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Bioprocesses For Air Pollution Control

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22 views18 pages

Bioprocesses For Air Pollution Control

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Review

Received: 25 February 2009 Revised: 8 April 2009 Accepted: 9 April 2009 Published online in Wiley Interscience: 2 June 2009

(www.interscience.wiley.com) DOI 10.1002/jctb.2216

Bioprocesses for air pollution control


Christian Kennes,∗ Eldon R. Rene and Marı́a C. Veiga

Abstract
Bioprocesses have been developed as relatively recent alternatives to conventional, non-biological technologies, for waste gas
treatment and air pollution control in general. This paper reviews major biodegradation processes relevant in this field as well
as both accepted and major innovative bioreactor configurations studied or used nowadays for the treatment of polluted air, i.e.
biofilters, one- and two-liquid phase biotrickling filters, bioscrubbers, membrane bioreactors, rotating biodiscs and biodrums,
one- and two-liquid phase suspended growth bioreactors, as well as hybrid reactor configurations. Some of these bioreactors
are being used at full-scale for solving air pollution problems, while others are still at the research and development stage at
laboratory- or pilot-scale.
c 2009 Society of Chemical Industry

Keywords: biotechniques; biodegradation; bioremediation; gas-phase bioreactor; waste gases

INTRODUCTION solubility in aqueous medium makes its removal from polluted air
Besides classical physical and chemical treatment technologies, in bioreactors a challenging task.4,5 Other parameters, such as the
bioprocesses have proven to be efficient technologies for the relative humidity in packed bed bioreactors, will also affect the
treatment of polluted air. The most popular and oldest bioreactor biodegradation efficiency.2
configuration is the conventional biofilter which has now been A few decades ago several industrial pollutants were thought
used for several decades.1 Its original application was for the not to be biodegradable at all because of their anthropogenic
removal of odours, mainly at wastewater treatment plants, nature (i.e. xenobiotics as chlorinated ethylenes) and because of
composting facilities, and similar sources.2 Biofilters have their the presumable lack of microbial enzymes able to attack chemical
specific niche of application and are best suited to the removal of structures that were rare or even inexistent in nature. However,
relatively low concentrations of pollutants over a wide range of extensive microbiological research undertaken since the late 1970s
gas flow rates (Fig. 1). Low flow rates are generally better when has proven that most volatile pollutants are biodegradable to some
dealing with high pollutant concentrations. It is usually advised extent by bacteria or fungi.6,7
not to work at pollutant concentrations exceeding 5–6 g m−3 Several different types of volatile air pollutants, either organic
air.3 Higher concentrations may be inhibitory to microorganisms. or inorganic, may be found in waste gases. Although the
This is not only true for conventional biofilters, but also for most accumulation of intermediate metabolites may occasionally take
other bioreactor configurations, although recent developments place under high load conditions, this is otherwise not expected
at laboratory-scale allow efficient treatment of somewhat higher to occur and the pollutants are generally completely biodegraded
concentrations and loads as well. into, basically innocuous, end products.
Since the 1980s the use of biofiltration has been extended to The overall reactions and the end products formed during
new sources and several full-scale plants have been developed and biodegradation of chief groups of air pollutants are briefly
built for the removal of volatile organic and inorganic compounds summarized hereafter.
from industrial waste gases. A new bioreactor configuration was
optimized around that same period for air pollution control, Most general case
namely the biotrickling filter.2 Since then and over the past In many cases, the volatile pollutant will only contain carbon and
two decades, extensive studies have been undertaken on the hydrogen atoms as, for example, in toluene (C7 H8 ) or methane
optimization of existing systems and on the development of (CH4 ). Additionally, the pollutant may sometimes also contain
other new types of bioreactors. The membrane bioreactor and the oxygen, as in the case of methanol (CH3 OH) or formaldehyde
rotating biological contactor (RBC) are two examples.2 Some of (CH2 O). In both cases, the final end metabolites of aerobic
these new reactor configurations have not yet been implemented biodegradation will be water and carbon dioxide. If the pollutant is
in full-scale applications. able to sustain growth, new biomass will also be formed, as shown
schematically in Fig. 2. The most common formula for biomass

BIODEGRADATION
Theoretically, any biodegradable pollutant could be removed in ∗ Correspondence to: Christian Kennes, University of La Coruña, Chemical
bioreactors. Nevertheless, other, non-biological, parameters also Engineering Laboratory, Rua Alejandro de la Sota 1, E – 15008 – La Coruña,
do play a key role in the efficiency and suitability of biological Spain. E-mail: [email protected]
reactors for waste gas treatment. For example, carbon monoxide
1419

University of La Coruña, Chemical Engineering Laboratory, Rua Alejandro de la


is a readily biodegradable compound; nevertheless its very low Sota 1, E – 15008 – La Coruña, Spain

J Chem Technol Biotechnol 2009; 84: 1419–1436 www.soci.org 


c 2009 Society of Chemical Industry
www.soci.org C Kennes, E R Rene, M C Veiga

100000 dominant.7 Other nitrogen sources such as nitrate would allow in


maintaining a more stable pH.
10000 The above mentioned equations refer to aerobic biodegradation
Gas flow rate (m3/h)

processes, which is the general case in waste gas treatment.


1000 Nevertheless, anaerobic gases may occasionally also be treated
OTHER
TECHNOLOGIES in bioreactors,2 such as the gas generated from the anaerobic
100 treatment of organic waste in landfills.
10 BIOREACTORS
Halogenated compounds
1 Several halogenated organic compounds are volatile and may ap-
0.1 1 10 100 1000 pear in waste gases. Chlorinated compounds are the most common
Pollutant concentration (g/m3) ones, and the most widely studied halogenated air pollutants are
Figure 1. Range of gas flow rates and pollutant concentrations suitable in chlorobenzenes, dichloromethane, and halogenated ethylenes as
bioreactors for waste gas treatment. trichloroethylene (TCE).9 The biodegradation of such compounds
will yield hydrogen chloride, besides water and carbon dioxide,
according to the following general equation:
composition is C5 H7 NO2 . Formulas such as C5 H9 NO2.5 , and other
similar ones, have also been used. This shows that microbial cells a R-Cl + b O2 −−−→ c CO2 + d H2 O + e HCl
are not only formed of carbon, hydrogen and oxygen atoms,
but also nitrogen as well as other elements such as phosphorus, where a, b, c, d and e are the stoichiometric coefficients and R-Cl
among others, not appearing in the simplified formula. Thus, in represents a chlorinated volatile organic pollutant.
order for biomass growth to take place and in order to optimize Thus, contrary to what happens with non-halogenated pollu-
microbial enzymatic activities, the presence or addition of macro- tants, in the present case acidification of the medium will take
and micro-nutrients (nitrogen, phosphorus, trace elements, etc.) place as a result of the pollutants biodegradation, and pH regula-
may sometimes be necessary in bioreactors. Biomass growth and tion will be necessary if the microbial activity is negatively affected
composition will depend on different parameters, as the type of by a pH drop, which is the most common situation.
microorganism (genus, species) and the environmental conditions. Two examples are given below for monochlorobenzene,
The overall biodegradation equation in this general case will be without considering biomass growth:

a VOC + b O2 −−−→ c CO2 + d H2 O C6 H5 Cl + 7 O2 −−−→ 6 CO2 + 2 H2 O + HCl

where a, b, c and d are the stoichiometric coefficients and VOC and with biomass growth, using ammonium nitrate as nitrogen
represents the pollutant or volatile organic compound, i.e. Cm Hn source:
or Cm Hn Op . An example is given hereafter for toluene, one of the
most widely studied air pollutants in bioprocesses:
C6 H5 Cl + 3.69 O2 + 0.265 NH4 NO3 −−−→ 2.65 CH1.8 O0.5 N0.2
1 C7 H8 + 9 O2 −−−→ 7 CO2 + 4 H2 O + 3.35 CO2 + 0.15 H2 O + HCl

If biomass growth is taken into account, the following equation Inorganic sulphur compounds
would be obtained when using ammonium chloride as nitrogen Hydrogen sulphide is a widely studied and common inorganic
source:8 sulphur compound in polluted air. As in the case of halogenated
pollutants the presence of sulphur in the molecule will generate
1.55 C7 H8 + 12.9 O2 + 0.2 NH4 Cl −−−→ CH1.8 N0.2 O0.5 an acid end-product as shown below and will result in medium
+ 9.85 CO2 + 5.6 H2 O + 0.2 HCl acidification:10

It is worth observing that the use of ammonium chloride as H2 S + 0.5 O2 −−−→ S0 + H2 O


nitrogen source will yield hydrogen chloride as an end product S0 + H2 O + 1.5 O2 −−−→ H2 SO4
and result in medium acidification. Therefore, the use of NH4 Cl
as nitrogen source may require pH regulation during bioreactor The amount of oxygen available plays a key role in the
operation, unless acid-tolerant microorganisms, such as fungi, are biodegradation process. As shown in the above equations, if

Biodegradation products

Pollutant

Biomass Biodegradation products


Endogenous
respiration
1420

Figure 2. Pollutant biodegradation pathways.

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c 2009 Society of Chemical Industry J Chem Technol Biotechnol 2009; 84: 1419–1436
Bioprocesses for air pollution control www.soci.org

oxygen is limiting, elemental sulphur will accumulate. Otherwise, BIOREACTOR CONFIGURATIONS


complete conversion to sulphate will take place. Although pH Conventional biofilter
drop may sometimes be inhibitory, above all at very low pHs, As mentioned earlier, the conventional biofilter is probably the
several hydrogen sulphide-degrading bacteria tolerate acidic oldest bioreactor configuration used for waste gas treatment.
conditions.11 Several review papers and book chapters have focused on that
Contrary to what happens with halogenated and non- system. Therefore, not too much space will be dedicated here to
halogenated VOCs, most H2 S degraders are autotrophic organ- the fundamentals of that reactor, although some recent data and
isms, which means that they usually use inorganic carbon, i.e. advances will be presented. In a nutshell, the conventional biofilter
usually CO2 , as carbon source. Heterotrophic VOC degraders is a fixed-film or packed bed bioreactor in which a natural filter
described above are microorganisms generally using the VOC- bed is most often used (Fig. 3(a)), although recently inert packing
pollutant itself as carbon and energy source. Nevertheless, in materials have proven successful as well (Fig. 3(b)). Polluted air
heterotrophic co-metabolic degradation processes, another car- is fed in either a downflow or an upflow mode through the
bon source may be required besides the pollutant itself. A typical reactor and the pollutants of the waste air are biodegraded by
stoichiometric equation considering biomass growth would be as the biocatalyst present in the packed bed. Contrary to what
follows for H2 S removal:12 happens with some other reactor configurations, such as the
trickling biofilter or the bioscrubber that will be described later,
0.444 H2 S + 0.4 HS− + 1.2555 O2 + 0.0865 H2 O + 0.346 CO2 in conventional biofilters there is no continuous feed of a liquid
phase. Therefore, this reactor will be especially suitable for the
+ 0.0865 HCO3 − + 0.0865NH4 + −−−→ 0.844 SO4 2−
treatment of hydrophobic and poorly water soluble compounds
+ 1.288 H+ + 0.0865 C5 H7 NO2 with a Henry’s constant up to about 1. Also, because of the
absence of a mobile liquid phase, conventional biofilters are not
the best choice for treating pollutants, such as, for example,
OPERATING PARAMETERS OF BIOREACTORS chlorinated compounds, leading to medium acidification. This can
Bioreactor operation and performance can in most cases be clearly be illustrated by comparing the results found in the few
described with the parameters defined hereafter.2 studies published on dichloromethane removal in biofilters to
Volumetric loading rate: those obtained with biotrickling filters in which a mobile liquid
phase is present (Table 1). With conventional biofilters, maximum
 
Q m3 elimination capacities do hardly reach 10 g m−3 h−1 while more
VLR = , than 100 g m−3 h−1 can easily be reached in biotrickling filters.
V m3 .h
Key elements of a biofilter are described hereafter.

Mass loading rate:


Filter bed
  The filter beds used in conventional biofilters were originally
Q.Sin g
MLR = , exclusively of natural material, i.e. soil, compost or peat.1 Such filter
V m3 .h beds are still widely used today, above all for the removal of low
odour concentrations, at wastewater treatments plants, municipal
Elimination capacity: solid waste treatment plants or composting facilities, among
  others. They present some advantages over inert and synthetic
Q.(Sin − Sout ) g materials, such as the natural presence of microorganisms and
EC = ,
V m3 .h nutrients, although the latter may not be available in optimal or
balanced concentrations. Besides, nutrients will also gradually be
Removal efficiency: consumed and eventually the filter bed may become depleted of
essential nutrients. A major drawback of such natural filter beds
(Sin − Sout ) is their gradual degradation and compaction over time, leading
RE = , [%]
Sin to pressure drop increase and decreased removal efficiencies. In

In the above equations, Q is the gas flow rate (m3 h−1 ), V is the
volume of the reactor (m3 ) and Sin and Sout are, respectively, the Table 1. Some examples of efficiencies of dichloromethane removal
inlet and outlet pollutant concentrations (g m−3 ). in conventional (BF) and trickling (BTF) biofilters (adapted from
Complete biodegradation is often assessed by the carbon Reference 9)
dioxide production rate, although it is not always easy to make Reactor Maximum EC
thorough mass balance calculations as carbon dioxide may also be configuration Filter bed (g m−3 h−1 ) References
generated through other processes in bioreactors as, for example,
BF Compost–perlite– 10.3 13
endogenous respiration. crushed oyster shell
CO2 production rate: BF Peat 6.4 14
  BTF Ceramix Novalox saddles 157 15,16
Q(CO2,out − CO2,in ) g
CO2 PR = , BTF Polypropylene packing 103.5 17
V m3 .h BTF Polypropylene saddles 152 18
BTF PVC 102 19
where CO2,out and CO2,in are the outlet and inlet carbon dioxide BTF Lava rock 160 20
1421

concentrations (g m−3 ), respectively.

J Chem Technol Biotechnol 2009; 84: 1419–1436 


c 2009 Society of Chemical Industry www.interscience.wiley.com/jctb
www.soci.org C Kennes, E R Rene, M C Veiga

(a)

(b)

Figure 3. (a) Conventional open–bed biofilter; (b) closed biofilter.

order to minimize head losses, inert or bulking materials have more to the water content, mainly in open biofilters (Fig. 3(a)) during
recently been added to natural filter beds (i.e. perlite) allowing one the summer period when the top layer of the bed may more
to control pressure drop more successfully. Humidification of the easily dry out. Some examples of natural and inert filter beds
waste gas is a prerequisite for successful operation of such systems used in laboratory- and pilot- scale biofilters are given in Table 2,
(Fig. 3(a), (b)), as microorganisms need a given level of relative together with their main characteristics and the corresponding
humidity for their optimal activity; while it should be recalled reactor performance.
that no continuous liquid phase is added to such conventional
biofilters. Filter beds composed exclusively of inert materials Biocatalyst
are nowadays also being used. In such a case, the intermittent The biocatalyst is another element playing a key role in efficient
feeding of a liquid solution is compulsory; otherwise filter bed bioreactor operation. Indeed, microorganisms present in biofilters
drying will quickly take place, resulting in a drop of performance should possess adequate enzyme systems in order to allow
and eventually reactor failure. Anew, maintaining optimal water biodegradation to take place. As mentioned above, natural filter
content in a biofilter is a key issue. Nowadays moisture control and beds contain indigenous microorganisms. If the pollutant is a
regulation can easily be done on-line with cost-efficient sensors.21 quite readily biodegradable substrate, for example, hydrogen
Water addition can be programmed at a frequency of once or a sulphide, suitable indigenous microorganisms will generally be
few times a week. At high loading rates, the frequency of liquid present and will easily develop in the biofilter. In the case of more
phase addition needs to be increased.22,23 It should be recalled recalcitrant pollutants, for example, MTBE or some halogenated
that biodegradation is an exothermic process generating heat. compounds, inoculation of specialized biocatalysts may become
Thus, the temperature of the filter bed will increase more at higher necessary. Inoculation is also a prerequisite when the packing
loading rates.24,25 Sprinklers are often installed when using natural material is inert or of a synthetic nature. Again, if the pollutant
1422

filter beds in order to maintain optimal conditions with respect is not highly recalcitrant, almost any type of sludge or mixed

www.interscience.wiley.com/jctb 
c 2009 Society of Chemical Industry J Chem Technol Biotechnol 2009; 84: 1419–1436
Bioprocesses for air pollution control www.soci.org

Table 2. Comparison of recent results of removal of single pollutants in mesophilic biofilters packed with natural or with inert filter beds. More
examples of older results can be found in previous publications1,2
Void Specific surface Maximum
space area Density EC Corresponding
Pollutant Filter Bed EBRT (s) (%) (m2 m−3 ) (kg m−3 ) (g m−3 h−1 ) RE (%) Ref

Acetone Sintered glass Pall 46.8 334 > 99 26


rings
Ammonia Compost 86 61.3 89.5 27
Carbon monoxide Peat + lava rock 180 50 (lava rock 875 (lava rock) 33 85 5
(75 : 25, W/W) only)
DMS Porous silica packing 40 35 585 0.2 6 28
DMS GAC : Peat (1 : 1, V/V) 20–50 480 (GAC) 670 90 gS/m3 .h ∼ 90 29
(Peat)
H2 S GAC ? 125 98 30
H2 S UP20 57 705 920 9 93 31,32
H2 S Exhausted AC 4 Up to ∼ 40 > 95 33
Methanol Porous ceramic 65 40 310 75 94 34
shperes
Methanol PP spheres 65 90 280 25 31 34
Methanol Wood chip 30 240–250 90 35
Methanol Lava rock 53.8 875 185 97 36
Mono– Compost 60 70 93 37
Chlorobenzene
Styrene Perlite 120 279 78 38
α –Pinene Wood chip 50 45 > 95 35
α –Pinene Lava rock 72 875 143 89 39
Styrene Compost : Shredded 120 54 611 45 75 40
plastic (25 : 75, V/V)
Styrene Perlite 120 260 > 95 41,42
20 196 > 95
Toluene Peat 57 93 80 43
Toluene Coir pith 118 80 606 96.8 80 44
Toluene Compost + Ceramic 42 ∼ 160 100 45
(1 : 1, V/V)
Toluene Compost + Ceramic 24.6 128 49 46
beads (6 : 4, V/V)
Toluene Compost + sea shells 27 75 82 82 47
(1 : 6, W/W)
Toluene Perlite 30 44 5.3 cm2 /cm3 100 ∼ 30 ∼ 62 48
Toluene Perlite 80 164.4 100 8
Toluene PU foam 30 56 1.7 cm2 /cm3 28 ∼ 28 ∼ 58 48

UP20 = mixture of CH4 N2 O, H3 PO4 , CaCO3 and organic binder (20%), PVA:Polyvinyl alcohol

culture can be inoculated in the biofilter; otherwise, for more performance. Different techniques make this possible, among
recalcitrant pollutants, seeding specialized microorganisms may which the use of a directional switching feed50 or the use of a
be required. Although both bacteria and fungi have been found in split-feed strategy.51
biofilters, under certain conditions such as at low water contents Several operating and environmental conditions may affect
or a low pH, favouring the growth of fungi may be useful since biofilter performance. They are briefly overviewed hereafter.
those organisms are more resistant to such adverse environmental
conditions.7 Nevertheless, the presence of filamentous fungi may Environmental conditions
sometimes lead to a faster increase in pressure drop than in Microorganisms exhibit their optimal activity in a specific range
bacterial-dominant systems. of pH and temperature. In most cases, for pollutants containing
The biomass concentration in biofilters is often not homogenous carbon, hydrogen and oxygen atoms (Cm Hn or Cm Hn Op ), the
along the filter bed height, above all in the case of inert carriers, optimal pH is near neutral (pH 6–7), above all when bacteria
which depend on the addition of nutrients for biomass growth are the dominant populations in the biofilm. Recent research has
and activity. Although biomass concentration is usually higher shown that when fungi are dominant, the optimal pH will generally
near the inlet of the bioreactor, some authors did occasionally be somewhat lower, often around 5.52 Besides, fungal cultures
observe the opposite, with higher biomass concentrations closer may even remain active at pH values below 4,52,53 although
to the outlet.8,49 Managing to obtain a more even biomass the biofilter may not reach its optimal performance under such
1423

distribution will result in optimization and increased biofilter conditions.8 Temperature is also an important parameter affecting

J Chem Technol Biotechnol 2009; 84: 1419–1436 


c 2009 Society of Chemical Industry www.interscience.wiley.com/jctb
www.soci.org C Kennes, E R Rene, M C Veiga

performance. Although the temperature effect is often not taken reported for conventional ‘bacterial, biofilters. Fungi will better
into account when comparing the performance of different resist to adverse conditions in terms of water content although
mesophilic biofilters operated at laboratory scale, the effect is such conditions may not be optimal.
not negligible. For a biocatalyst exhibiting its optimal activity at
30 ◦ C, removal rates and performance may drop by more than 50% Flow rate and inlet concentration
if the temperature is lowered to 20 ◦ C.54 Biofilters are mainly recommended for the treatment of waste
Regarding the treatment of halogenated (mainly chlorinated) gases with concentrations below about 5 g m−3 . They are also
pollutants, it was previously mentioned that their aerobic more suitable for the treatment of relatively low or moderate
biodegradation will lead to pH drop. Microorganisms degrading flow rates, although high flow rates exceeding 100 000 m3 h−1
halogenated substrates are often quite sensitive to medium can occasionally be treated in such reactors as well, provided
acidification. Therefore, as explained above (Table 1) conventional the pollutant concentrations are not excessively high. Nowadays,
biofilters will not be the best choice in this case. For example, full-scale biofilters are able to treat gas loading rates exceeding
studies undertaken with Hyphomicrobium strains degrading 200 m3 m−3 h−1 , although complete pollutant removal is not
dichloromethane have shown that the optimal pH for that always possible at such high loads. Complete pollutant removal can
organism is near neutral. At lower pH values, microbial activity often be reached up to 100 m3 m−3 h−1 .57 At inlet concentrations
will quickly drop. The biodegradation of sulphur compounds such exceeding 5–10 g m−3 and at high flow rates other, non-biological,
as hydrogen sulphide is also known to release acidic products. treatment processes are usually recommended. Under such
Nevertheless, many H2 S degraders are resistant to very low pH conditions, the reactor size and footprint for biofilters would be
values. High activities have sometimes even been detected at pH quite high. Besides, biofiltration would, in many cases, not be cost
as low as 2 or 3.11 effective anymore compared with physico-chemical technologies.
Most biofiltration studies are done under aerobic conditions. Generally, the empty bed residence time (EBRT) will range
Pollutants with a low number of chlorine atoms can rapidly be between about 10 and 60 s. Theoretically, the shortest residence
degraded in such aerobic environments. Nevertheless, highly times should be recommended. However, for the treatment of
halogenated compounds are better and more rapidly degraded hydrophobic volatile organic compounds as, for example, α-
under anaerobic conditions. Despite extensive research efforts pinene or styrene, it was shown that the critical load (maximum
made over the past two decades, some highly chlorinated load allowing near complete pollutant removal, i.e. RE near 100%)
aliphatic substrates, as perchloroethylene (PCE), have so far been in fungal biofilters may significantly decrease when the EBRT is
biodegraded only under anaerobic conditions.55,56 decreased (i.e. gas flow rate is increased) from 1 min or more to
less than 25 s.39,41,42

Water content Biotrickling filter


Much information has been published on the importance of The use of biotrickling filters for waste gas treatment has been
maintaining an optimal water content in biofilters, suggesting investigated for over two decades and the number of research
that optimal values are between 40 and 60% on a wet basis.1,2 studies and industrial applications has increased dramatically
A too low water content will reduce microbial activity while too since the 1990s. The reactor configuration is similar to that for the
much water may lead to pressure drop increase, compaction and conventional closed biofilter (Fig. 4). One major difference is the
the formation of anaerobic zones in the reactor. Biofilters in which continuous feed of a liquid trickling phase and the use of inert
fungi are dominant have shown to be somewhat more resistant packing materials in all cases. Some of the packing materials that
to low water contents.7 Nevertheless, in some studies it has have been used in biotrickling filters are listed in Table 3, together
been observed that optimal conditions are rather similar to those with their main characteristics and reactor performance.
1424

Figure 4. Biotrickling filter.

www.interscience.wiley.com/jctb 
c 2009 Society of Chemical Industry J Chem Technol Biotechnol 2009; 84: 1419–1436
Bioprocesses for air pollution control www.soci.org

Table 3. Recent examples of inert packing materials used in mesophilic biotrickling filters and performance data for each case
Void Specific
space surf. area Density Maximum EC Corresponding
Pollutant Packing material EBRT(s) (%) (m2 m−3 ) (kg m−3 ) (g m−3 h−1 ) RE (%) Ref.

Ammonia Porous ceramic 37.5 59.9 gN/m3 .h 99.8 58


Ammonia Pall rings + 51 4.5 100 59
Alginate beads
Dimethyl PE rings 60 30 ∼ 99 60
Sulphide
Ethanol PP spheres 30 90 280 970 60 61
Ethylacetate PP Pall rings 84 319 600 ∼ 97 62
Formaldehyde Lava rock 46.5 875 68 93.5 63
H2 S IOPF (contains 20–60 53 40.9 (biological + > 95 64
Fe2 O3 ) abiotic)
H2 S PU foam 15 94 500 218 ∼ 85 65
H2 S PP Pall rings 24 91 350 24 > 99 10
H2 S PU foam ∼ 2 95–105 95 66
H2 S (from Glass Raschig 75/bed 55 95 67,68
biogas) rings
H2 S (from PU foam 167 97 600 35 ∼ 240 ∼ 90 69
biogas)
Methanol PP spheres 30 90 280 2160 (biological + 58 70
abiotic)
MCB PVC Pall rings 150 14 70 71
NO (from flue Porous ceramic 90 35 (ceramic ∼ 30 (abiotic + 85–94 72
gas) beads + PP beads) 90 (PP bio–denitrification)
spheres (1 : 1, spheres)
V/V)
2–Cl–Phenol Ceramic 120 640 350 81 98 73
Toluene Ceramic 66.5 55–70 3.99 m2 /g 1.52 g/cm3 224–229 94–97 74

PU:PolyUrethane, PE:PolyEthylene; PP:PolyPropylene; IOPF:Iron Open Pore Foam; MCB:MonoChloroBenzene

Characteristics of the trickling liquid phase and the gas phase and biofilm sloughing. The influence of the liquid flow rate on
Compared with conventional biofilters, the presence of a mobile performance has been shown to be less significant at low pollutant
liquid phase in biotrickling filters allows, among others, for a much concentrations than at higher ones.76 This was also confirmed in a
easier pH control, temperature control and removal of accumu- study showing that modifying the liquid recirculation rate between
lated metabolites, if any. It is shown in Table 1, that, generally, a 3.63 and 9.55 m h−1 had only a minor effect on the performance
much higher performance can be reached in biotrickling filters of a biotrickling filter treating ethyl ether, at a relatively low
than in conventional biofilters treating dichloromethane polluted load of 38 g m−3 h−1 .77 Similarly, at low H2 S concentrations
air. The easy pH regulation in biotrickling filters plays a key role (25–150 ppmv ), other authors did not found any major influence
in this, but the removal of inhibitory compounds is also crucial. of the liquid flow rate on the removal of that pollutant when the
Indeed, in order to maintain a constant pH, sodium hydroxide is flow rate was varied between 0.63 and 2.75 m h−1 .10 Other work
usually added to neutralize hydrogen chloride generated during
done with H2 S demonstrated that the effect of the trickling liquid
the biodegradation of dichloromethane. This leads, in this exam-
rate was nil at low gas velocities while it became significant at
ple, to the formation of sodium chloride as shown in the following
high gas velocities.78 More recent research on hydrogen sulphide
equation:
HCl + NaOH −−−→ NaCl + H2 O removal showed that the removal efficiency (load not specified)
was basically 100% at G/L ratios between 200 and 500.65 At a
Sodium chloride which is inhibitory to DCM-degrading bacteria, as higher ratio of 1000, the RE dropped to 88%. It also dropped to
Hyphomicrobium sp., at concentrations exceeding about 200 mmol
97% at a lower G/L ratio of 100. Besides its effect on wetting,
L−1 , can easily be removed from the reactor by regularly renewing
other factors may affect the influence of the liquid flow rate on
part of the trickling liquid solution.
the reactor’s performance, such as the type of pollutant (among
Other key parameters are the gas (G) and liquid (L) flow rates
and the (G/L) ratio. Some studies have shown that the flow rate others its hydrophobic or hydrophilic nature) and its effect on pH
of the trickling phase may affect the overall reactor’s performance stability or product accumulation, as well as the characteristics of
under certain conditions. In studies undertaken with pollutants the packing material, among others. Plastic packings were used
as toluene,75 mono-chlorobenzene,76 and dichloromethane,15,17 in most of the above mentioned examples. In a research study
it has been recommended to apply a high superficial liquid flow in which the liquid supply was maintained constant (0.63 m h−1 ),
rate (L), which will result in a low G/L ratio. This would ensure a while the gas flow rate was modified, it appeared that methanol
high degree of wetting, resulting in a high reactor’s performance. removal (in terms of maximum elimination capacity and critical
1425

However, high liquid flow rates also increase operation costs load) increased when decreasing the superficial gas velocity from

J Chem Technol Biotechnol 2009; 84: 1419–1436 


c 2009 Society of Chemical Industry www.interscience.wiley.com/jctb
www.soci.org C Kennes, E R Rene, M C Veiga

136 m h−1 (G/L = 217) to 31 m h−1 (G/L = 130), i.e. increasing the advantage of being able to adsorb pollutants and buffer shock
EBRT from 17 s to 28 s.79 loads, thus minimizing microbial inhibition.89 Conversely, the void
Biotrickling filters are usually operated in either co-current space (Table 3) is significantly higher in biotrickling filters packed
or counter-current mode. In the few studies that compared with PU foam and plastic rings, which will slow down clogging
performance data under both conditions, it was observed that problems and pressure drop increase.
very similar results were obtained irrespective of the mode of
operation.12,15,16,80 Cross-flow is also possible, but rather unusual. Biomass accumulation and clogging
The optimal G/L ratio was estimated in a horizontal cross-flow
Pollutant biodegradation and the feed of a continuous nutritive
biotrickling packed with activated carbon and fed H2 S polluted
trickling solution will lead to biomass growth on the packing
air. G/L values ranging between 32 and 160 were applied, showing
material. Biomass accumulation is necessary since sufficiently
that an intermediate range between 60 and 80 yielded optimal
high biomass concentration will allow fast pollutant removal.
conditions in term of bioreactor performance.81
Nevertheless, if biomass concentration becomes too high, pressure
Regarding the gas phase residence time, typical values for the
drop will increase to such a point that it will lead to clogging
removal of VOCs (aliphatic and aromatic VOCs as formaldehyde
problems and eventually reactor failure. Under thermophilic
or toluene) are between about 15 s and 1 min. Recent studies
conditions, biomass build-up has been observed to be less
have shown that the removal of readily biodegradable pollutants
than under mesophilic conditions.24,25 The lower overall biomass
such as H2 S can be done in biotrickling filters operated at very low
yields at higher temperatures could result from high maintenance
residence times, comparable with those used in absorption towers,
energy requirements or temperature induced growth uncoupling.
i.e. 5 s or less.66,81,82 However, for more recalcitrant pollutants,
Besides, biomass distribution along the reactor is often not
higher residence times reaching more than 1 min may be required
homogenous, as also mentioned above in the case of conventional
(Table 4). This was the case, for example, in laboratory-scale studies
biofilters, and significant amounts of non-active microorganisms
done with TCE, where EBRT of several minutes were needed even
may be present, which will contribute to increase the pressure
at relatively low loads in order to reach reasonable pollutant
drop. As a result of this non-homogenous biomass distribution,
removal, although such long residence times may not be feasible
as much as 80 or 90% of the pollutant removal may sometimes
nor cost-effective at full-scale.
take place in the first half of the reactor,90 meaning that the other
half is under-used compared with the reactor volume closest to
Packing material the inlet. Different strategies have been suggested to slow down
Inert packing materials are used in biotrickling filters and may microbial growth or remove excess biomass from the reactor.23
play a major role in the performance and long-term stability of Methods aimed at slowing down biomass accumulation consist in
the reactor. Such packing is devoid of essential macro- and micro- lowering the concentration of one or more essential nutrients in
nutrients, but the trickling phase allows one to continuously the trickling phase. Generally, studies on nutrient limitation have
provide the essential nutrients in balanced concentrations. Some been done for nitrogen, phosphate or phosphorus. Reducing the
packing materials commonly used in scrubbers, i.e. plastic rings availability of such macronutrients does indeed reduce biomass
and saddles, have been tested in biotrickling filters (sometimes growth. Nevertheless, in all cases this does also negatively affect the
called fixed film bioscrubbers).54 Other frequently used filter beds reactor’s performance, resulting in lower pollutants removal. Other
are silicate-based materials such as perlite,8,22 celite50 or lava methods consist in removing part of the accumulated biomass
rock.63 Materials such as activated carbon and polyurethane (PU) once the pressure drop becomes too high. Either biological or non-
foam have also been tested.23,66,89 The latter has a low water biological techniques can be used for this purpose. In the case of
holding capacity compared with the others, which is unfavourable biological methods, organisms such as, for example, protozoa or
from that specific point of view. Activated carbon presents the nematodes, or mites are added to the reactor and help to control
the biofilm thickness and pressure drop.91 – 93 So far, only little
research has been performed on the optimization of predation
methods in biotrickling filters. Non-biological methods are mainly
Table 4. Some selected examples of EBRT used in biotrickling filters
for different groups of pollutants (inorganic, organic-aliphatic, organic- backwashing and air sparging. Backwashing consists in feeding
aromatic, poly-halogenated) water at a relatively high flow rate to the bioreactor. This can be
done with or without fluidization of the packing material and with
Maximum Corres
EC ponding or without addition of specific chemicals. The addition of chemicals
Pollutant(s) EBRT (g m−3 h−1 ) RE (%) References and the use of higher water temperatures usually improve biomass
removal.23 In air sparging, the bioreactor is filled with water, and
H2 S 1.6–2.2 s 95–105 > 95 66 air flowing at a high rate through the packed bed allows removal
5 s NR > 90 82 of excess biomass. All these strategies have been described in
5 s NR > 99 83 more details elsewhere.23 Finally, some mechanical methods have
4–16 s 113 96 81 been tested as well, consisting in most cases in mixing or stirring
Formaldehyde 20.7 s 111.8 78.6 84 the inert packed bed (i.e. plastic rings, polyurethane foam)94,95 at
Methanol 48 s 173.1 95.1 36 given time intervals by means of impellers or agitators.
Toluene 45 s 79.4 NR 85
Trichloroethylene 5.6 min 2.8 > 97 86 Bioscrubber
7.2 min 0.15 30–40 87 Much less research has been undertaken on bioscrubbers than on
20 min NR 98 88 conventional and trickling biofilters. There are also many fewer
NR = Not Reported full-scale bioscrubbers in operation than packed bed biofilters. The
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first full-scale plant was installed in German foundries in the 1970s

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for the removal of amines, phenol, formaldehyde and odours liquid phase allows for an easy control of some parameters as,
from waste gases.57 Compared with biofilters and biotrickling for example, pH, as was also the case in biotrickling filters. Since
filters, bioscrubbers can be operated at higher gas loads, up to pH may affect the optimization of both the scrubbing process
3000–4000 m3 m−2 h−1 . In biofilters, loads do normally not exceed and the biodegradation stage, the addition of acid or alkali may
500 m3 m−2 h−1 .2 be required in either the scrubbing tower or the bioreactor, or
It is important to remember that microorganisms need a both. Bioscrubbers have been used for the removal of inorganic
minimum moisture content to be active and exhibit their microbial compounds such as, for example, H2 S absorbed in alkaline
activity in the aqueous phase, either in the form of a biofilm or water, and, more recently, SOx absorbed in water containing
through suspended growth. Thus, biological air pollution control sodium bicarbonate, as well as NOx .96,97 Waste gases containing
would normally only be possible if the air pollutant is first absorbed hydrophilic VOCs such as, for example, methanol can also be
in the aqueous phase and then biodegraded. Although some treated efficiently in bioscrubbers.98 Several full-scale systems have
authors have used the words fixed-film bioscrubber for biotrickling been commercialized worldwide for the desulphurisation (H2 S
filters, in this paper, bioscrubber will refer to its most common removal) of biogas, landfill gas and natural gas.99 Another process,
definition, i.e. a combination of a suspended growth bioreactor the BioDeNOx technology, has been tested for NOx removal
and a scrubber in two separate units. In such a system, polluted air from flue gas.100 It is based on NOx absorption into an aqueous
is fed to an absorption tower first (scrubber). By doing so, target Fe(II)EDTA2− solution followed by a biological regeneration tank
compounds are transferred from the gas phase (air) to the liquid (i.e. bioreactor). So far, the technology has not been tested at full-
phase (water). Clean air is then released to the atmosphere from scale, and it has not been proven to be cost-effective compared
the scrubber, while polluted water is fed to a bioreactor (Fig. 5), with more conventional technologies.101
where microorganisms take care of the biodegradation of the Different types of bioreactors are potentially suitable for the
pollutant(s) in the aqueous phase. The scrubber may also be placed biodegradation process, but activated sludge units are most com-
on top of the bioreactor, in which case the water phase reaches monly used. In bioreactors used specifically for bioscrubbing, the
the bioreactor by gravity. A pumping system allows clean water hydraulic retention time is generally higher than in conventional
leaving the bioreactor to be reused as absorbent in the scrubber. activated sludge reactors used for wastewater treatment, and
Bioscrubbers are suitable for the treatment of pollutants that are enough sludge retention is often not a problem, except some-
relatively well soluble in water, as biodegradation is performed times for slow growing microorganisms such as nitrifiers.102 In any
by suspended biomass in the bioreactor. Besides, poor water case, biomass wash out would not occur if the reactor’s dilution
solubility would also negatively affect the absorption rate and rate does not exceed the average biomass growth rate. Since
efficiency. Therefore, this technology is mainly recommended for microorganisms need adequate concentrations of macro- and
pollutants with a Henry’s coefficient not exceeding approximately micro-nutrients for their activity, it is necessary to make sure those
0.01.1 – 3 are present in balanced amounts. The addition of nitrogen and
Absorption can take place either in a spray tower or in a phosphorus as the only nutrients is often enough, above all if tap
packed bed column. In order to remove volatile, poorly water water is used. On the other hand, since the bioreactor is typically
soluble pollutants, packed-bed absorption towers are often a suspended growth reactor, it will not suffer clogging problems,
recommended because they generally perform better in terms of contrary to what may occur in fixed film reactors. Conversely, a
removal efficiency. Most often, the absorption tower is randomly major challenge related to biomass growth consists in dealing
packed with a plastic packing material that allows maintainance with sludge accumulation and disposal. Two major alternatives
of a minimal pressure drop, but structured packings are suitable as have been suggested to limit sludge accumulation:103 (i) increase
well. Counter-current operation is the most general case, with (G/L) the requirement for maintenance energy by increasing the mean
ratios ranging typically between 300 and 500 and gas residence cell residence time; (ii) decrease efficiency of energy generation for
times not exceeding a few seconds. The presence of a mobile biomass growth by limiting nutrient supply. A too high biomass

1427

Figure 5. Bioscrubber.

J Chem Technol Biotechnol 2009; 84: 1419–1436 


c 2009 Society of Chemical Industry www.interscience.wiley.com/jctb
www.soci.org C Kennes, E R Rene, M C Veiga

concentration in the bioreactor, usually above 15 g L−1 , could gen-


erate clogging problems in the scrubber. Ideally, biofilm growth
should not take place inside the scrubber, although avoiding this
is not always easy in practice. High liquid flow rates and the use
of packing materials with a high void space allow minimizing
biomass growth in packed scrubbers. It is also worth observing
that flocs in bioreactors used in bioscrubbers are often smaller
than in activated sludge reactors used in wastewater treatment,
and sludge separation may thus be more difficult.
In most cases, aerobic microorganisms will take care of the
biodegradation stage and enough oxygen should be available
for the removal of the corresponding organic loading rate of
the water phase. Co-metabolic aerobic removal of VOCs, such
as TCE, needing the presence of a primary carbon source, is
more common in bioscrubbers than in packed bed reactors as
biofilters or biotrickling filters. One advantage of bioscrubbers is
that they can also be used for the anaerobic biodegradation of
volatile pollutants. This may be of interest in the case of pollutants
that are hardly biodegradable, or even not biodegradable at all,
under aerobic conditions, such as the highly chlorinated organic
compound tetrachloroethylene (PCE).56

Gas diffusion into suspended-growth bioreactors


Instead of feeding polluted air to a scrubber and then treating
the polluted aqueous phase in a suspended growth bioreactor as
in bioscrubbers, polluted air can be fed directly to a stirred tank Figure 6. Different parts of a membrane and mass transfer of compounds
in liquid and gas phases.
bioreactor. The latter could be an activated sludge reactor already
available on-site, for example in case of an industrial plant that
needs to treat both wastewaters and waste gases. It can also be a
polymeric matrix and being degraded by the attached (i.e. as
bioreactor built exclusively for the treatment of the waste gas. In
a biofilm) or suspended biocatalyst on the biofilm side. The
such a case, the reactor can be optimized for gas treatment only,
biodegrading activity of that biofilm creates a driving force for the
since no wastewater is fed. Significantly shallower reactors can
continuous transfer of the gas molecules through the membrane.
then be used, resulting in less pressure drop and much less energy
Microporous membranes provide high gas permeability, but
requirements.104 Other types of suspended growth bioreactors
do not allow the transport of water through the membrane,106
such as, for example, the airlift bioreactor, would be suitable as
avoiding physical contact between both phases. Water molecules
well. A more detailed description of this technology can be found
are generally unable to cross the membrane because of the
elsewhere.104
hydrophobic nature of such membranes.108 The pollutant is
transferred from the gas phase to the aqueous biofilm by diffusion
Membrane bioreactors through the pores, mainly as a result of the pressure gradient
In membrane bioreactors used for air pollution control, both a between both sides of the membrane and depending also on
gas phase and an aqueous phase are fed to the reactor. The two the solubility of the pollutant in the aqueous phase. Composite
phases are separated by a membrane. The gas phase is polluted membranes combine a dense membrane and a porous material.
air generally containing a carbon source, i.e. the volatile pollutant, Comparing the performance of membrane bioreactors with
while the aqueous phase is a source of nutrients for the biofilm other, mainly packed bed, bioreactors used for waste gas treatment
growing on the aqueous side of the surface of the membrane. is not easy since elimination capacities are expressed in terms of
The membranes are placed inside the reactor either in a tubular grams pollutant removed per m3 an hour in both packed bed and
configuration or in the form of flat sheets. Most often, the gas phase suspended-growth bioreactors, while it would be more logical
flows through the lumen, while the aqueous phase is fed through to express performance data in amount pollutant removed per
the shell side (Fig. 6). Contrary to what happens in conventional m2 membrane per day in membrane bioreactors (Table 5). In any
biofilters, where the pollutant is directly transferred from the air to case, performance of membrane reactors is of the same order of
the biofilm, in membrane bioreactors the membrane itself creates magnitude as for other more conventional bioreactors, and they
an additional resistance to mass transfer. Nevertheless, good are, in several cases, able to operate efficiently at relatively low
mass transfer rates have been reported in the literature.105 Two residence times of only a few seconds.
different types of membranes may be used; dense membranes Since a mobile liquid phase is present in membrane bioreactors,
and microporous membranes,106 but a combination of both is also a preliminary humidification step is not necessary. Besides,
possible. as in bioscrubbers and biotrickling filters, the aqueous phase
Dense membranes are limited to polymeric materials such as allows for easy pH regulation and optimization of nutrients
latex or silicone rubber. The mass transfer depends on the solubility supply. Biodegradation products can easily be removed. Another
and diffusivity of the permeating compound in the dense matrix.106 interesting feature of such reactors is that the transfer of
In the transport mechanism, the gas molecules absorb or dissolve microorganisms from the biofilm to the air can be avoided. This is
1428

first in the membrane surface,107 before diffusing through the above all true with microporous membranes, in which the small

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substrate transfer, leading to decreased reactor performance. It has


Table 5. Removal of volatile air pollutants in membrane bioreactors
been reported that biofouling problems are usually less significant
Membrane Maximum EC Corresponding in dense membranes than in microporous membranes.106 Aging
Pollutant material (g m−2 d−1 ) RE (%) References is also an important issue and may result in a lower permeability
Benzene PP 2.6 98 109 of dense membranes with time or gradual porosity problems in
LR 65 80 109 microporous membranes.
Butanol PS 471 99 110
PS 1567 38 110 Rotating biodiscs and biodrums
DCE PDMS 0.53 92 111 Different types of bioreactors containing rotating discs or rotating
DMS Zirfon 1.9 74 112 drums as the main part have recently been developed for waste
Nitric Oxide PO 0.15 74 113 gas treatment.
Propylene PP 3.6 58 114
PP 4.2 26 115
Rotating biological contactor
PP 1.3 20 116
TCE PP 0.018 52 117 The rotating biological contactor (RBC) is one example of reactor
PP 118 that has already been implemented at full-scale in a limited
Toluene PS 3.9 84 119 number of cases, mainly in Canada.123 RBC have been used for
PE 1.6 97 120 decades in the field of wastewater treatment. They have more
PP 3.0 35 121 recently been adapted to waste gas treatment, maintaining a
PVDF 17.7 84 122 similar reactor configuration as for wastewater treatment (Fig. 7).
An RBC consists of an airtight vessel containing bundles of discs,
DCE:DiChloroEthylene; DMS:DiMethylSulphide; TCE:Tri usually made of polystyrene, PVC or polyethylene, and mounted
ChloroEthylene; PP:PolyPropylene; LR:Latex rubber; on a shaft. The diameter of the discs may reach 1–4 m in full-scale
PS:PolySulfone; PDMS:PolyDiMethyl Siloxane; PO:Poly Olefin;
PVDF:PolyVinyliDeneFluoride reactors. The discs are tightly spaced, in order to maximize the
available surface area, and slowly rotating at a constant speed,
typically between 1 and 5 rpm. Part of the discs – about 40% of
the total surface area – is submerged in a nutritive liquid solution,
size of the pores does not allow the migration of microorganisms while the remaining disc surface is in contact with the polluted
from the liquid phase to the gas phase. Therefore, their potential air stream flowing through the system. A biofilm progressively
use in closed environments such as, for example, spacecraft has develops on the surface of the rotating discs, alternating its
been considered.105 exposure to soluble nutrients in the aqueous phase and exposure
Although numerous research data have been published for to air and the volatile pollutants present in the gas phase.
wastewater treatment in such bioreactors and the full-scale Part of the biomass is gradually sloughed off and will appear
application of this technology is relatively well established in in suspension in the aqueous phase, eventually needing to be
wastewater treatment, no full-scale results have yet been reported separated in a clarifier or sedimentation tank. Similar gas flow
for waste gas treatment. The relatively high cost, mainly of the rates and pollutant concentrations to those in other bioprocesses
membranes, compared with conventional bioprocesses is one can be treated in RBC. An advantage of this system is the absence
major drawback. Other factors are the lack of information, and of clogging, typical of packed bed biofilters. Laboratory-scale
possibly lack of stability, of such membrane bioreactors under studies undertaken with dichloromethane-polluted air showed
long-term operation and under unsteady-state conditions such that the reactor’s performance was similar or somewhat lower
as shock load operation. Another aspect to be considered is than with biotrickling filters, when feeding the polluted air stream
excess biofilm growth and membrane fouling resulting in reduced tangentially to the discs.123 A modified RBC was later used in which

1429

Figure 7. Rotating biological contactor (RBC) for waste gas treatment.

J Chem Technol Biotechnol 2009; 84: 1419–1436 


c 2009 Society of Chemical Industry www.interscience.wiley.com/jctb
www.soci.org C Kennes, E R Rene, M C Veiga

the packing material, with attached biomass, is continuously


moving, giving good mixing and avoiding clogging. Water can
Polluted air be continuously trickled over the drum in order to ensure a
good humidification level. The polluted air stream may either be
fed through the horizontal shaft or through the outer part of
the drum, which allows for good contact between the polluted
stream and the attached biomass. A similar system was used
more recently in which a set of six grid-structured polypropylene
drums were spinning in a concentric spiral form around a vertical
shaft.126 Nozzles allowed a scheduled trickling liquid supply. In
such a reactor, a relatively constant biofilm thickness can be
Liquid level
maintained. Periodic removal of excess biomass is by liquid shear
stress forces generated by jet nozzles feeding the aqueous phase,
which minimizes pressure drop. The efficiency of the rotor biofilter
was shown at pilot-scale to reach similar results to those for other
types of bioreactors.

Figure 8. Radial polluted air flow out of the shaft. Rotating drum biofilter
Another related configuration is the rotating drum biofilter (RDB).
In such a system, a single drum, made of reticulated polyurethane
the air was fed through the hollow shaft on which the discs were
foam, is rotating around a horizontal shaft.127 The drum itself
mounted.124 Under such condition, the polluted air flew in a radial
represents thus the packing or support material for the biomass.
direction with respect to the discs (Fig. 8). With such configuration,
Instead of using a trickling aqueous phase as in the rotor biofilter,
very good gas–liquid contact is reached and it was observed that
the polyurethane drum, rotating at a low speed rate, is partly
a quite constant biofilm thickness was maintained over a long
submerged in a nutritive solution (about 30% of the drum) while
operating period of about 1 year.
the remaining part is in contact with air, similarly to the RBC
design.128 Operating conditions (flow rate and gas residence time,
Rotor biofilter inlet concentrations) are similar as in other reactor configurations,
In a rotor biofilter, a rotating drum is used instead of a series of as well as the reactor performance. The RDB has also been show to
rotating discs (Fig. 9).125 The hollow drum is partly filled with a be suitable for the anaerobic removal of pollutants as nitric oxide
given packing material. As a result of the rotation of the drum, through denitrification.129,130 Contrary to the RBC and the rotor

Port for adding new


filter material

Treated air

Polluted air inlet Liquid outlet

Liquid inlet

Material outlet
1430

Figure 9. Rotating biofilter.

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biofilter, which have been tested in large-scale units, the RDB has solvents.133,134 Other organic solvents that have been tested are
only been studied at laboratory-scale so far. oleyl alcohol,135 and 1-octadecene.136

Two-liquid phase bioreactors Two-liquid phase suspended growth bioreactors


In the aforementioned reactors, water is used as single free or The organic solvent is expected to increase the overall treatment
moving liquid phase. Studies have been performed over the costs and the volume ratio of organic to aqueous phase should
past two decades on the use of a second, water-immiscible, generally not exceed 30% in full-scale systems, but ratios ranging
liquid phase in both biotrickling filters and suspended growth between 5 and 50% have been used and reported in the literature
bioreactors. To the best of our knowledge, some of the first for suspended growth laboratory-scale bioreactors. That organic
research papers on the use of an organic solvent in bioscrubbers phase should be dispersed in the form of small droplets in the
for waste gas treatment appeared around the early 1990s.131,132 aqueous phase. Small droplets will be more favourable in terms
The addition of an organic liquid phase is mainly useful for of mass transfer area. However, some researchers reported that
the removal of poorly water soluble pollutants, although the when the ratio of organic to aqueous phase exceeds 40%, larger
removal efficiency of less hydrophobic pollutants may also be drop sizes are formed and phase inversion may be observed.137,138
significantly increased in such systems.20 This type of system In the presence of an organic solvent, volatile pollutants relatively
presents interesting characteristics and significant advantages soluble in aqueous phase will generally not reach high, potentially
under certain conditions. Some of the most important are: (i) as inhibitory, concentrations in the suspended-growth water phase.
the pollutant is gradually degraded in the aqueous phase, a Thus, microorganisms in that water phase will not be inhibited.
driving force allows for the continuous and slow release of more Conversely, in the presence of a single aqueous liquid phase high
pollutant from the highly concentrated organic phase to the pollutants concentrations may lead to inhibitory conditions and
poorly concentrated water phase; (ii) as microorganisms are mainly biomass washout,139 although the toxic effect may be somewhat
present in the water phase, they will never be exposed to high, less significant in such a completely mixed reactor than in
inhibitory, pollutant concentrations accumulating in the organic packed bed biotrickling filters.20 It was observed that under given
reservoir; (iii) this type of system is potentially highly favourable operating conditions the biomass concentration in the reactor
for the removal of high concentrations and high loads (including will naturally reach and stabilize at a rather constant value.140,141
shock loads) of very poorly water soluble compounds. Non-steady-state load conditions are not unusual in full-scale
operation. In the case of occasional shock loads, the system may
become inhibited and may need some time to recover in the case
Organic phase of a single aqueous phase bioreactor. In such a case, the presence
The organic phase should meet the following criteria;102,131 of an organic phase has shown to be favourable as it will play
a buffering role and avoid or, at least, reduce inhibition.20,141 A
(i) immiscible with water similar effect will also be reached if an organic phase absorber is
(ii) non-biodegradable put in front of a conventional single aqueous phase stirred tank
(iii) not-toxic for the biocatalyst bioreactor, instead of directly mixing both the aqueous and the
(iv) low vapour pressure organic phase in the bioreactor itself.139 Some typical examples
(v) relatively low viscosity of performance data for two-liquid phase stirred tank bioreactors
(vi) density different from the density of water are summarized in Table 6.
(vii) odourless
(viii) inexpensive.
Two-liquid phase biotrickling filters
Although it might not necessarily always be the best choice In biotrickling filters, organic to aqueous phase volume ratios fed
from a chemical engineering and thermodynamic point of view, continuously to lab-scale reactors and reported in the literature,
silicone oil is the most popular and most commonly used range between 5 and 50%.20,138,143,146 It is not recommended to
organic phase. It fulfils pretty well the requirements mentioned use higher ratios in full-scale systems, and solvents with high
above. Some authors who tested various solvents among which, viscosities should be avoided since this would lead to higher
silicone oil, hexadecane, tetradecane, 1-decanol, diethyl sebacate, energy costs for pumping.138 In some studies, the performance
and 2-undecanone, observed that silicone oil was the only in presence of the organic phase is not systematically compared
non-biodegradable compound and one of the few non-toxic with control systems without a second liquid phase. However,

Table 6. Removal of volatile air pollutants in two-liquid phase stirred tank bioreactors

Pollutant Organic phase Organic/water ratio (Vol-%) Maximum EC (g m−3 h−1 ) Corresponding RE (%) References

Benzene n–hexadecane 33 133 95 142


DCM Silicone oil 10 195 42 20
Hexane Silicone oil 10 140 77 133
Hexane Silicone oil 10 120 67 143
IPB Silicone oil 10 240 61.5 140
Toluene n–hexadecane 33 733 98 144
Toluene n–hexadecane 33 145
1431

DCM:DiChloroMethane; IPB:IsoPropylBenzene

J Chem Technol Biotechnol 2009; 84: 1419–1436 


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www.soci.org C Kennes, E R Rene, M C Veiga

Table 7. Removal of volatile air pollutants in two-liquid phase biotrickling filters


Max. EC Corresponding
Pollutant Packing material Organic phase Organic/water ratio (Vol-%) (g m−3 h−1 ) RE (%) Ref

DCM Lava rock Silicone oil 10 195 42 20


Hexane PA structure wire mat Silicone oil 50 83–97 89 138
Hexane Perlite Silicone oil 5 180 > 90 143
Mixture of PP Ralu rings Silicone oil 10 33.6 NR∗∗ 146
polyalkylated
benzenes∗
Styrene Lavarock was soaked in silicone oil before starting up the BTF. No more oil was added later on. 2900 97.2 147
∗ Mainly C9 –and C10 –compounds (pseudocumene, methylethylbenzenes, diethylbenzene, etc.),
∗∗ Calculated RE:42%, DCM = DiChloroMethane

when such comparison was done, performance appeared always Another example of hybrid system using two different reactors
to improve with the addition of an organic solvent, by about in series has been described recently. When treating pollutants
25 to 240%, either in terms of elimination capacity,20 removal typically found in waste gases from resin- producing industries
efficiency,146 or both.143 In most cases, when the performances of (mainly formaldehyde and methanol), it has been shown that
biotrickling filters are compared with those of two-liquid phase higher maximal elimination capacities could generally be reached
stirred tank bioreactors, improvements were generally higher in in BTF while higher removal efficiencies were reached in BF.4
the latter than in the former.20,143 It is interesting to note the When connecting a biotrickling filter in series with a biofilter, it
surprising and unusual result obtained in one study performed was possible to simultaneously reach higher elimination capacities
with styrene.147 In that study the packing material was only soaked and higher removal efficiencies than with a single-stage system.4
once in silicone oil before starting the experiment, no further Still another set-up composed of a bioscrubber–biofilter in series
addition was done during the continuous reactor operation, and was evaluated for the treatment of odours released at composting
a maximum EC as high as 2900 g m−3 h−1 was reached (Table 7), facilities.151 The exact nature of the pollutants was not reported,
which is about 10 to 100 times more than in any biofiltration study but it was observed that only a small fraction, less than 30%, of the
reported in the literature. In a conventional biofilter packed with pollutants was removed in the bioscrubber. Most of the remaining
perlite partially coated with silicone oil on start-up, a maximum odour load was eliminated in the biofilter. The bioscrubber acts
hexane elimination capacity of 167 g m−3 h−1 was reached in that as a humidifier for the biofilter and as a potential buffering unit.
silicone oil amended biofilter compared with 114.9 g m−3 h−1 in a A similar bioscrubber–biofilter system was built for the treatment
control biofilter without addition of any oil.148 of waste gases from fat and oil processing industries.152 Pollutants
such as aldehydes and ketones were removed in the bioscrubber.
Hybrid and multi-stage systems Remaining aliphatic pollutants and aromatic compounds, terpenes
The removal of pollutants in two steps has recently been evaluated. and furanes were degraded in the biofilter. The idea of combining
It generally consists in using two bioreactors in series in order to a bioscrubber and a biofilter was suggested more than two
achieve a complete or, at least, higher removal of mixtures of target decades ago in the case of mixed pollutants, in which hydrophilic
compounds than in a single bioreactor. The reactors may either be compounds would be better removed in the bioscrubber, while
the same or two different reactors may be used. In such a way, the the biofilter would take care of degrading the more hydrophobic
activity of different types of microorganisms may be specifically fraction of the load.153
stimulated in each compartment by means of parameters as, for
example, pH, moisture content, or nutrients.21 Even more than Other bioreactors
two reactors could be used. In which case, a coarse filter material A few other reactor configurations have been tested as well,
in the first stage could separate particles or dust, for example.21 although they will not be described in detail here because in most
A common example is the use of two biofilters in series for the cases only a limited number of studies and results have been
removal of sulphur compounds such as H2 S mixed with VOCs. reported so far, mainly at laboratory-scale. Some examples are the
The optimal pH for bacteria degrading VOCs is generally near external loop airlift bioreactor,154,155 the spouted bed and fluidized
neutral, while the biodegradation of sulphur compounds leads to bed bioreactors,156,157 the monolith bioreactor,158 and the foamed
medium acidification and strong pH drop (see above). Some H2 S- emulsion bioreactor.159 Studies have also been performed, mainly
degrading bacteria are more tolerant of acid conditions than most over the past 10 years, on the combination of bioreactors and
VOC degraders.11 A pilot-scale facility operated at a wastewater non-biological processes, i.e. advanced oxidation processes.160,161
treatment plant showed that combining a first stage low-pH
inorganic biofilter with a second stage neutral-pH organic biofilter
led to the best results.149,150 Alternatively, some authors tried CONCLUSIONS
to stimulate the growth of acid tolerant organisms, for instance Biofilters and biotrickling filters are among the most extensively
fungi, and acid tolerant H2 S-degraders together in single stage used bioreactors for air pollution control and are highly suitable for
low pH bioreactors, to try to eliminate both sulphur compounds many full-scale applications. Recently, new bioreactor configura-
and VOC in the same unit. This appeared to be feasible in many tions have been developed specifically for air treatment, which has
situations leading to the development of mixed acid tolerant allowed a broadening of the range of pollutant concentrations and
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populations.79,150 gas flow rates treatable biologically. New or modified bioreactors

www.interscience.wiley.com/jctb 
c 2009 Society of Chemical Industry J Chem Technol Biotechnol 2009; 84: 1419–1436
Bioprocesses for air pollution control www.soci.org

have also been studied in an attempt to increase the number of 17 Hartmans S and Tramper J, Dichloromethane removal from waste
pollutants that could be treated using bioprocesses. This has also gases with a trickling bed bioreactor. Bioprocess Eng 6:83–92
widened the fields of application of bioreactors. Present and future (1991).
18 Okkerse WJH, Ottengraf SPP, Diks RMM, Osinga–Kuipers B and
research focuses on further broadening the fields and ranges of Jacobs P, Long term performance of biotrickling filters removing a
applications of such bioprocesses. Recent studies have focused mixture of volatile organic compounds from an artificial waste
on the removal of highly recalcitrant pollutants, very hydrophobic gas:dichloromethane and methylmethacrylate. Bioprocess Eng
ones, as well as on the removal of pollutants over a wider range of 20:49–57 (1999).
concentrations (from trace odour levels up to several g m−3 ) and 19 Okkerse WJH, Ottengraf SPP, Osinga–Kuipers B and Jacobs P,
Biomass accumulation and clogging in biotrickling filters for
at very low residence times of only a few seconds. waste gas treatment:Evaluation of a dynamic model using
dichloromethane as a model pollutant. Biotechnol Bioeng
63:418–430 (1999).
20 Bailón L, Nikolausz M, Kästner M, Veiga MC and Kennes C,
ACKNOWLEDGEMENTS Removal of dichloromethane from waste gases in one–and
The authors would like to thank the Spanish Ministry of Education two–liquid–phase stirred tank bioreactors and biotrickling filters.
and Science for financial support through project CTM2007- Water Res 43:11–20 (2009).
62700/TECNO, as well as the financial support of this research 21 Sabo F, Prechel S and Schneider T, Latest developments in high
through European FEDER funds. ERR thanks the Spanish Ministry efficiency biofiltration. in Proceedings of Ist International Congress
on Biotechniques for Air Pollution Control, ed. by Kennes C and
of Innovation and Science for a Juan de La Cierva research contract Veiga MC. University of La Coruña Publisher, La Coruña, Spain,
at the UDC. pp. 203–209 (2005).
22 Prado OJ, Mendoza JA, Veiga MC and Kennes C, Optimization of
nutrient supply in a downflow gas–phase biofilter packed with an
inert carrier. Appl Microbiol Biotechnol 59:567–573 (2002).
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