFs for deodorization and treatment of
a rate-limiting step, and so one frequently assumes that the gas and
VOCs.
liquid are at equilibrium. At equilibrium, the partition between air
BFs are typically used for the treatment of large volumes of air
and water is generally described by Henry’s law, which is given by
streams containing low concentration of VOCs or odorants. The
the equation:
advantages and disadvantages of BFs are discussed below.
Advantages: Cgi ¼ Hi Cli

(a) Cost effective with (low operating and capital costs) where Cgi is the concentration of pollutant i in the gas phase, Hi is
(b) Low pressure drop Henry’s coefficient and Cli is the concentration of i in the liquid
(c) Treat large volumes of low concentration VOCs or odorants phase (Shareefdeen and Singh, 2005).
(d) Secondary waste streams are not produced Henrys’ coefficient (constant of proportionality Hi in above
equation) has been described in different units in literature. Using
Disadvantages: a non-dimensional Henrys’ coefficient, substances with values over
0.01 are considered volatile, and the higher the value, the less
(a) Clogging of the medium due to particulate matter soluble the substrate is in water. For example, the non-dimensional
(b) Problem of medium deterioration Henrys’ coefficient (at 25  C) for ammonia is reported to be 0.0005,
(c) Less treatment efficiency at high concentrations of pollutants while for H2S it is 0.92. Henrys’ coefficient depends on the
(d) Difficulty in moisture and pH control temperature and the chemical potential in the liquid phase
(Shareefdeen and Singh, 2005).
There are two BF configurations conventionally used for VOC In general, the elimination capacity of a BF declines with
and odour treatment viz. increasing Henry’s law constant since this indicates a tendency to
partition away from the liquid/biofilm phase where degradation is
 The open design BFs, with ascending gas flows, installed taking place.
outside the VOC/odour generating units. These reactors require
large areas, and are also exposed to climate changes. 3.1.2. Biofilm
The biofilm is a key element of the BF, which brings about the
biodegradation of the pollutants viz. VOC and odorous compounds.
‘‘Biofilm’’ is the mass of organisms growing on the surface of the
solid support; it carries out the catabolic activity and transforms the
pollutants to harmless products.
The thickness of the biofilm is influenced by several factors.
These include the type of pollutant, its rate of flow through the BF,
the bedding material used, and the design and configuration of the
treatment system being used. Biofilm thickness usually varies from
tens of micrometers to more than 1 cm, although an average of
1 mm or less is usually observed (Shareefdeen and Singh, 2005).
The activity increases with the thickness of the biofilm, up to a level
termed the ‘active thickness’. Above this level, the diffusion of
nutrients becomes a limiting factor (Devinny et al., 1999). Various
steady state and dynamic mathematical models have been reported
in literature to predict the substrate, oxygen and nutrient pene-
tration profile in the biofilm and facilitate evaluation of overall
biofilm effectiveness factor (Mudliar et al., 2008a,b; Shareefdeen
and Singh, 2005; Metris et al., 2001).

3.1.3. Biofilter bed


The BF bed constitutes the heart of the biofiltration process
because it provides the support for microbial growth. Bohn (1992)
Fig. 1. Schematics of a biofilter unit. established a list of characteristics that an ideal BF bed should
S. Mudliar et al. / Journal of Environmental Management 91 (2010) 1039–1054 1041

possess. The most important desirable characteristics of the BF bed et al., 1998), elimination of hydrophobic compounds, and better
include (a) high specific surface area for development of a microbial control of loading variations (Mason et al., 2000).
biofilm and gas-biofilm mass transfer, (b) high porosity to facilitate
homogeneous distribution of gases, (c) a good water retention 3.1.4. Oxygen levels
capacity to avoid bed drying, (d) presence and availability of Oxygen levels play a very vital role in the performance of a BF.
intrinsic nutrients, and (e) presence of a dense and diverse indig- However, this is very case specific as can be seen from experiments
enous microflora. discussed below, conducted by separate authors, on the effect of
Peat, soil, compost, and wood chips, are the most frequently oxygen limitation on biofiltration. Experiments by Shareefdeen
employed basic materials in BF beds. These materials satisfy most of et al. (1997) using air enriched with oxygen improved the perfor-
the required desirable criteria, and are widely available at low cost. mance of the BF and demonstrated that oxygen was indeed
Each of these materials has their own merits and demerits. The a limiting factor. In another experiment, Deshusses et al. (1996)
main advantage of soil is that, it offers a rich and varied microflora. found that there was no significant improvement in the simulta-
It however, contains only a few intrinsic nutrients, presents low neous removal of a mixture of methyl ethyl ketone (MEK) and
specific surface area and generates high-pressure drops (Swanson methyl isobutyl ketone (MIBK), when the oxygen content in air was
and Loehr, 1997). Peat has high amounts of organic matter, high increased. In this case, the fact that significant cross-inhibition of
specific surface area, and good water holding capacity and good MEK and MIBK biodegradation occurred suggested that kinetic
permeability. However, peat contains neither high levels of mineral effects were more important than diffusion effects. This was further
nutrients nor a dense indigenous microflora as in the case of soil or demonstrated in transient experiments where spikes of either
compost. Composts are materials that are most frequently compound were injected into BFs, and both cross- and self-inhi-
employed in biofiltration for a variety of reasons. Compost offers bitions were observed. Thus, role of oxygen in BF performance
a dense and varied microbial system, good water holding capacity, seems to be case specific. Oxygen is most likely to affect high-
good air permeability, and contains large amounts of intrinsic performance BFs or when thick biofilms exist.
nutrients. Moreover, the utilization of compost in BFs constitutes an In general principal in most applications, BF operations seek to
effective way of recycling and utilizing waste residual organic avoid anaerobic conditions. This is because, existence of even
matter, such as activated sludge from wastewater treatment plants, micro-anaerobic conditions lead to the formation of compounds,
forest products (branches, leaves, barks), domestic residues, etc. which themselves are odorous and this deviates from the overall
(Alexander, 1999). However, composts are often less stable than soil goal of eliminating odorants and VOCs. Some studies, however
or peat and have the tendency to break down and become compact, suggest that, fortuitous anaerobic microenvironment conditions
leading to increase in pressure drop in BF beds. This among other that exist in BFs, help in the degradation of organic pollutants
reasons is attributed to their high water holding capacity. Some (Shareefdeen et al., 1997).
authors have studied biofiltration using wood chips or barks as
packing material (Smet et al., 1996a,b, 1999; Hong and Park, 2004). 3.1.5. Nutrients
However, in general these authors have concluded that perfor- The pollutants introduced into the BFs, form the major carbon
mances obtained with such filtering materials are less satisfactory and energy source for microbial activity. Hydrogen and oxygen are
than those obtained with compost or peat. This has been explained found in the air, in the growth medium, and sometimes in the VOCs.
by the low pH-buffering capacity, the low specific surface areas and The availability of the other macronutrients (N, P, K, and S) and
the low nutrient content of such materials. Despite these defi- micronutrients (vitamins, metals) is partially fulfilled by the
ciencies, wood barks are still widely used in BFs as support mate- filtering materials used in the BF. Materials such as composts are
rials, in association with peat or compost. well known to contain various nutrients.
Indeed, to prevent bed crushing and compaction, most authors Studies have demonstrated that irrespective of the filtering
suggest materials that provide the bed with good structure, easy material employed, the steady addition of nutrients is necessary to
maintenance and rigidity, which consequently delay the clogging sustain a satisfactory microbial degradation activity. For example,
phenomena which thereby increases the bed lifespan. Examples some studies have shown that long-term utilization of compost-
include wood chips or barks (Luo, 2001), perlite (Woertz et al., based beds lead to progressive exhaustion of the intrinsic nutritive
2002), vermiculite (Pineda et al., 2000), glass beads (Zilli et al., resources (Morgenroth et al., 1996). This progressive nutrient
2000), polyurethane foam (Moe and Irvine, 2000), polystyrene deficiency then becomes a limiting factor for the long-term bio-
(Arulneyam and Swaminathan, 2000), lava rock (Chitwood and filtration performance (Delhomenie et al., 2001a,b).
Devinny, 2001), etc. Ibrahim et al. (2001) prepared a filter bed Models of biofiltration performance as a function of nutrient
composed of activated sludge immobilized on gel beads. Christen supply, and of nitrogen in particular have been developed and
et al. (2002) and Sene et al. (2002) developed a sugarcane-baggase- experimentally validated (Delhomenie et al., 2001a,b; Alonso et al.,
based bed, for the treatment of ethanol and benzene. Some bed- 2001; Metris et al., 2001; Dorado et al., 2008). Nutrients for
structuring agents also possess interesting chemical characteristics microbial growth are supplied either in the solid form which is
which they impart on the bed such as pH-buffering capacity directly inserted into the filter bed (Gribbins and Loehr, 1998), or as
(limestone), or general adsorbing capacity (activated carbon; aqueous solutions, which is the most frequently used method. Wu
Abumaizar et al., 1998). et al. (1999) reviewed the most common nutrient solutions used in
The efficiency of a BF material with respect to the pollutant for BFs. These include KH2PO4, NaxH(3x)PO4, KNO3, (NH4)2SO4, NH4Cl,
treatment is given by its adsorption coefficient or partition coeffi- NH4HCO3, CaCl2, MgSO4, MnSO4, FeSO4, Na2MoO4, and vitamins
cient. Tang and Hwang (1997) reported partition coefficients of (B1, etc.). Given the wide range of elements and compounds
toluene as 1.43 mg g1 with compost, 2.00 mg g1 with diatoma- influencing microbial behavior, the optimization of nutrient solu-
ceous earth, and 0.89 mg g1 with chaff. Beds containing activated tions for BFs is a challenging area of study.
carbon (granulated or powdered) provide adsorption coefficients
for toluene approximately 10–20 times greater (50.6 mg g1 of 3.1.6. pH
granulated activated carbon) (Tang and Hwang, 1997; Acuna et al., As is the case with several biological processes, pH has an
1999). Literature reports indicate that addition of activated carbon important influence on biofiltration efficiency. Above or below an
leads to improvement in biofilter degrading capacity (Abumaizar optimum pH range, microbial activity is severely affected. Most of
1042 S. Mudliar et al. / Journal of Environmental Management 91 (2010) 1039–1054

the microorganisms in BFs are neutrophilic i.e. their optimum pH is water evaporation from the packing material as a consequence of
7. Lu et al. (2002), observed maximum degradation of BTEX metabolic heat generation and variations of the relative humidity
between pH values of 7.5 and 8.0. Lee et al. (2002) also reported of the inlet air stream, and also the resulting decrease in biofilter
a pH of 7.0 to be optimal for BTEX degradation. Veiga et al. (1999), performance (Devinny and Hodge, 1995; Devinny et al., 1999;
studied the effect of pH on alkyl benzene degradation (between pH Metris et al., 2001; Morales et al., 2003).
3.5 and 7.0), and found that alkyl benzene degradation increased
with pH. Arnold et al. (1997) stated that styrene elimination 3.1.8. Microorganisms
improved in a neutral medium. Microorganisms are the catalysts for biodegradation of VOCs
VOCs that contain hetero-atoms (S, O, and N) are converted into and odours. For the degradation of VOCs, heterotrophic microor-
acidic products, which tend to reduce the pH (Christen et al., 2002), ganisms have been extensively reported (most often bacteria or
affect microorganisms and cause corrosion problems in down- fungi). The bed inoculation depends on both the nature of the
stream conduits (Webster and Devinny, 1998). Similar observations filtering material and the biodegradability level of the VOC to be
during VOC degradation due to formation of acidic intermediates treated. Many scientific workers prefer taking advantage of the
have also been reported by various authors (Shareefdeen and Singh, ecosystems already prevailing in the beds (Delhomenie et al.,
2005; Maestre et al., 2007). Kennes and Thalasso (1998) reported 2001a,b, 2002; Mohseni and Allen, 2000). After an acclimatization
that among the organic materials employed in BFs, soil exhibited period, the most resistant population to the toxic VOC is naturally
the best intrinsic pH-buffering capacity followed by composts and selected and a microbial hierarchy is established in the bed. In other
wood chips. Peats are naturally acidic (pH 3.0–4.0), and have low cases (such as for recalcitrant VOCs), researchers inoculate the BF
buffering capacity. To maintain the pH (at neutral) some authors beds with consortia extracted from sewage sludge, or strains
have reported insertion of buffer materials into the filter beds, for derived from either commercial sources or isolated from previously
e.g. – calcium carbonate (Smet et al., 1996a,b), and dolomite (Smet operated BF. In general, in terms of biomass density, a BF contains
et al., 1999). The pH can also be controlled by bed irrigation with between 106 and 1010 cfu of bacteria and actinomycetes per gram of
nutrient solutions that contain pH buffers, for example Ca (OH)2, bed (Krailas et al., 2000). Pedersen and Arvin (1995), Pedersen et al.
NaOH (Zilli et al., 2000), NaHCO3 (Tang and Hwang, 1997), and urea (1997), and Delhomenie et al. (2001a), have reported that in BFs,
(Delhomenie et al., 2002), etc. the degrading species represents between 1 and 15% of the total
population.
3.1.7. Moisture content
The moisture content of the filter bed is a critical factor for 3.1.9. Biofilm architecture
biofilter performance because microorganisms require water to VOC elimination is the result of many, interdependent processes
carry out their normal metabolic activity. Sub-optimal moisture that simultaneously take place inside the biofilter. To date, little
levels leads to drying of the bed and development of fissures that information exists about biofilm architecture in BFs. Previous work
cause channeling and short-circuiting (Shareefdeen and Singh, with scanning confocal laser microscopy has revealed the existence
2005). Deprivation of water to microorganisms causes a significant of cell-free channels extending from the biofilm-liquid interface to
reduction in the biodegradation rate. Excess water inhibits transfer the substratum and their possible role in enhancing pollutant and
of oxygen and hydrophobic pollutants to the biofilm, thereby oxygen mass transfer (Cox and Deshusses, 1998). A new and
promoting the development of anaerobic zones within the bed and promising development is the use of computed axial tomography
limiting the reaction rate. Too much water can also result in foul (CAT) X-ray scanning to characterize the biofilm macro- architec-
smelling emissions due to the lack of oxygen, increasing back- ture (Shareefdeen et al., 1997). CAT scans of a toluene-degrading BF
pressure due to reduced void volume, and channeling of the gas containing a large amount of biomass immobilized on poly-
within the bed. propylene pall rings showed a heterogeneous distribution of
Optimal water levels vary with different filtering material, biomass with large areas completely filled with biomass whereas
depending on medium, surface area, porosity and other factors. other sections of the reactor covered by <1 mm thick biomass.
Moisture content for optimal operation of the biological filter Further, image analysis revealed the presence of air/water channels
should be within 30–60% by weight, depending on the filtering ranging in area from <5 to380 mm2, with smaller channels (0–
medium used. Moisture levels in a biofilter are often maintained 60 mm2) contributing to more than 80% of the interfacial area. In
through pre- humidification of the inlet gas stream. Also, it is often future, further application of high resolution X-ray and possibly CAT
necessary to provide direct application of water to the bed through scanning techniques could contribute to a better understanding of
a sprinkler system at the top of the bed. More advanced controls the architecture of biofilms. Such progress could lead to a better
include the use of load cells that sense the weight of filter bed and understanding of pollutant mass transfer in BFs and ultimately to
are connected to sprinkler controls. Supplemental moisture supply a better design of materials for stable culture support (Shareefdeen
may be required because bio-oxidation is an exothermic reaction, et al., 1997).
and so drying can occur within the bed. Drying of the packing
material can lead to localize dry spots, and can result in non- 3.2. Future needs
uniform gas distribution and reduction in the activity of microor-
ganisms (Shareefdeen and Singh, 2005). Recently, it has been Biofiltration has clearly been shown to be a cost and energy
reported that, biofilters tend to experience drying at the air inlet efficient technology for treatment of a range of waste emissions
port, which causes decreased pollutant removal over time (Sakuma containing VOCs and odours. There is a need to work on innovative
et al., 2009). strategies such as pretreatment of VOCs and odours to remove
Control of moisture requires a better understanding of the particulates and/or enhance biodegradability and improve tech-
drying of the support due to changes in inlet air temperature and niques to treat more complicated polluted airstreams especially
relative humidity and from production of metabolic heat during multiple pollutant mixtures. Moreover, BF technology found field
pollutant oxidation. Various models are now available to study application well before its fundamental principles were under-
drying and its effect on biofilter performance. These models stood. This has resulted in several cases of unsuccessful or subop-
describe the variations in pollutant concentration, air relative timum operation of large-scale BFs. Today, with much better
humidity, temperature, and water content of the media, to predict understanding of the fundamental principles underlying the
S. Mudliar et al. / Journal of Environmental Management 91 (2010) 1039–1054 1043

biofiltration process, scope exists for designing better bioreactors The filtering material used in a BTF has to facilitate the gas and
with optimal operating conditions. A number of fundamental liquid flows through the bed, favor the development of the
questions however remain unanswered These include the quanti- microflora, and should resist crushing and compaction. BTF packing
fication of biomass turnover, the understanding of biodegradation that best meet these specifications are made from inert materials
kinetic relationships and factors influencing these relationships, such as resins, ceramics, celite, polyurethane, foam (Centinkaya
complex ecological complexity of BFs, and the interrelationships et al., 2000) etc. However, most of these materials present limited
between pollutants, oxygen and essential nutrients (Cox and specific surface areas between 100 and 300 m1 (Roh, 2000) with
Deshusses, 1998). All these factors have been shown to significantly exceptions in some cases where >1000 m1 for polyurethane-
influence both the performance and the long-term stability of BFs, based beds have been reported. As they are made from inert or
and thus require further investigation. In particular, quantitative synthetic material, BTFs need to be inoculated with suitable
studies are necessary. This would be made easier with the microbial culture. The use of activated sludge as initial microbial
expanding use of modern tools of biotechnology. Further, there is inoculum has been extensively reported (Lu et al., 2002; Oh and
need to develop design correlations on mass/heat transfer, diffu- Bartha, 1997).
sion coefficient in biofilm, gas/liquid holds up to facilitate improved The advantages and limitations of BTFs include the following.
biofilter design. Furthermore, the conventional phenomenological Advantages:
models are best with difficulties such as requirement of the
detailed knowledge of the underlying physicochemical phenomena (a) Less operating and capital costs
and extensive time required for their development, testing and (b) Low pressure drop
validation. Hence, there is also a need to develop generic mathe- (c) Capability to treat acid degradation products of VOCs
matical models of the biofiltration process using biological inspired
computing techniques for quantitative robust prediction and Disadvantages:
design optimization (Narendra et al., 2006; Omkar et al., 2008).
Finally, the largest problem to overcome will be the translation of (a) Accumulation of excess biomass in the filter bed
recent and future basic advances into real process improvements. (b) Complexity in construction and operation
(c) Secondary waste streams

Due to the permanent trickling mechanism, biofiltration


4. Biotrickling filter processes are more adapted for the elimination of water soluble
VOCs. Nevertheless, as the contact between microorganisms and
The schematic description of a typical biotrickling filter (BTF) is the pollutants occur simultaneously (Cox and Deshusses, 1999), the
provided in Fig. 2 (Delhomenie and Heitz, 2005). In such a filter, the solubility specifications are less stringent than for bioscrubbers
gas is carried through a packed bed, which is continuously irrigated (Henry coefficient <0.1; Van Groenestijn and Hesselink, 1993). In
with an aqueous solution containing essential nutrients required by a typical BTF, VOC inlet concentrations are generally less than
the biological system. Several studies have shown that the choice of 0.5 g m3. The continuous distribution of the nutrient solution
a co- or counter-current configuration for liquid and gaseous pha- facilitates the control of the biological operating parameters (viz.
ses does not influence the biodegradation performance (Cox and pH etc.).
Deshusses, 1999). Microorganisms grow on the packing material of As the contact between the microorganisms and the pollutants
the biofilter as biofilm. The pollutant to be treated is initially occurs after the VOC diffusion in the liquid film, the liquid flow rate
absorbed by the aqueous film that surrounds the biofilm, and then and the recycling rate are recognized to be critical parameters for
the biodegradation takes place within the biofilm. BTF operation. Research has suggested that an increase in the liquid
flow rate should result in proportional increase in the active
exchange surface for gas–liquid mass transfer, and then improve
the degradation rate (Alonso et al., 2000). Some researchers have
shown that maintaining minimum water and nutrient supply is
sufficient to achieve good performance (Lu et al., 2002; Thalasso
et al., 1996). In addition, as the distribution and the recycling of
nutrient solutions add to energy costs, other studies suggest that
the optimum recycling and distribution flow rates have to be found
experimentally and on a case-by-case basis (Dolfing et al., 1993).
The major drawback of BTFs is the accumulation of excess
biomass in the filter bed. Some researchers have demonstrated
that, in the course of the degradation process, the biofilm thickness
can be several millimeters (Janni et al., 2001; Cohen, 2001) which
can cause clogging, an increase in pressure drop, bed channeling,
creation of anaerobic zones and can ultimately lead to performance
loss (Alonso et al., 2001). Several studies have been attempted to
develop solutions to the clogging problem in BTF. The control
strategies suggested are of three types: mechanical, chemical or
biological. Mechanical treatment includes bed stirring (Wubker
et al., 1997; Laurenzis et al., 1998) or bed back washings with water
(counter-current washings), which permit the draining of excess
accumulated biomass (Smith et al., 1996). Chemical treatments
include dissociation of the chemical binding between the biomass
and the bed particle surface either by damage to the biomass by
Fig. 2. Schematics of a biotrickling filter unit. creating nutrient or water deficiency, or utilization of disinfecting
1044 S. Mudliar et al. / Journal of Environmental Management 91 (2010) 1039–1054

agents (Diks et al., 1994; Schonduve et al., 1996; Cox and glucose as a carbon and energy source and observed TCE elimina-
Deshusses, 1999; Armon et al., 2000; Chen and Stewart, 2000). tions up to 200 times higher than previously reported. As observed
Biological methods utilize biomass predators, such as protozoa in other bioreactors for TCE aerobic co-metabolism, rapid inacti-
(Cox and Deshusses, 1999). Amongst all of these methods, back vation of the TCE-degrading enzyme by TCE breakdown products
washings with water are the most efficient and certainly cause less (e.g. TCE epoxide) remained a problem.
disruption to the biotrickling filter ecosystem and performance Biotrickling filtration is a maturing technology, and the number
(Cai et al., 2004). of full-scale BTFs is rapidly increasing. In the past few 2–3 years,
several successful conversions of full-scale chemical scrubbers to
4.1. Operation and applications of biotrickling filters biotrickling filters have been demonstrated (Kraakman, 2001;
Kraakman, 2003; Gabriel and Deshusses, 2003). Until recently, it
The important parameters of bioreactors in general (nutrients, was thought that successful bio-treatment in BTFs required a gas
pH, microorganisms, oxygen levels, etc.) have been described in contact time ranging from 10 to 30 s (Wu et al., 2001). However,
detail for BFs in the preceding section. They will therefore not be some researchers have shown that in BTFs the residence time can
dealt with individually for all reactors. be reduced to 5 s (Shareefdeen and Singh, 2005). Recently, an
BTFs find wide application in VOC and odour treatment. As alkaline biotrickling filter was shown to be very effective for
compared to conventional compost or soil bed BFs which are treatment of H2S odours (Sanchez et al., 2008).
generally limited to the elimination of odorous compounds and non-
chlorinated volatile organic compounds, a wider range of pollutants 4.2. Future needs
can potentially be treated in BTFs. This is because, environmental
conditions can be better controlled in the BTFs and potentially toxic Recent research in the field of biotrickling filtration for air
dead-end metabolites can be purged out of the system. Also, labo- pollution control have focused on various aspects pertaining to the
ratory BTFs offer the opportunity to work with monocultures, microbiology of pollutant-degrading microorganisms, kinetics of
especially using genetically engineered microorganisms. pollutant uptake, and means to control biomass accumulation.
Oh and Bartha (1997) first reported the elimination of nitro- Nevertheless, additional information on the fundamental princi-
benzene vapors in a laboratory scale BTF. They used a stable ples underlying biotrickling filtration is needed. Key questions to be
microbial consortium enriched from sewage sludge and immobi- addressed are mainly concerned with the complex ecology of bio-
lized it on perlite. During the start up period of four weeks, the inlet films. In particular, studies are needed to understand the overall
nitrobenzene concentration was kept relatively low (<80 mg m3) role of secondary processes (i.e. those processes not directly asso-
to avoid poisoning of the culture, after which high and sustained ciated with the elimination of the primary pollutant) and how
nitrobenzene elimination was observed with 80–90% degradation these can be controlled in practice. In the future, the ability to
for inlet concentrations ranging from 100 to 300 mg m3 and an control the ecology of biofilms in BTFs may enable optimal
empty bed gas contact time of 21 seconds. This corresponds to an balancing of the net growth of biomass, so that reactor stability can
elimination capacity of 50 g m3 h1, a high value that could lead to be ensured over a very long period. Additional research is needed
an economically viable process. A nitrogen balance showed that for better understanding of the kinetic relationships for pollutant
98% of the nitrobenzene nitrogen was converted into ammonia biodegradation. Particularly, understanding of the biodegradation
while a small amount of nitrite was produced. of mixtures of pollutants, role and impact of oxygen and ancillary
Two other compounds of interest, namely diethyl ether (Bauerle nutrients on the rate of biodegradation and on the biomass yield,
and Fischer, 1987) and gasoline additive methyl tert-butyl ether and to determine the influences of various stresses, such as
(MTBE) (Fortin and Deshusses, 1999) were reported to be bio- changing conditions and mass transfer limitations, is important.
degraded in laboratory BTFs. Fortin and Deshusses (1999) achieved These studies are extremely relevant for future implementation of
75% removal efficiency for an inlet MTBE concentration of 0.8 g m3 BTFs in actual field conditions (Cox and Deshusses, 1999).
with empty bed residence time less than a minute in BTF. This In a nutshell, review of the recent research work emphasizes on
corresponds to an elimination capacity of 50 g m3h1, an the need of fundamental understanding of the degradation process
extremely high value for a compound for which biodegradation in through in situ analysis and extended application of modern tools
situ still remains a challenge. The reactor studied by Fortin and in biotechnology. This is essential in order to establish baseline
Deshusses (1999) was originally inoculated with various samples of information (presently not available) for rational reactor design and
aquifer material and soil contaminated with MTBE. Interestingly, optimum process operation. This, together with number of pilot
MTBE removal was significant only after addition of traces of a peat scale application and demonstration of techno-economic viability,
humic substance (PHS) extract to the recycle liquid. As biomass would transfer this technology from lab to the field.
accumulated in the reactors, the benefits of the PHS were no longer
significant. While several reports exist on bio-stimulation using 5. Bioscrubber
PHS in wastewater treatment, the exact mechanisms involved in
bio-stimulation using PHS are yet to be elucidated. A bioscrubber unit (Fig. 3, Delhomenie and Heitz, 2005) consists
Also noteworthy, is a study by Sun and Wood (1997), who of two subunits namely (1) an absorption unit and (2) a bioreactor
immobilized a pure culture of Burkholderia cepacia PR123 (TOM23C) unit. In the absorption unit, input gaseous contaminants are
constitutively expressing toluene ortho-monooxygenase to co- transferred to the liquid phase. Gas and liquid phases flow counter-
metabolize the biodegradation of trichloroethylene (TCE) vapors in currently within the column, which may contain the packing
a BTF. Aerobic biodegradation of TCE only occurs through co- material. Nevertheless, the addition of inert packing provides
metabolism, and addition of a growth substrate (usually toluene, increased transfer surface between the VOC and the aqueous phase
methane, propane, phenol, or ammonia), which is required to (Van Groenestijn and Hesselink, 1993). The washed gaseous phase
induce the expression of the appropriate TCE-degrading enzyme. is released at the top of the column whereas the separated
Bacterium B. cepacia PR123, however, expresses toluene ortho- contaminated liquid phase is pumped to an agitated, aerated
monooxygenase constitutively, which circumvents the problem of bioreactor. This reactor unit contains the appropriate microbial
competitive inhibition of TCE oxidation by the usual inducers strains suspended in the aqueous phase in nutrient solution
during the growth phase. The authors Sun and Wood (1997) used (media) essential for their growth and maintenance.
S. Mudliar et al. / Journal of Environmental Management 91 (2010) 1039–1054 1045

column and any biodegradation in the absorber lowers


the pollutant concentration in the liquid, which increases the
concentration gradient and gas transfer. Biodegradation in the
bioreactor unit continues to drive the pollutant concentration to
low levels. The carbon is regenerated as the VOCs desorb and
degrade, and is then recycled to the absorber. PAC also provides
a surface for the growth of biofilms, and may assist in treating peak
loads and in decreasing inhibition by toxic compounds. Addition of
2–5% PAC to biomass slurry is recommended to improve bio-
scrubber performance (Hammervold et al., 2000).

5.1.2. Anoxic bioscrubber


Aerobic bioreactors are used to transform inorganic pollutants
and degrade organic pollutants in conventional bioscrubbers,
whereas systems combining scrubbers and up flow anaerobic
sludge blanket (UASB) bioreactors have been used for the degra-
dation of perchloroethylene and also to treat waste gases contain-
ing NOX and SOX (Centinkaya et al., 2000; Janssen et al., 2000;
Shareefdeen and Singh, 2005).

Fig. 3. Schematics of a bioscrubber unit. 5.1.3. Two-liquid phase bioscrubber


The concept of two-liquid phase bioscrubber unit originates
from the fact that application of conventional bioscrubbers
Most of the bioscrubbers being operated presently use activated becomes limited for the treatment of pollutants that are readily
sludge derived from wastewater treatment plants as inoculum soluble in water. Consequently, the addition of an organic solvent to
(Ottengraf, 1987). In some cases, bioreactors are directly inoculated the water phase can enhance biodegradation of more hydrophobic
with specific degrading strains. The residence time for such compounds (Deziel et al., 1999), and facilitate the elimination of
bioreactors range between 20 and 40 days and these are operated a range of hydrophilic and hydrophobic compounds. Besides
practically as activated sludge processes including recycle of sludge. improving bioavailability, solvents can reduce the toxicity of
Part of the treated solution is recycled for absorption of VOCs to the contaminants, and can act as a buffer system for fluctuating loads of
absorption unit. pollutants. The addition of 10–30% water immiscible high boiling-
The advantages of bioscrubbers are as follows. point solvent to the liquid phase facilitates the absorption of
hydrophobic compounds from the gas phase in the absorber. Two-
(a) Operational stability and better control of operating parame- liquid phase bioreactor systems have been tested for the removal of
ters (pH, nutrients); alkanes, benzene, styrene, phenol, naphthalene, and pentachloro-
(b) Relatively lower pressure drops phenol. Solvents such as silicon oil, paraffin oil, dibutyl phthalate,
(c) Relatively smaller space requirement. di-n-octyl phthalate, di-n-nonylphthalate, and pristine are good
candidates for this application, and among them silicon oil has been
Disadvantages of bioscrubbers include- found to be the best for two-liquid phase systems (Yeom and
Daugulis, 2001).
(a) Bioscrubbers are adapted to treat readily soluble VOCs (alco-
hols, ketones), with low Henry coefficients (<0.01), and at 5.1.4. Airlift bioscrubber
concentrations less than 5 g m3 in the gaseous phase Edwards and Nirmalakhandan (1999), have described an airlift
(b) Provides low specific surface area for gas–liquid mass transfer bioscrubber having a combined absorption/biodegradation reactor
(generally <300 m1) configuration, for the removal of air phase benzene, toluene and
(c) Excess sludge generation xylene (BTEX) compounds. The reactor comprises of two concentric
(d) Generation of liquid waste tubes, with the inner tube shorter than the outer tube. As in some
conventional airlift bioreactors, the inner tube serves as the down
Some studies have shown that the addition of emulsifying comer, and the annular space between the two tubes works as
agents (silicon oil, phthalate) in the aqueous solution can signifi- a riser (Ward, 1989). Air is introduced into the reactor through the
cantly improve the elimination of less soluble compounds, because sparger, which is located near the bottom of the riser. The combined
they favor the VOC mass transfer from gas to the liquid phase medium of mixture of air and water in the riser has lower density
(Mortgat, 2001). than the water in the down comer, resulting in a fluid circulation
within the reactor. A mathematical model developed for this
5.1. Variations in bioscrubber design process indicated that removal rates of >99% can be achieved for
benzene and toluene in the air stream with concentrations
Substantial modifications in bioscrubber design have been done <1000 ppmv, and that the airlift bioscrubber should be operated at
in the recent past to enhance their performance for VOC and odour biomass concentrations of 2 g 11 or greater for operational
treatment. Some modified bioscrubber units are listed below. stability. Recently, Jianping et al. (2005) reported the simultaneous
removal of ethyl acetate and ethanol in air streams using a gas–
5.1.1. Sorptive-slurry bioscrubber liquid-solid three-phase flow airlift bioreactor.
The sorptive-slurry bioscrubber consists of a suspended growth
bioscrubber with powdered activated carbon (PAC) added to the 5.1.5. Spray column bioscrubber
biomass slurry (Kok, 1992). Gaseous VOCs partition into the slurry Bioscrubbers have been suitably modified as per the demand
in the absorber unit and adsorb onto the carbon. Adsorption on the and nature of the odorants to be treated. A modified bioscrubber for
1046 S. Mudliar et al. / Journal of Environmental Management 91 (2010) 1039–1054

treatment of large volumes of waste gas and industrial emissions Application of membrane bioreactors for waste gas treatment has
with low concentration of odorants with poor solubility was been reviewed before (Reij et al., 1998; Kumar et al., 2008a,b). The
investigated by Cesario et al. (1992). The modified system consists concentration difference between the gas phase and the biofilm
of two bioreactor units, which include (a) a spray column bioreactor phase provides the driving force for diffusion across the membrane.
with liquid impelled loop reactor (LILR) and (b) a spray column A pressure difference is not applied. The driving force depends
bioreactor connected to an airlift loop reactor (AIR). In both the strongly on the air–water partition coefficient of the diffusing
systems, gaseous odorants/liquid contactor is a spray column for volatile component. For components with a high partition coeffi-
transfer of the odorants from gas to the water phase. This is inter- cient the driving force for mass transfer is small. The concentration
connected to either liquid impelled loop reactor or airlift loop in the liquid, which depends on the biodegrading activity of the
reactor. Both the attached systems (LILR and ALR) contain culture microbial population, also affects the driving force. The surface of
medium and the biomass. The spray column and LILR/ALR are the membrane forms the contact area (Reij et al., 1998).
interconnected having a provision for recycling of the contents of In a BF bioreactor unit, waste gas is blown through a bed of
the reactor (Cesario et al., 1992). compost or soil, where microorganisms consume or degrade the
The spray column reactor with LILR contains nutrient medium. gaseous organic pollutants. No separate water phase is present. An
It is necessary that the nutrient medium in the reactor must possess advantage of the membrane bioreactor over the BF is the presence
characteristics such as immiscibility with water, non-biodegrad- of a discrete water phase allowing optimal humidification of the
ability, should be non-toxic to the biocatalyst, should have low biomass and removal of the degradation products, thus avoiding
vapor pressure, relatively low viscosity, and a density different from inactivation of the biomass. In a membrane bioreactor, the
the density of water. The water immiscible liquid is recycled membrane serves as the interface between the gas phase and the
between the absorber and the bioreactor. However, the operation liquid phase (Fig. 4, Reij et al., 1998). The gas–liquid interface thus
(recycling) depends upon (a) the volume of industrial emission to created (e.g. in hollow fibre reactors) is larger than in other types of
be treated, (b) physicochemical characteristics and (c) the gas–liquid contactors (Yang and Cussler, 1986). Moreover, in bio-
concentration of the odorants in the gaseous emission and also (d) trickling filter and the bioscrubber, a packed bed of inert material is
the targeted removal efficiency. present on which water is continuously sprayed. The pollutants in
The novel reactor of a spray column system with LILR/ALR is still these reactors have to diffuse through the water phase before it is
on laboratory scale and requires extensive investigations to ascer- consumed by the microorganisms. For pollutants with poor water-
tain the odorant transfer from gas to the liquid absorber (ALR). solubility such a layer of water causes a substantial additional
resistance for mass transfer (De Heijder et al., 1994). In the
5.2. Future needs membrane bioreactor, on the contrary, the liquid phase is situated
at the opposite side of the biofilm and hardly forms a barrier for
Bioscrubber are generally considered to be useful for the treat- mass transfer of the poorly water soluble pollutants (Fig. 4). As
ment of waste gases containing water soluble pollutants (Henry’s mentioned before, large gas–liquid interfaces of 1000–
law coefficient, H < 0.01), but depending on the concentration and 10,000 m2m3 can be created in hollow fibre reactors (Rautenbach
type of pollutant, bioscrubbers may also efficiently be used for and Albrecht, 1989), allowing high mass transfer rates. The pressure
odorous gases with other characteristics. Bioscrubbers, provide drop in the gas phase is much lower than observed in BFs, where
substantial advantages for waste gas treatment because of their pressure drop may become significant.
smaller space requirements, high loading rates, reliable operation, Advantages of membrane bioreactors include.
process control, low risk of clogging, and low operating cost. When
high concentrations of contaminants are to be treated, bioscrubbers (a) No moving parts
offer more advantages than conventional BFs, BTFs, and chemical (b) Process easy to scale up
scrubbers. Combination of bioscrubbers and some polishing steps (c) Flow of gas and liquid can be varied independently, without the
may improve the treatment efficiency for gases with mixture of problems of flooding, loading, or foaming
hydrophobic and hydrophilic compounds.
Bioscrubbers offer higher elimination efficiencies for gases Disadvantages of the bioreactor are-
generated from liquid wastes, viz. H2S, NH3, and organic sulfur
compounds. However, due to the acidifying nature of these (a) High construction costs
substances, substantial oxidation and sulfuric acid production in (b) Long-term operational stability (needs investigation)
the scrubber may cause the pH to drop and decrease mass transfer
efficiency. The capacity of the adsorption section for handling
higher H2S concentration needs to be further improved. This could
be achieved by increasing the buffering capacity of the scrubbing
medium and also through pH control.
The bioscrubber application can be made more attractive than
the use of other conventional BF or BTF at relatively high pollutant
concentration (>0.5 g m3) with necessary modifications. There is
also a need to develop integrated/hybrid reactor configurations to
achieve optimal and efficient bio-treatment of VOCs/odours, indi-
vidually and in mixtures.

6. Membrane bioreactors

Membrane bioreactors were designed as an alternative to


conventional bioreactors for waste gas treatment. The membrane
bioreactor allows the selective permeation of the pollutant, which Fig. 4. Schematics of a membrane bioreactor containing microporous hydrophobic
is not allowed in any of the reactors discussed previously. membrane, a biofilm and suspended cells.
S. Mudliar et al. / Journal of Environmental Management 91 (2010) 1039–1054 1047

(c) Possible clogging of the liquid channels due the formation of Dense material is available as tubes (usually silicone tubing),
excess biomass with a wall-thickness of at least several hundred micrometers, and
as composite membranes. Composite membranes consist of a thin,
selective top layer (<1–30 mm) of dense material, supported by
6.1. Membrane materials a highly porous support layer of, for, e.g. non-woven polyester or
a microfiltration membrane. Composite membranes can be applied
Two types of membrane materials have been used to prevent in spiral-wound, plate-and-frame and in hollow fibre modules.
mixing of the gas and liquid phases and simultaneous transfer of Examples of the application of both micro porous and dense
volatile components. These types are hydrophobic micro porous membranes as gas–liquid contactors are given in the following
membrane and dense membrane. section (Reij et al., 1998).

6.1.1. Micro porous membranes 6.3. Applications of membrane bioreactors in waste gas treatment
A micro porous membrane has a highly porous structure, with
a typical commercial membrane containing 30–85% pore space In addition to the relatively new process of membrane-based
(Hartmans et al., 1992), including open pores in the surface of the gas absorption (Sirkar, 1992), membrane contactors have recently
membrane. The surface pores are generally sub micrometer in size, been tested for biological treatment of gas streams. In such
which prevents organisms from passing through the pores. If the a process, the pollutants diffuse through the membrane and are
pore size distribution is not sufficiently controlled or pore size is too degraded by the microbial population present in the liquid phase.
large, then intrusion by organisms and organics will occur, signifi- In this context, various publications were critically reviewed and
cantly reducing mass transfer and potentially plugging the gas the summarized results are presented in Table 1. In general, the
phase (Hartmans et al., 1992; Attaway et al., 2002; Fitch et al., 2003). biomass is supplied with carbon and oxygen from the gas phase,
Hydrophobic micro porous membranes consist of a polymer matrix while water and mineral nutrients are supplied through the liquid
of polypropylene or Teflon and contain pores with a diameter in the phase. Microorganisms grow as a biofilm on the membrane, but
range of 0.01–1.0 mm. Since the membrane material is hydrophobic, may also be suspended in the liquid phase.
the pores are filled with gas. Water does not enter the pores, unless Most studies on membrane bioreactors concern the removal of
a certain critical pressure at the liquid side is exceeded. hydrophobic pollutants from air. Hydrophobic pollutants, like
If the transferred component disappears by chemical reaction, xylene, toluene, hexane, and propene, have a high air–water
its mass transfer rate increases (Prasad and Sirkar, 1992). Active partition coefficient. The driving force for the transfer of these
microorganisms present in the liquid will thus enhance it signifi- pollutants to the water phase is very small and as a consequence,
cantly. If the microorganisms are present as a biofilm on the mass transfer limits the biodegradation and therefore the design of
membrane, liquid flow close to the membrane is absent and as the bioreactor becomes critical (Dingemansa et al., 2008a,b; Witte
a consequence the mass transfer coefficient does not apply at all. In et al., 2009). The large gas–liquid interface and excellent mass
this case (biofilm), simultaneous diffusion and reaction in a stag- transfer properties of membrane reactors (Yang and Cussler, 1986;
nant layer need to be calculated (Reij et al., 1995). Karoor and Sirkar, 1993) have inspired several workers to test
membrane bioreactors for the removal of less water soluble
6.1.2. Dense membranes pollutants from air (Reij et al., 1995; Bauerle et al., 1986, 1987). A
A dense-phase membrane has no pores for removal to occur. The dual tube dense-phase silicone membrane bioreactor was investi-
contaminant must dissolve in to the membrane and diffuse through gated for control of cyclohexane-contaminated air as part of a jet
the membrane. In case of transport through a dense membrane, the propulsion fuel remediation investigation strategy (Roberts, 2006).
diffusing volatile component is absorbed in the membrane material Mass transfer characteristics for VOC permeation through flat sheet
and diffusion takes place in the dense polymer (Reij et al., 1998). porous and composite membranes showed that the contribution of
The mass transfer coefficient inside a dense membrane depends the porous ‘‘backing’’ layer for mechanical support can be
on both the solubility and the diffusivity of the volatile component substantial in comparison to the porous layer in contact with the
in the dense matrix (Crank and Park, 1968). Interaction between the dense layer (Dingemans et al., 2008). Removal in the bioreactor
various gaseous components is assumed to be absent, i.e. inde- ranged from 29.4 to 596.6 mg m2 m1 in and measured elimina-
pendent diffusion. For each volatile component, the solubility and tion capacities ranged from 46.7 to 947.9 g m3 h1.
diffusivity are different and the mass transfer resistances of dense The membrane materials used in several studies were chosen
membranes for various gases may differ considerably due to such that they were impermeable to microorganisms (Hartmans
specific interactions between the components in the gas phase and et al., 1992; Freitas dos Santos et al., 1995). As a consequence, these
the membrane material. As a consequence, components can be organisms could not contaminate the gas phase. This precaution
selectively extracted from or retained in the gas phase by a proper was considered to be important in case the membrane bioreactor
choice of the membrane material (Reij et al., 1998). was applied for the treatment of indoor air or manned space cabin
(Binot et al., 1994).
6.2. Gas–liquid contactors for membrane bioreactors Freitas dos Santos et al. (1995) tested a reactor with silicone
tubes to remove 1,2-dichloroethane from air. For the destruction of
Both micro porous and dense membranes have been used for trichloroethene (TCE), Parvatiyar et al. (1996a,b) designed a new
a variety of processes that involve gas–liquid contact. Micro porous membrane bioreactor in which both an aerobic and an anaerobic
material is generally applied in hollow fibres, although spiral- region were present (Fig. 5). In the anaerobic zone, TCE is partially
wound and plate-and-frame modules have also been used (Sirkar, dechlorinated and the products are supposedly degraded further in
1992; Wickramasinghe et al., 1992). Micro porous membranes can the aerobic zone of the biofilm.
be applied as gas–liquid contactors when selective action of the The silicone membranes due to their selectivity for hydrophobic
membrane is not required. Volatile components diffuse through components, retains acid vapors (SO2) that hamper biodegradation
this material depending on their diffusion coefficient in air and of 1,2-dichloroethane (Freitas dos Santos et al., 1995).
their vapor pressure, while the membrane serves as gas–liquid Dense membranes may also serve as a buffer, in case the supply
contact area. of pollutants is variable. It should be noted, however, that due to
1048 S. Mudliar et al. / Journal of Environmental Management 91 (2010) 1039–1054

Table 1
Application of membrane bioreactor for VOC and odour treatment.

Contaminant Membrane Load EC Operation Gas HRT Flux References


(g m3) (g m3 h1) (g m3 h1) (days) (s) (mg m2 h1)
Xylol (0.1–0.6) HF silicone rubber 1.8-8.1 1.8–7.9 n.r.a 2.5-14 67–302 Bauerle et al. (1986)
Butanol (0.1–0.5) 1.8–7.3 1.3–5.4 48–207 Weckhuysen et al. (1993)
DCM (0.2–0.4) 2.4-11 1–4 37–151
Toluene (0.38) HF polyporous pp 2-31 33–1500 w90 0.9–6.3 13–180 Ergas and McGrath
(1997)
Toluene (0.7–3.4) HF polyporous PP 23-121 16-42 > 20 0.9-1.8 15–35 Ergas et al. (1999)
Nitrogen oxide (0.1) HF polyporous PP 1.3 0.1–0.9 105 1.9 3–8 Min et al. (2002)
DCM (0.65) Spiral-wound silicone rubber 14–35 12–28 11 n.r.a 25–55 Freitas dos Santos et al.
(1995)
Methane, TCE in Silicone rubber tubing n.a.b 12 w120 n.a.b 130 Clapp et al. (1999)
liquid (264)
Dimethyl sulfide Flat composite silicone 5–270 5–200 79 8–24 De Bo et al. (2002)
(0.036–1.81) rubber on polysulfone (De Bo, 2003)
a a
Toluene (0.75–1.5) HF polyporous polysulfone, n.r. n.r. >140 16 or 32 80 Parvatiyar et al.
two in series (1996a,b)
a a
Methanol (0.01–2.6) Composite with silicone 36 25 n.r. n.r. 420 Resier et al. (1994)
Toluene (0.03–4.2) rubber 58 40 – – 670
Hexane (0.03–2.4) 33 24 – – 400
Xylol (0.1–0.6) Composite with silicone 600 360 52 4.3–15 170 Attaway et al. (2001)
BBTEX (7.7–15.4) rubber
BTEX (2.2–9.8) HF polyporous PP 118 105 20 8–16 312 Attaway et al. (2002)
DCM (0.16) Flat polyporous PP 180 80 <1 1.6–9.6 320 Hartmans et al. (1992)
Toluene (0.075) Flat composite, 84 29 117 De Bo et al. (2002)
Toluene (0.004–3.18) Silicone rubber on PVDF 32–470 30–395 339 2–24 790
Toluene (0–0.97) Flat composite, silicone 0–170 0–170 20 24 n.r.a De Bo et al. (2002)
rubber on PVDF
TCE (0.04) Flat composite, silicone rubber 6 0–6 n.r.a De Bo et al. (2002)
Dimethy1 sulfide On PVDF 5–170 5–130 20–144 4–24
(0.011–1.63)
Toluene (0.5–0.75) HF polyporous PP 16–96 32–72 >8 1.8–7.2 6–60 Dolasa and Ergas (2000)
TCE (0.04–0.2) 3–9 0–6 3.6–7.2 0–5 Dolasa and Ergas (2000)
Butanol (0.6–2.3) HF polyporous polysulfone 13–26 3.8–13 105 1.6 and 2.9 13–326 Fitch and England (2002)
TCE (0.13–0.21) HF polyporous PP 0.03–0.1 0.01–0.06 21 96–300 0.06–0.2 Pressmann et al. (2000)
Benzene (0.1) HF polyporous PP 7–60 4.8–58 100 0.17–1.4 4.2–20.4 Fitch et al. (2003)
Benzene (0.1) Latex rubber tubing 7-28 2.5–18 40 0.55–1.4 670–2700 Fitch and England (2002)
Cyclohexane Dual tube silicone rubber 395–2189 47–947 40 – 29–597 Robert et al. (2006)
DMS Thermophilic membrane 64 54 270 24 128 Munkhtsetseg et al.
(2008)
Toluene Composite porous PAN 0.72 0.6 165 2–24 – Kumar et al. (2008a,b)
Cyclohexane Dual tube silicone rubber 46.7 947 46.7 40 1764–35,760 Robert et al. (2006)

Configurations: HF: hollow fibre (i.d. < 0.5 mm); C: capillary (0.5 mm < i.d. < 10 mm); PP: polypropylene; PDMS: polydimethylsiloxane; PVDF: polyvinylidenefluoride;
Zrf: zirfon.
Compounds: MeOH: methanol; BuOH: 1-butanol; NH3: ammonia; BENZ: benzene; TCE: trichloroethylene; TOL: toluene; PROP: propylene; NO: nitric oxide; HEX: hexane;
DMS: dimethylsulfide; BTEX: mixture of benzene, toluene, ethylbenzene and xylenes; DMS: dimethylsulfide; DCM: dichloromethane; DCE: dichloroethane.
a
n.r., Not reported or not sufficient data to calculate.
b
n.a., Not applicable (e.g., static gas phase).

simple thermodynamics, the equilibrium concentration in the reactor performance decreased over a period of 3–6 months as the
water phase would never change upon the insertion of any type of biofilm matured. These results suggest that, even if clogging is
membrane between the gas phase and the water phase. prevented, biofilms are prone to aging (Reij and Hartmans, 1996).
Irrespective of the membrane resistance, the driving force for During the degradation of dichloromethane (Bauerle et al., 1986)
mass transfer depends on the concentration to which the pollutant a good biofilm did not develop on the reactor membrane. The bio-
is reduced in the liquid phase. Therefore, the removal rate in film growing on dichloromethane sheared off the membrane after
a membrane bioreactor depends largely on the activity of the 94 days, causing a drop in reactor performance (Reij et al., 1995).
microbial population. In most of the reported studies, biofilm Recently investigation on DMS removal in thermophilic membrane
formation was observed to be an essential part of reactor operation bioreactor indicated an elimination capacity of 54 g m3 h1 with
(Ergas et al., 1999). Both mixed cultures and pure cultures were the removal efficiency 84% at gas retention time (GRT) 24 s
used for biofilm generation. The hydrophobic nature of both micro (Munkhtsetseg et al., 2008). The reason suggested for this was that
porous and silicone membranes facilitates microbial adhesion. The hydrochloric acid was produced during the degradation of
microorganisms located close to the membrane are exposed to dichloromethane, which accumulated in the biofilm to toxic levels
higher substrate concentrations than suspended cells, making it and destabilized the biofilm.
more likely that most cell growth occurs close to the membrane. Aziz et al. (1995) purposely repressed biofilm formation in
Biofilm growth may cause serious problems if excess biomass is a membrane reactor for wastewater treatment by the addition of
not sloughed off. Freitas dos Santos et al. (1995) attributed the a sequestering agent. This membrane reactor was part of a two-
decreasing reactor performance and the increasing pressure drop stage bioreactor, in which methanotrophs were circulated. In the
over the liquid phase to extensive biofilm formation in the spiral- membrane reactor, the methanotrophs degraded trichloroethylene
wound membrane module they studied. Clogging of hollow fibres (TCE) and in a separate reactor, growth substrate was supplied.
with a biofilm of propene-degrading Xanthobacter cells could be Separate reactors were required for the study, since TCE itself did
prevented by applying a very high liquid velocity, but still the not support microbial growth and could be degraded only co-
S. Mudliar et al. / Journal of Environmental Management 91 (2010) 1039–1054 1049

In addition to the durability of the membrane material, the


stability of the biomass is essential as well. The formation of thick
biofilms (Freitas dos Santos et al., 1995) and clogging of the liquid
channels (Kreulen et al., 1993) were shown to deteriorate reactor
performance. Even when clogging was prevented by a very fast
liquid flow, the performance of hollow fibre modules decreased
with time (Kreulen et al., 1993). Therefore, strategies have to be
developed to monitor the biofilm, to stabilize its activity, and to
remove excess biomass from the membrane modules.
The removal of poorly water soluble pollutants from air can be
considered to be the most promising application for membrane
bioreactors. The mass transfer resistance of membranes for this
group of pollutants is negligible. Recently, Kumar et al. (2009), have
reported enhance performance of a composite membrane biore-
Fig. 5. Aerobic and anaerobic biodegradation of trichloroethene (TCE) in membrane actor for treating toluene vapors. The composite membrane con-
bioreactor.
sisting of a porous poly acrylonitrile (PAN) support layer coated
with a very thin (0.3 microm) dense polydimethylsiloxane (PDMS)
metabolically when a primary substrate was supplied. Such a two- top layer indicated maximum elimination capacity of
stage process may not only be used for wastewater treatment but 609 g m3 h1 along with the flux 1.2 g m3 h1. Moreover, the
also for the removal of TCE from waste gas. large gas–liquid interface of membrane modules enables efficient
A completely new strategy for the removal of TCE from air was removal of these pollutants that in general are difficult to remove
designed by Parvatiyar et al. (1996a,b). In their newly designed from air.
membrane bioreactor, acetate was added to the liquid phase as Other niches for the application of membrane bioreactors are
carbon source and as electron donor to lower the oxygen tension in indoor applications and the removal of pollutants that require
the biofilm. Under anaerobic conditions created in this way, TCE a specific microbial population (like TCE and nitrogen monoxide).
was partially dechlorinated. Subsequently, the products of the Recently, the membrane bioreactor with both an anaerobic and an
anaerobic dechlorination were degraded further in the aerobic aerobic zone was proposed (De Heijder et al., 1994). Such a biore-
zone of the biofilm (Fig. 5, Cesario et al., 1992). Their work, however, actor might enable the biodegradation of pollutants, such as highly
did not contain experimental evidence that both the aerobic and chlorinated hydrocarbons, that until now were considered to be
the anaerobic zone are present, but it is the first report on the beyond the reach of aerobic biological waste gas treatment.
continuous removal of TCE from air in the absence of volatile
growth substrates. 7. Comparison of conventional bioreactors and membrane
While reviewing literature (Table 1), it was found that the bioreactor for VOC and odour control
experiments reported are very varied and the approach in each case
is different. For example-in most studies oxygen was made to diffuse The application areas and comparative performance evaluation
through the membrane along with the compound to be removed of bioreactors (biofilter, biotrickling filter, bioscrubber, membrane
from air, but Freitas dos Santos et al. (1995) supplied oxygen in the bioreactor) widely reported for VOC and odour control is presented
water phase. Parvatiyar et al. (1996a,b), on the other hand, main- in Tables 2a and 2b, respectively. The target pollutant concentration
tained the liquid phase anaerobic, to allow anaerobic degradation. for bioscrubber is relatively higher than biofilter and biotrickling
Secondly, the time period in each experiment varied, while some filter, while in case of membrane bioreactor the membrane flux
lasted for more than a year, some were completed within a few days. limit should allow for higher VOC and odour concentration. Bio-
filters usually have a media layer of 1–2 m to prevent excessive air
6.4. Future needs velocities through the media, which easily results in high-pressure
drop or airflow preferences. Biotrickling filters and bioscrubbers do
All studies carried out on membrane reactors are laboratory scale not require an upfront humidifier, like biofilter do, to increase the
experiments. To the best of our knowledge, no reports are available inlet air humidity up to a preferable 100%. The footprint of bio-
on pilot-plant investigations or full-scale applications of membrane trickling and bioscrubber reactors is normally much smaller, since
reactors in biological waste gas treatment. Membrane modules they usually contain a more open packing that can be more than
appear relatively easy to scale up given their modular nature (Karoor 2 m high. The media in biofilters needs to be replaced frequently,
and Sirkar, 1993); however an extensive long-term performance due to the deterioration of the (usually organic) media, or the
testing is necessary before they can be applied on full-scale. increasingly worse process conditions like pH decrease, nutrient
The effect of biomass on the membrane material, in the long run depletion, or extensive biomass accumulation, salt content or
has not sufficiently been tested. During prolonged operation pressure drop. In biotrickling and bioscrubber reactors, no medium
microbial polysaccharides might get absorbed to the membrane change-out is required, since inert packing material is used and
material, decreasing the critical pressure, and allowing liquid to process conditions can be better controlled. Operational costs can
penetrate the pores of hydrophobic micro porous membrane. This be saved with biotrickling or bioscrubber reactors, since up to 40%
wetting of the membrane may significantly increase membrane of the operational cost of a biofilter is typically related to the
resistance (De Heijder et al., 1994) and will be a bottleneck for long- medium change-out. Further, the biofilter reactor do not have
term operation of reactors with micro porous membranes. No a continuous and distinct liquid phase as found in the case of bio-
experimental evidence on this subject has been reported so far. trickling and bioscrubber. Therefore, important process conditions
Wetting of the membrane could be prevented by a thin coating of like pH, salt content, nutrients, toxic intermediates or end products
dense material applied on the liquid side of a porous membrane. of microbial degradation are much easier to analyze and to control
Such composite membranes have been used in blood oxygenation in biotrickling and bioscrubber. Also, the liquid phase itself (the
to suppress blood-trauma and prevent the pores from filling with water content) can be better controlled to obtain the optimal water
liquid and cell debris (Sirkar, 1992). content through the bioreactor system, and to minimize drying out
1050 S. Mudliar et al. / Journal of Environmental Management 91 (2010) 1039–1054

Table 2a
Comparative performance evaluation of bioreactors for VOC and odour control.

Bioreactor Target VOCs Treatment efficiency for Pressure Capital Operational Bioprocess
Type and Odours drop cost cost controla
Low conc. High conc. High water Low water Fluctuating
conc. g/m3
of VOCs of VOCs soluble insoluble feed conditions
/Odours /Odours VOCs VOCs
Biofilter <1 High Low High Low Low Low Low Low Low
Biotrickling <0.5 High Low High Low Low Low Low Low Low
filter
Bioscrubber <5 High High High Low High Very low Medium Medium High
Membrane High High High High High Need long- Need long- High High Need long-
reactor term evaluation term evaluation term evaluation
a
Comparative evaluation on bioprocess control parameter is given in Table 2b.

Table 2b
Critical bioprocess control parameters for different bioreactor configurations.

Type Moisture Nutrient/pH Clogging Transient response Airflow channeling Startup


Biofilter Highly sensitive Highly sensitive Sensitive Sensitive Highly sensitive Sensitive
Biotrickling filter Not sensitive Not sensitive Highly sensitive Highly sensitive Sensitive Highly sensitive
Rotating contactors Not sensitive Not sensitive Not sensitive Highly sensitive Not sensitive Highly sensitive
Bioscrubber Not sensitive Not sensitive Not sensitive Highly sensitive Not sensitive Sensitive
Suspended growth Not sensitive Not sensitive Sensitive Sensitive Not sensitive Sensitive
Membrane reactor Not sensitive Not sensitive Highly sensitive Sensitive Not sensitive Highly sensitive

of the packing material or the biofilm on the packing material. a membrane bioreactor with both an anaerobic and an aerobic
Heslinga (1994) mentioned that probably 50–75% of the problems zone was proposed. Such a bioreactor might enable the biodeg-
with conventional biofilters are related to a poor control of the radation of pollutants, such as highly chlorinated hydrocarbons,
water content in the biofilter media. that until now are considered to be beyond the reach of (aerobic)
An important disadvantage of biotrickling and bioscrubber biological waste gas treatment.
reactors is the higher complexity to construct and to operate. The Disadvantages of membrane bioreactors are the high invest-
startup of biotrickling and bioscrubber reactors is also more ment cost, particularly compared to other bioreactor, and possible
complicated, since the inert medium does not contain microor- clogging of the liquid channels due the formation of excess
ganisms at the start. As soon as the microorganisms are present, biomass. Compared to other types of bioreactors, the membrane
they can be washed out by the required drainage of the process may form an additional barrier for mass transfer. So far, membrane-
water; a problem that is encountered with full-scale operations of based biological waste gas treatment has only been tested on
bioscrubbers. Pressure drop control is more complex especially laboratory scale. If the long-term stability of these reactors can be
with biotrickling reactors. Compared to a biofilter, higher air demonstrated, membrane bioreactor technology can be useful in
velocities through the media results more easily in a higher pres- the treatment of gas streams containing poorly water soluble
sure drop. When biotrickling or bioscrubber reactors are applied for pollutants and highly chlorinated hydrocarbons, which are difficult
the treatment of pollutants like hydrogen sulfide, ammonia or to treat with conventional methods for biological waste gas
chlorinated compounds, the degradation produces acid end prod- treatment.
ucts in the drain water, which needs further processing. Biotrickling
and bioscrubber reactors make a better process control possible, 8. Other bioreactor configurations
which require, on the other hand, measurement or control
instrumentation. Apart from bioreactors described in the preceding sections for
The location of the water film with respect to the biomass VOC and odour treatment, several other bioreactors have also been
differs in biotrickling filter, bioscrubber and membrane bioreactor. reported. An innovative design was reported by Yang et al. (2002),
In the trickling bed reactor and in the bioscrubber pollutants have which consists of a rotating drum BF. Open pore reticulated poly-
to diffuse through the water phase, before they can be consumed urethane foam was used as the BF packing medium and this new
by the microorganisms. For pollutants with a poor water-solu- design resulted in better distribution of VOCs, oxygen, nutrients,
bility, such a layer of water causes a substantial additional resis- and biomass, over conventional BFs. Two types of rotating drum BFs
tance for mass transfer. In the membrane bioreactor, on the were investigated to study the effect of medium configuration on
contrary, the liquid phase is situated at he opposite side of the BF performance for VOC treatment. One was a single-layer BF that
biofilm and hardly forms a barrier for mass transfer of the poorly consisted of a thick layer of open pore reticulated polyurethane
water soluble pollutants. Therefore, the removal of poorly water foam media. The other was a multi-layer BF that used a set of four
soluble pollutants from air can be considered as the most prom- concentric thinner layers of the media. The effect of the two
ising application for membrane bioreactors. The mass transfer different media configurations was examined using diethyl ether at
resistance of membranes for this poorly water soluble pollutants is various organic loading rates. The results showed that the multi-
negligible. Moreover, the large gas–liquid interface of membrane layer BF could maintain more stable and higher ether removal
modules enables efficient removal of these pollutants, which in efficiencies at gas empty bed contact time (EBCT) of 30 s, when
general are difficult to remove from air. Other niches for the compared to the single-layer BF at gas EBCT of 90 s, and at organic
application of membrane bioreactors are indoor application and loading rates ranging from 32.1 to 128.4 g (ether) m3 l1. The multi-
the removal of pollutants that require a specific microbial pop- layer BF also exhibited a more even biomass distribution on the
ulation, like TCE and nitrogen monoxide. Very recently, concentric surface at medium depth than the single-layer BF, which
S. Mudliar et al. / Journal of Environmental Management 91 (2010) 1039–1054 1051

suggested a reduced possibility of short-circuiting of gas streams require improvement, and confirmation of significantly better
and, consequently, better performance (Yang et al., 2002). performance compared to existing designs. For example, consid-
A novel rotating rope bioreactor was described by Mudliar et al. ering the volatile nature of VOCs and odourous compounds, sus-
(2008a,b), especially for the treatment of VOCs characterized by pended growth reactor systems/bioscrubbers may find limited
high volatility along with high water-solubility. The bioreactor application in the field at higher substrate concentration and
could be used for treatment of vapor phase VOCs by suitably loadings, and oxygen transfer can become a limitation, since air
scrubbing the compound in water and subjecting it to the new purging cannot be used in such systems. In future, improved
bioreactor referred to as the rotating rope bioreactor (RRB) for ‘‘rational bioreactor design’’ techniques need to be gradually
treatment. The novel bioreactor provided higher interfacial area developed. The knowledge needed to do this can be developed by
(per unit reactor liquid volume) along with high oxygen mass further research on topics such as the mechanisms of clogging, the
transfer rate, greater microbial culture stability and consequently kinetics of biofilm growth, and fundamental microbial ecology.
higher substrate loadings and removal rates in comparison to other Flow characterization through the bioreactor is important, since gas
conventional reactors (e.g. BFs) widely used for the treatment of flow, liquid flow and gas velocity have an important impact on
VOCs. Pyridine was used as a model compound to demonstrate the process parameters like mean gas resident time, gas dispersion in
enhanced performance of RRB. The experimental results showed the reactor, and pressure drop over the system. These parameters
that the novel RRB system was able to degrade synthetic waste- are important to scale up and to operate a bioreactor at optimum
water containing pyridine with removal efficiency of more than conditions. The bioreactor development should be also focused on
85% up to a loading of 66.86 g m3 h1. Further, the authors also issues like robustness (flexible to process fluctuations/failures),
described a single stage reactor called the rotating rope biofilter for large pollutant loadings, high temperatures, halogenated
direct treatment of VOCs instead of a two-stage process described compounds and poorly water soluble compounds. It is a big and
above. This reactor is a modified closed RRB where the waste air challenging task to design a bioreactor from fundamental theory,
containing the VOC is directly sparged through the water hold-up but definitely the understanding of biological treatment is growing
of the reactor and the water soluble VOCs are absorbed in the with time.
aqueous phase. It is then degraded by the microbial consortium Further, developments of innovative combined bioreactor
immobilized on the RRB rope media. designs remain a high priority, since a single bioreactor configu-
Kan and Deshusses (2003) reported a new type of bioreactor for ration will never provide a universal solution to existing VOC and
air pollution control referred to as a foamed emulsion bioreactor odour problems. In many instances, progresses in reactor design
(FEBR). The new reactor was based on an organic-phase emulsion and development will require similar advances in understanding
and actively growing pollutant-degrading microorganisms, made the fundamentals of the bioprocess, so that a more logical, creative
into foam with the air being treated. As there is no packing in the and focused approach in bioreactor design can be implemented.
reactor, the FEBR is not subjected to clogging. Mathematical Hence, to improve the performance of the biological air treatment
modeling of the process and proof of concept using a laboratory system for VOCs and odours, there is a need for continuous inno-
prototype revealed that the foamed emulsion bioreactor greatly vation in bioreactor configurations.
surpasses the performance of existing gas phase bioreactors.
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