Rene 2012

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Combined biological and physicochemical waste-gas

cleaning techniques
a a a
Eldon R. Rene , María C. Veiga & Christian Kennes
a
Chemical Engineering Laboratory, Faculty of Sciences, University of La Coruña, La Coruña,
Spain
Version of record first published: 09 Apr 2012.
To cite this article: Eldon R. Rene, María C. Veiga & Christian Kennes (2012): Combined biological and physicochemical waste-
gas cleaning techniques, Journal of Environmental Science and Health, Part A: Toxic/Hazardous Substances and Environmental
Engineering, 47:7, 920-939
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Journal of Environmental Science and Health, Part A (2012) 47, 920–939
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ISSN: 1093-4529 (Print); 1532-4117 (Online)

DOI: 10.1080/10934529.2012.667289
Combined biological and physicochemical waste-gas

cleaning techniques
ELDON R. RENE, MARÍA C. VEIGA and CHRISTIAN KENNES

Chemical Engineering Laboratory, Faculty of Sciences, University of La Coruña, La Coruña, Spain
Downloaded by [Dalhousie University] at 21:19 17 December 2012
This review presents a general overview of physical, chemical and biological waste-gas treatment techniques such as adsorption,
absorption, oxidation and biodegradation, focusing more extensively on combined processes. It is widely recognized that biological
waste-gas treatment devices such as biofilters and biotrickling filters can show high performance, often reaching removal efficiencies
above 90 % for pollutant concentrations below 5 g/m3. However, for concentrations exceeding this limit and under transient shock-
load conditions that are frequently encountered in industrial situations, a physicochemical gas cleaning process can sometimes be
advantageously combined with a biological one. Besides improving the overall treatment efficiency, the non-biological, first-stage
process could also serve as a load equalization system by reducing the pollutant load during periodic shock-loads, to levels that
can easily be handled in the second-stage bioreactor. This article reviews the operational advantages of integrating different non-
biological and biological processes, i.e., adsorption pre-treatment+bioreactor, bioreactor+adsorption post-treatment, absorption
pre-treatment+bioreactor, UV pre-treatment+bioreactor, and bioreactor/bioreactor combinations, for waste-gas treatment, where
different gas-phase pollutants have been tested.
Keywords: Waste-gas treatment, volatile organic compounds, two-stage reactors, transient-state operations, load equalization, biore-
actor performance.
Introduction sions of pollutants to the atmosphere as they affect climate

change, growth of plants and overall the health of human
The environmental effects of air pollutants are a matter of beings and all forms of life.
increasing regulatory concern. Volatile organic and inor- Deteriorating air quality has contributed to stringent
ganic compounds are common air pollutants emitted from regulations all over the world and meeting regulatory stan-
a variety of both mobile and stationary sources. The emis- dards in process industries has been a major challenge for
sions of VOCs to the atmosphere originate from breathing environmental engineers and plant managers. Besides re-
and loading losses from storage tanks, venting of process ducing the emissions at their source, various techniques are
vessels, leaks from piping and equipments, contaminated available for the treatment of waste-gas streams loaded with
wastewater streams, and heat exchanger systems, among VICs and VOCs. Sometimes, combinations of techniques
others.[1] may be required to reduce the pollutant levels below legal
Apart from this, industries such as petrochemicals, re- limits. A large number of treatment options exist for the
fineries, plastic processing and moulding, carbon black, removal of volatile pollutants from industrial waste-gases,
rubber processing, vegetable and fish processing units, an- which are primarily selected based on the characteristics
imal farming and rendering units, coke production and of the gas-phase pollutants and on the composition of the
polymeric resin producing units also contribute to substan- waste-gas, gas-flow rate, and other factors such as safety or
tial amount of VOC emissions.[2,3] VICs such as hydrogen economic considerations.[4]
sulphide are commonly found in polluted air at wastewater Biological treatment systems such as biofilters and
treatment plants, among others. From an environmental biotrickling filters appear to be both cost-competitive and
point of view, it is necessary to limit and control the emis- highly efficient for the complete mineralization of relatively
low concentrations of pollutants (<5 g/m3), to harmless
end-products such as H2 O and CO2 , at ambient tempera-
Address correspondence to Christian Kennes, Chemical En- ture.[1, 4–7] In field situations, industrial effluents may show
gineering Laboratory, Faculty of Sciences, University of La variable loading patterns and several gas-phase bioreactors
Coruña, Rúa da Fraga, 10, E-15008 – La Coruña, Spain; E-mail: can tolerate moderate shock-loads. However, when sub-
Kennes@udc.es jected to a sudden high shock-load, the microorganisms
Biological and physicochemical waste-gas cleaning techniques 921
generally find it extremely difficult to tolerate such situa- following: vegetable oils, mineral oil, diesel oil, alkylptha-
tion over a long period of time. lates, alkyladipates, polyethylene glycol, dimethyl ethers,
For such situation and conditions where the treatment amongst others.
system is expected to receive varying levels of shock- With regard to reactor configurations for performing ab-
loads, some reports have suggested the addition of a non- sorption, the most commonly used reactor types are the
biological technique as the first treatment step followed by a packed and plate columns, spray chambers (Figure 1) and
bioreactor in order to reduce high loads down to levels that towers, cyclonic spray chambers and combinations of spray
can easily be handled in the bioreactor. Physical and chem- and packed chambers, jet and venturi scrubbers. In order
ical air pollution control processes (destructive or recovery to facilitate rapid mass transfer, absorption towers should
based) have proven to be effective for handling exceedingly be designed to provide a large liquid to vapour contact
high concentrations of volatile pollutants in the waste-gas area. This can be achieved, for example, by selecting opti-
stream.[7] mized tower packings or liquid atomization systems.[1] The
Physicochemical waste-gas treatment techniques collec- predominant choice for waste-gas treatment is the packed
tively include processes such as absorption, adsorption, scrubber, using either water and/or chemicals.[7]
condensation, thermal and catalytic incineration, mem-
brane separation, and several advanced oxidation processes
Water scrubbing in packed towers
(AOPs). This paper provides a general overview of some of

the most commonly used physical, chemical and biological Countercurrent operation is most common in packed
treatment techniques in industrial situations. The advan- scrubbers for air pollution control. In a countercurrent wa-
tages of coupling a non-biological process with a bioprocess ter scrubber, the waste-gas is fed through the bottom of an
are discussed. absorption column, contacting a counterflowing stream of
water. The column is filled with a packing material in order
to have a high contact surface area between the liquid and
the waste-gas. The treated gas leaves the top of the col-
Physicochemical waste-gas treatment techniques umn, while the liquid collected at the bottom contains the
pollutants. The liquid stream is transferred to a stripper,
The most common non-biological treatment technologies where water is regenerated by desorption with a counter
are absorption, adsorption, and oxidation, that can be used flow of air. Water scrubbing requires large amounts of wa-
as stand-alone processes or in combination with bioreac- ter, so single pass scrubbing is neither very economic nor
tors. These different technologies, used as stand-alone pro- an eco-friendly option. Hence, in most cases regenerative
cesses, will briefly be reviewed hereafter. absorption is preferred.[10]
Absorption Chemical scrubbing

Absorption is a diffusional mass transfer operation by Chemical absorption involves the reversible formation of
which soluble gaseous pollutants are removed by direct weak chemical bonds, i.e., intermolecular interactions, be-
dissolution in a solvent liquid.[8] The driving force for mass tween the pollutants and the solvent. Regeneration of the
transfer is the concentration difference of the solute be- solvent, therefore, involves breaking of these bonds and
tween the gaseous and liquid phases. The water-soluble correspondingly, a relatively high energy input.[11] The
VOCs present in the waste-gases are physically transferred most commonly used chemicals are highly oxidative by
to the liquid phase. A key variable of this process is the nature (examples: ozone, hydrogen peroxide, and sodium
selection of a suitable liquid absorbent, and for waste-gas hypochlorite), but some of these chemicals have their own
treatment applications, water and low volatile organic liq- practical limitations. For instance, when hypochlorite is
uids are commonly used as the absorbing liquid.[9] For hy- used for removing amines, it cannot only oxidize the pollu-
drophobic VOCs, as for example α-pinene, water cannot be tants, but also chlorinate the compounds, releasing chlorine
used, and literature suggests the use of water-oil emulsions, gas and chlorinated amines that will have to be eliminated
water-solid suspensions, and high-boiling absorbents.[4] by placing additional sulphuric acid scrubbers.[12]
According to Heymes et al.,[4] an organic absorbent
should possess the following characteristics: (i) high ab-
Adsorption
sorption capacity for a wide variety of VOCs, (ii) low vis-
cosity and high diffusion coefficient, which can control the Adsorption is a surface phenomenon in which the gas-
absorption kinetics, (iii) low vapour pressure in order to phase pollutants are brought into contact with a suitable
reduce loss of absorbent by stripping and to prevent ad- solid adsorbent. This technique is widely used to clean
ditional air pollution problems, (iv) easy availability and waste-gas streams containing odours, VOCs and other air-
low cost, and (v) no toxicity nor fire or explosion risks. borne pollutants appearing at relatively low to moder-
Some typical examples of organic absorbents include the ate concentrations. Generally, this process is classified as
922 Rene et al.
Fig. 1. Example of an absorption column: spray chamber.
either physical adsorption or chemisorption, based on the iii. Brunauer-Emmett-Teller (BET) model for multilayer
interactions between the adsorbate and adsorbent. Physical qmono α CCsve
adsorption qe BET =
adsorption can be further classified as pressure swing ad- 1− CCsve
( ) 1+(α−1) CCsve
sorption (PSA) and temperature swing adsorption (TSA).
For VOC control, physical adsorption has been found to Activated carbon is widely recognized as a highly efficient
play a more significant role than chemisorption. adsorbent because it provides a large surface area, which
It occurs when organic molecules are held on the sur- is the result of its vast infrastructure of pores, micro-pores
faces and in the pores of the adsorbent by weak van der and micro-pores within micro-pores.[1] A typical activated
Waals forces of attraction, characterized by low heat of carbon based VOC removal system together with a sol-
adsorption and by the fact that adsorption equilibrium is vent recovery plant is shown in Figure 2. It consists of a
reversible.[13] The solid can thus be regenerated (desorption) fixed bed of activated carbon through which the waste-gas
and reused. The most commonly used adsorbent for waste- is passed. The gas-phase pollutants get adsorbed onto the
gas treatment is activated carbon. The adsorption capacity surface of the activated carbon, until the carbon reaches
of a typical activated carbon process for a given pollutant its breakthrough. During the solvent recovery step, the ac-
is represented by an adsorption isotherm representing the tivated carbon is heated with steam, and the pollutant is
amount of volatile compound adsorbed at constant tem- released and flushed away by steam.
perature. After achieving the breakthrough point, the pol- The mixture of steam and solvent can then be condensed
lutant should be released (desorption) from the surface in by a cooling system, and subsequently separated by gravity
order to reuse the carbon, which is commonly done with decanting. In practical situations, multiple carbon beds are
steam. Some useful adsorption models are given below: used in series. The saturated bed can be kept off-line dur-
ing the regeneration process. Moisture content, retention
ability, pressure, concentration, type of adsorbent and des-
i. Langmuir model for homogenous monolayer adsorp- orption method used are some of the critical parameters
qm bCe
tion qe L = 1+bC e
; that decide the efficiency of an adsorption process. Dur-
ii. Freundlich model for heterogeneous surface and inter- ing the design of fixed bed adsorption units, the two most
1/n
molecular interactions qe F = KCe ; and, critical dimensions to be taken care of are the diameter
Fig. 2. Schematic of an adsorption column with a solvent recovery system. After breakthrough is attained, the adsorbent is regenerated
by steam.
of the adsorber and the depth of the adsorbent bed. Gas- Heterogeneous photocatalysis is one such process that is
phase pollutants such as acetone, benzene, toluene, xylenes, based on the photonic excitation of a catalyst (mostly
TCE, hydrogen sulphide, mercaptans, sulphur dioxide, TiO2 ) at the appropriate wavelength of an incident UV
and many others, have successfully been removed by this light. In general, organic compounds have a redox poten-
technique.[14,15] tial at higher energy than the valence band edge of com-
mon semiconductor oxides and therefore can act as an
electron donor yielding a radical cation, which can fur-
Pressure swing adsorption
ther react with H2 O or O2 . The chemistry occurring at the
In pressure swing adsorption, adsorption of gas-phase pol- surface of a photo-excited semiconductor is based on the
lutants takes place at elevated pressure and the material is radical formed from O2 , H2 O and electron rich organic
regenerated by reducing the pressure and subsequent appli- compounds.
cation of a light vacuum. However, this process requires a This mechanism primarily depends on the characteristics
pre-treatment step in order to remove water vapor present of irradiation, mass of photocatalyst, and concentration of
in the inlet stream. This is normally done by adsorption the reactants.[16] Most of the recent studies on the removal
onto impregnated activated carbon, followed by an increase of VOCs have chosen TiO2 as the catalyst for the following
in the temperature between 60◦ C and 90◦ C. Water vapor reasons: (i) inexpensive and easily available, (ii) operation
competes with the VOCs in the emission stream for adsorp- at room temperature and pressure, and (iii) effective degra-
tion sites on the carbon surface. Additionally, the presence dation of VOCs into CO2 and H2 O.[17–20] Moreover, recent
of water can destroy the structure of the adsorbent. studies have shown greater removal of VOCs by a combined
O3 /TiO2 /UV process, as excess ozone molecules could
scavenge hydroxyl radicals produced from the excitation
Photocatalytic oxidation of TiO2 by UV radiation.[21,22] Large scale installations for
The destruction of volatile pollutants, such as VOCs, by air purification by TiO2 photocatalysis have been built by
photocatalytic means is one of the emerging purification Trojan Technologies in North America and by the United
techniques for both wastewater and waste-gases, due to Technologies of Connecticut, among others, as reported
its versatility and high effectiveness at low temperatures. elsewhere.[16]
924 Rene et al.
These systems were designed to strip hydrocarbons from gen molecules accept the electrons preventing hole-electron
soil or groundwater and photo-catalytically irradiate (treat) recombination.
them to acceptable limits. However, because of the poor At the surface of the coated catalyst, the hydroxyl rad-
yield of photon utilization, the treatment of gaseous VOCs icals (OH∗ ) drive the chemical reaction by attacking ox-
may require reactor sizes that are prohibitive in some cases. idizable contaminants, producing a progressive breaking
Though this technique has been reported to be simple, ro- of molecules yielding CO2 , H2 O, mineral acids and other
bust and flexible, its operating cost arises mainly from the end-products. The sequence of redox reactions involved in
UV lamps and the corresponding electrical consumptions. a PCO is summarized here:
i. Excitation by high-energy wavelength light to gener-
Mechanism of photocatalytic oxidation ate pair of electron (e−) and hole (h+): TiO2 +hυ →
The mechanism of photocatalytic oxidation is illustrated TiO2 (h+ + e− )
in Figure 3. The generation of electron-hole pairs caused ii. Oxidation of adsorbed water molecules to give hy-
by the excitation of the catalyst (TiO2 ) with UV light is droxyl radicals: TiO2 (h+ ) + H2 O → OH∗ + H+
crucial for the photocatalytic oxidation process.[23] Semi- iii. Reduction of oxygen to super oxide: TiO2 (e− ) + O2 →
conductors like TiO2 are characterized by a filled valence O−2
iv. Generation of an oxidizing agent: O− + −
2 +2H +3e →
band and an empty conduction band, and the energy dif-

ference between the lowest energy level of the conduction H2 O2
band and the highest energy level of the valence band is v. Dissociation of the oxidizing agent to produce hydroxyl
called the band-gap energy. This corresponds to the mini- radicals: H2 O2 → 2OH∗
mum energy of light required to make the semiconductor vi. Recombination of electron and hole releases heat:
(photocatalyst) electrically conductive. TiO2 (e− ) + TiO2 (h+ ) → Heat
When a photon’s energy, hν, exceeds the energy of the vii. Overall gas-phase photochemical reaction: Organic
band gap, an electron, e−, is promoted from the valence pollutant + OH∗ + O2 → CO2 + H2 O + Mineral
band to the conduction band, leaving a hole, h+, behind.[24] acids
The electrons and holes photo-generate in the bulk of the
semiconductor and move to the particle surface (Figure
Formation of intermediate products
3), where electrons reduce the electron acceptors such as
molecular oxygen, and holes oxidize the electron donors In an ideal photocatalytic oxidation reaction, the gas-phase
including adsorbed water or hydroxide anion to give hy- pollutant is completely oxidized, mainly to carbon dioxide
droxyl radical.[25,26] Photocatalysis over TiO2 is initiated by and water. However, in many cases, complete mineraliza-
the absorption of a photon with energy equal to or greater tion of the gas-phase pollutant to innocuous end-products
than the band gap of the semiconductor (3.2 eV for TiO2 ), is not possible, and other toxic and problematic by-
producing electron-hole (e−/h+) pairs. The adsorbed oxy- products are identified during the course of photocatalytic
O2
-
O2 , H2O2
Conduction
Electron, e-
band
Reduction reaction
UV photon Bulk recombination
Band Surface
gap recombination
energy
(3.2 ev)
Excitation Oxidation reaction
*
OH
Valence +
band
Hole h
-
H2O/OH
Fig. 3. Mechanism of photocatalytic oxidation.

reactions.[27,28] For instance, during the photocatalytic ox- nol were identified as the oxidation products in that study.
idation of dichloromethane, the following intermediates Other identified photocatalytic oxidation products of dif-
were observed: chloroform, carbon tetrachloride, phos- ferent gas-phase pollutants are summarized in Table 1.
gene, methyl chloride, CO and CO2 .[29] For chlorinated
compounds like trichloroethylene, the formation of par- Assessing biodegradability and toxicity of intermediates
tial oxidation products such as phosgene, dichloroacetyl
chloride, monochloroacetyl chloride, dichloroacetic acid It is clearly evident that toxic intermediates and easily
and monochloroacetic acid has been reported in the lit- biodegradable compounds, such as aldehydes, alcohols,
erature.[27] Some of these compounds are more toxic than or acids may be produced during photocatalytic oxida-
the parent compound. According to Fan and Yates,[30] tion, irrespective of the gas-phase pollutant (whether
dichloroacetyl chloride is a reaction intermediate that can hydrophilic, hydrophobic or chlorinated organics), and
undergo continued photooxidation to generate phosgene it is important to evaluate or assess the biodegradability
(COCl2 ), CO and HCl, according to the following equation: of these intermediates and by-products if one wants to
develop adequate biological post-treatment options. Some
1 TiO2 /hv well known water quality parameters such as biological
Cl2 HCCOCl + O2 −−−−→ COCl2 + HCl + CO oxygen demand, chemical oxygen demand, total organic
2
carbon, and their ratios, BOD/COD and BOD/TOC,

This reaction is expected based on the relatively strong UV inhibition of oxygen consumption, dissolved organic
absorptivity and high extinction coefficient (103/m.s) of carbon, amount of organic matter, assimilable organic
dichloroacetyl chloride, and its weak acylchloride bonds.[31] compound (AOC), EC50 toxicity tests, amongst others,
Phosgene can react with TiO2 surfaces in the dark to un- have frequently been used by researchers working on PCOs
dergo hydrolysis to yield HCl and CO2 , and this surface to estimate biodegradability.[33–35]
hydrolysis reaction principally depends on the amount of Photocatalytic oxidation reactions will change the
adsorbed water or hydroxyl groups present in the TiO2 sur- molecular structure of the parent compounds (gas-
face.[27] phase pollutants), and break them down into smaller
Mohseni[28] reported phosgene and chloroform as the molecules.[36] These smaller molecules or by-products of
two major quantified by-products, along with trace oxidation can be classified as either readily biodegrad-
amounts of carbon tetrachloride during the photocatalytic able compounds or poorly biodegradable compounds. In
degradation of TCE in an annular type photoreactor us- the former case, a typical high oxidation capacity process
ing a low-pressure mercury lamp emitting UV at either 254 decomposes the target organic pollutant to smaller or-
(light intensity – 7.3 to 9.8 × 10−3 W/cm2) or 365 nm (light ganic compounds having high oxidation states and higher
intensity – 3.5 × 10−3 W/cm2), at a retention time of 0.5 s. biodegradability (example: oxalic and carboxylic acids),
A mass balance calculation revealed that 0.4 and 0.6 mol of while in the latter case, low oxidation capacity processes
phosgene were formed for every mole of TCE removed, in- can only partially decompose the parent organic pollutant
dicating that about 25% of the carbon in the TCE molecule resulting in by-products having low oxidation states and
was converted to phosgene, a planar molecule and a highly high molecular weights.
toxic compound. Large values of BOD/COD ratios indicate high
In another study, toluene photooxidation was carried biodegradability of the compounds and a value of 0.3 is
out in a cylindrical photoreactor by Augugliaro et al.[32], usually considered to be the cut-off point between non-
using TiO2 as the catalyst (BET surface area 4 m2/g), and biodegradability and biodegradability.[35] Chen et al.[35]
illuminated with a 400 W medium pressure mercury lamp carried out direct UV photodegradation experiments in
having a light intensity of 5 mW/cm2. Benzaldehyde, ben- a spiral quartz type photoreactor, using α-pinene as the
zene, benzyl alcohol and traces of benzoic acid and phe- model VOC. The intermediates were identified to be
Table 1. Photocatalytic oxidation products of gas-phase pollutants in photocatalytic reactors.

Pollutants Degradation products References
Trichloroethylene, Methylene chloride, carbon tetrachloride Phosgene, CO2 and dichloroaceyl [23, 83]
Perchloroethylene chloride
Benzene Phenol, hydroquinone, benzoquinone, and malonic acid [84]
Toluene Benzaldehyde, benzene, benzyl alcohol, formic acid, acetic acid, CO2 and [32, 85]
trace amounts of benzoic acid and phenol
Formaldehyde Formic acid [86]
α-Pinene Pinocamphone, 3-hydroxyl - α-pinene, acetaldehyde, acetone, formic acid, [35]
acetic acid, glycolic acid, propionic acid, propanedioic acid, CO, and CO2
2-Propanol Acetone, mesityl oxide, CO2 and H2 O [87, 88]
926 Rene et al.
Fig. 4. Schematic of a biofilter.
pinocamphone, 3-hydroxyl-α-pinene, acetaldehyde, ace- Biological waste-gas treatment techniques

tone, formic acid, acetic acid, glycolic acid, propionic acid,
and propanedioic acid, which were formed under different Treatment of VOCs and VICs from industrial sources, such
test conditions (in the presence of air or nitrogen with a as emissions from point sources, is a relatively new applica-
relative humidity of 2–3% or 75–80%). The authors con- tion of bioreactor technologies. Biological waste-gas treat-
ducted toxicity tests on the unicellular green microalgae C. ment systems have gained support as an effective, reliable,
vulgaris and performed alga growth inhibition tests. eco-friendly, simple and economical option in compari-
It was observed that the BOD/COD ratio increased from son to the different physical and chemical VOC removal
0.2 to 0.35 when experiments were performed in the pres- technologies such as absorption, adsorption, thermal and
ence of air, suggesting that these intermediates were more catalytic incineration, and photocatalytic destruction.[3, 7,
easily biodegradable than α-pinene. Results from inhibition 37]
Biological waste-gas treatment techniques explore the
tests showed that the inhibition decreased with an increase ability of microorganisms to destroy environmental con-
in the removal of α-pinene in the photoreactor. The inhi- taminants present in waste-gases. The contaminants are
bition ratio was 68% when α-pinene was used alone, while often utilized by microorganisms as a source of carbon
this ratio decreased to 24% when the intermediates were and energy. Not only organic but also inorganic volatile
tested for their biodegradability. Al Momani and Jarrah[34] compounds may be effectively removed, although some of
collected gas-phase toluene oxidation intermediates in wa- those pollutants (example: hydrogen sulphide) may require
ter impingers and measured the BOD, COD and dissolved the presence of an additional carbon source.
organic carbon values of that water. The authors reported The most commonly used bioreactor configurations
that high organic matter was present in the solar+O3 as- in industrial waste-gas treatment are biofilters and
sisted process, and the average DOC, COD and BOD values biotrickling filters. For practical reasons, while choosing
for the solar+O3 +TiO2 process were found to be 8 mg C/L, an appropriate treatment technique, focus is placed on the
18 mg O2 /L, and 7 mg O2 /L, respectively. Furthermore, microbial ecology and its activity, operational and control
the authors observed that the average biodegradability in- requirements needed to ensure an optimal chemical and
dex was found to be 0.41 for the solar+O3 +TiO2 system, physical environment for mass transfer and biodegrada-
indicating the suitability of a biological technique as a post- tion of the pollutant in order to achieve high removal
treatment option. efficiencies.[38] In addition to this, reactor configurations
Fig. 5. Schematic of a biotrickling filter.
such as air-lift bioreactors, spiral bioreactors, membrane line measurement devices. Biofiltration is typically an aero-
bioreactors, two-liquid phase biotrickling filters, two- bic degradation process in which a contaminated air stream
liquid phase suspended-growth bioreactors, monolith is passed through a porous packed medium that supports a
bioreactors, and rotating biological contactors have been thriving population of microorganisms (Fig. 4). Anaerobic
tested experimentally at the laboratory- or pilot-scale for biofiltration is, however, also possible. The principles gov-
waste-gas treatment.[7, 39–41] erning this are similar to other common biofilm processes.
The following categories of industrial chemicals in waste- The contaminant in the gas-phase is first absorbed from the
gases have been treated in different bioreactor configura- air phase to the water of the biofilm interphase. Then, this
tions: (i) aliphatic compounds, (ii) aromatic hydrocarbons, contaminant diffuses through the biofilm to a consortium
(iii) chlorinated hydrocarbons, (iv) nitrogen containing of well-acclimated microorganisms. The microorganisms
carbon compounds, (v) sulphur containing carbon com- play a major role in converting the pollutant into CO2 , wa-
pounds, (vi) oxygenated carbon compounds, and (vii) inor- ter and sometimes other end-products (example: sulphur
ganic compounds. or sulphate from H2 S). They generally obtain sufficient en-
ergy from the oxidation of the chemical, while utilizing it
as a primary substrate via non-specific enzymes.
Biofilters
In other cases, the pollutants may be degraded co-
The design of conventional biofilters has varied and im- metabolically. The degree of treatment depends on the
proved over the past sixty years, from simple open soil beds type and composition of the waste-gas stream, its
to closed systems equipped with automated control and on- water-solubility, activity of the microbes, media pH,
928 Rene et al.
Fig. 6. Schematic of a bioscrubber with a scrubber and a bioreactor unit.
temperature, moisture content of the filter bed, nutrient techniques to identify microbial community and its distri-
and O2 availability and other suitable conditions needed for bution within the biofilter, identifying interaction effects
aerobic biodegradation. Biofiltration has been considered during the removal of pollutant mixture, modeling tran-
economically advantageous to treat air streams containing sient operating conditions (shock-loads), process model-
low concentrations of organic contaminants at large flow ing, and the development of sophisticated control systems
rates.[7, 42, 43] for biofilters.
A wide variety of both organic and inorganic compounds
such as alcohols, aldehydes, ketones, hydrocarbons, car-
Biotrickling filters
boxylic acids, H2 S and NH3 have been treated in biofil-
ters.[44] More complex constituents such as chlorinated In biotrickling filters, the pollutant laden waste stream is
organics can be handled as well, but at slower rates and their passed over a microbial consortium immobilized on an in-
degradation may sometimes require the presence of a co- ert support material having a high surface area (Figure
metabolite. For example, dichloromethane was shown to be 5). The process of gas absorption, liquid phase regenera-
eliminated in a biofilter with 98% efficiency in the presence tion and subsequent degradation occurs simultaneously in
of toluene[45], although other studies have also reported one reactor configuration. A continuous stream of recir-
the biodegradation of DCM as single carbon source.[46] culating water containing essential nutrients for microbial
Moreover, competitive/inhibitory effects between chem- growth is distributed over the filter bed. This water flows
icals and microorganisms can play a vital role in the re- down as a thin film and wets the biofilm layer. The waste-gas
moval of pollutants in biofilters. Due to such complexities, stream passes through the trickling biofilter, either as co- or
removal rates for mixtures may need to be determined using counter current flow to the liquid, and supplies the essential
case-by-case treatability studies. The removal of VOCs us- carbon source for microorganisms. Some factors affecting
ing fungi-inoculated biofilters was initiated recently. Fungi pollutant removal are: (i) composition and concentration
may show some advantages over bacterial cultures, espe- of the waste-gas stream, (ii) structural configuration of the
cially for the treatment of hydrophobic VOCs, because of packing material, (iii) flow pattern, (iv) nutrient composi-
their ability to degrade the substrate under extreme envi- tion, (v) gas-flow rate or residence time, (vi) pH, and (vii)
ronmental conditions of pH (2 to 7) or low water content. It temperature.[48] Typical filter media can be inert materi-
was also hypothesized that the large surface area of hyphae als such as ceramic or plastic structures, activated carbon,
provided by filamentous fungi would enhance absorption celite or mixtures of materials.[7, 49]
and transport of hydrophobic compounds from the gas- Biotrickling filters have been used successfully to treat
phase to the cell surface.[47] compounds that produce acidic or alkaline metabo-
Recent developments in this field include: understanding lites such as halogenated hydrocarbons, H2 S, NH3 and
pollutant degradation pathways, use of molecular profiling dichloromethane.[46, 50] The metabolites generated from
Fig. 7. Schematic of an adsorption column+biofilter used for flow equalization and handling periodic shock-loads.
microbial degradation can be easily removed by the re- unit and the bioreactor unit (usually an activated sludge
circulating liquid stream. In addition they are able to reactor). In the first-stage scrubber, the contaminants are
withstand high pollutant loadings due to high biomass absorbed by a continuously moving water phase, while in
concentrations.[51] Biotrickling filters have also proven to the bioreactor contaminants in water phase are degraded
be highly efficient in handling mixtures of hydrophilic and by aerobic microorganisms (Figure 6). The scrubbing liq-
hydrophobic VOCs, as they are able to maintain dominant uid can also be continuously recycled after regeneration in
species of both fungi and bacterial cultures within the same the bioreactor unit. However, the degree of regeneration
reactor configuration. depends on the size of the bioreactor unit and the retention
López et al.[50] investigated the combined removal of H2 S, time of the scrubbing liquid.[12]
methanol and α-pinene vapours in a single-stage biotrick- The bioscrubbing process is easily controlled be-
ling filter, at empty bed residence times of 38 and 26 s, and cause pH, temperature, nutrient balance and removal of
reported maximum elimination capacities of 191, 307 and metabolic end-products can easily be altered in the water
123 g/m3.h, for H2 S, methanol and α-pinene, respectively. phase of the reactor.[56] Bioscrubbing systems have been
The main drawback of this system is the problem associ- used for the biodegradation of odorous compounds and
ated with mass transfer, especially for compounds that are some of the target industries are the following: rendering
hydrophobic. Biotrickling filters are effective for the treat- plants, livestock farming, public owned treatment works,
ment of gaseous compounds with an air/water partitioning food industries and foundries.
coefficient of less than 0.1.[51] Gas-phase pollutants such as H2 S, SO2 and highly water
The other drawbacks include channelling, filter material soluble compounds such as alcohols, aldehydes and fatty
degradation, high pressure drop, and the accumulation of acids have successfully been removed using bioscrubbers.
excess biomass.[52,53] Several methods have been proposed The important types of scrubbers are: (i) counter and co-
in the literature to remove the accumulated biomass, and current packed towers, (ii) cross flow packed towers, (iii) wet
thereby reduce pressure drop: backwashing, air sparging, cyclones, (v) spray towers, and (vi) Venturi scrubbers.[57]
increasing the trickling rate of the medium, mechanical ag- Whaley et al.[58] treated isopropyl alcohol, acetone and
itation, biological predation, and adopting improved oper- heptane in a pilot-scale bioscrubber in a concentration
ational modes.[41, 54, 55] range of 200–500 mg/m3 and observed removal efficien-
cies greater than 99%, two weeks after start-up. In a study
aimed at removing odorous sulphur compounds from ven-
Bioscrubbers (Absorption pre-treatment + bioreactor)
tilation air in a wastewater treatment plant, Heist et al.[59]
A bioscrubber is a biological waste-gas treatment system achieved oxidation rates of 155 mg/g.h at a pH of 9, for sul-
consisting of two individual units, namely the scrubbing phur concentrations above 2 mg/l. Studies by Schippert[60],
930 Rene et al.
Fig. 8. Schematic of a two-stage reactor (UV photoreactor -or UV Photocatalytic reactor+biofilter) for handling periodic shock-loads.
on the removal of mixtures of butyl glycols, n-butanol, transfer coefficient and gas-liquid interfacial area), lead-
ethyl glycol, isobutanol, xylene and methyl-isobutyl-ketone ing to a higher rate of transfer of the solute gas across the
(MIBK) showed that xylene and MIBK were poorly re- boundary layer.
moved (70%), compared to other VOCs (99%) in bioscrub- In that study, the total load applied to the bioscrub-
bers. In general, the scrubbing liquid and vapour stream ber was 852 g VOC/m3.h, while the liquid to gas (L/G)
should be carefully selected, as they lose their cost efficiency ratio was maintained at 0.0094. The authors reported
for compounds having a Henry’s coefficient > 0.01.[52] Typ- steady state VOC removal efficiencies of 40–47% in the
ical superficial air velocities in bioscrubbers vary in the bioscrubber, and the addition of cutting oil did not affect
range of 0.5 to 2.5 m/s. the metabolic activity of the microorganisms in the bio-
Though bioscrubbing presents high potential for devel- logical reactor. In another study, a semi-industrial type
opment because VOC transfer and biodegradation could scrubber fitted with atomizing spray nozzles was tested
be separately improved[61], they have not been used widely for the removal of 11 VOCs (methanol, acetone, methyl-
due to complex start-up procedure, high operational cost ethyl-ketone, methyl-isobutyl-ketone, ethyl acetate, butyl
and sludge generation. If packed towers are used in the acetate, toluene, ethylbenzene, xylene, 1,2-dichloroethane,
scrubbing unit, during the start-up or acclimation phase, and dichloromethane) over a period of 13 months,
microorganisms start to grow on the packing and form a using a non-defined washing liquid as the scrubbing
biofilm, which would play a major role in affecting the per- medium.[63]
formance of the scrubber. Hence, adequate care should be That bioscrubber was started with a load of 852 g
taken to avoid clogging of the scrubbing unit. VOC/m3.h for 6 months, and the load was subsequently
However, recent advancements have been made in this increased to 1704 g VOC/m3.h for 3 months, and then
system in order to optimize VOC mass transfer in the scrub- decreased to 426 g VOC/m3.h for 4 months. The authors
ber. Lalanne et al.[62] proposed a two-phase partitioning reported removal efficiencies ranging from 35 to 50% dur-
bioscrubber as a high performance biotechnology alterna- ing these phases of operation, and most of all the absorbed
tive for the treatment of waste-gases containing a mixture compounds were degraded in the bioreactor.
of oxygenated, aromatic and halogenated compounds. The Among the above-mentioned three biological waste-gas
addition of cutting oil (2.5 to 10 mass-%) to the water phase, treatment systems, biotrickling filters and bioscrubbers are
according to the authors, changed the physical properties applicable mainly for the treatment of polluted air contain-
(density, gas solubility and gas diffusivity) of the liquid mix- ing moderately water soluble compounds, while biofilters
ture, and the gas-liquid characteristics (droplet distribution are particularly successful for handling poorly water sol-
inside the boundary layer, mass transfer mechanism, mass uble compounds. Biotrickling filters are more complex to
build, but they have been widely used to handle waste- Performance of combined non-biological and biological
gases containing acidifying contaminants such as sulphur techniques for waste-gas treatment
and/or nitrogen containing compounds and halogenated
compounds, wherein acidic end-products are continuously Shock-loads, in the form of sudden fluctuating load-
removed by the recirculating aqueous solution.[64] ing rates, have always posed a major challenge for the
design and operation of any bioreactor system. Short-
term/temporary high loads can result in diminished treat-
Performance parameters of waste-gas treatment systems ment performance because of limitations in the biological
The performance of a biological waste-gas treatment sys- reaction capacity of the suspended or attached microor-
tem can be estimated using the following equations.[3, 7] ganisms, and the pollutant mass transfer rates.[7, 40, 41, 65]
Unit flow: On the other hand, low contaminant loading can lead to
unexpected starvation conditions of the microorganisms
Q present in the bioreactor, which eventually decreases cell
UF = , [1/h]
V activity and reactor performance after the starvation pe-
riod. Different strategies can be used in order to limit the
Mass loading rate: effects of non-steady-state conditions, among which is the
use of a non-biological pre-treatment step.

Q × Ci n
MLR = , g/m3 .h
V Adsorption pre-treatment + bioreactor
Elimination capacity: A general schematic of a combined adsorption+biofilter
system for VOC treatment is shown in Figure 7. Weber
Q × (Ci n − Cout ) and Hartmans[66] used an activated carbon bed, prior to
EC = , g/m3 .h
V a biofilter, to minimize fluctuations in toluene loads. It
was observed that the buffering capacity of the adsorbent
Removal efficiency:
depended highly on the desired concentration range of
(Ci n − Cout ) the contaminants entering the bioreactor and on the time
RE = × 100, [%] available for desorption. For relatively high gas-phase
Cin
toluene concentrations, up to 1000 mg/m3, the activated
Carbon dioxide production rate: carbon bed was able to reduce that concentration to a value
of about 300 mg/m3, which was then completely degraded
Q × (CO2,out − CO2,in ) in the biofilter. Later, Li and Moe[67] also demonstrated
PCO2 = , g/m3 .h the use of a granular activated carbon (GAC) packed bed,
V
as a load-equalization step, before a biofilter, to handle
Table 2 shows typical elimination capacities achieved in dynamically varying pollutant loads of gas-phase acetone
different lab-scale waste-gas treatment systems. and toluene.
Table 2. Typical maximum elimination capacities (ECmax ) achieved in waste-gas treatment systems.
Pollutants ECmax (g/m3.h) Bioreactor configuration EBRT (s) References
Ethyl acetate 180 BF 180 [89]

Hydrogen sulphide 101 BF 36 [90]
101 BF 162.6 [91]
Methanol 185.3 BF 53.8 [92]
234 MB 30 [93]
α-Pinene 143 BF 72 [94]
232 BTF 60 [95]
Toluene 165 BF 78 [96]
Styrene 336 BF 91.2 [97]
110 CSTB 64
Dichloromethane 160 BTF 90 [46]
BTEX 218 BTF 96
188 BTF 96 [98]
n-Hexane 64 BF 120 [99]
Methanol 307
H2 S 191 BTF 26, 38 [50]
α-Pinene 123
932 Rene et al.
This combined system was operated to simulate load tions of n-hexane (10 to 470 ppm) and benzene (30 to
variations in industrial situations by passing contaminated 1410 ppm).
air (8 h/d) and uncontaminated air (16 h/d) to the com- The cyclic adsorption/desorption bed systems were de-
bined system, where the empty bed residence time was 2.5 signed to run on a short-term cycle that depends on con-
s for the GAC bed and 14.5 s for the biofilter. The exper- taminant pressure variation and were designed to operate
imental results showed that, the passively operated GAC in a two-step cycle, i.e., feeding (adsorption) and purg-
load-dampening system leads to more uniform loadings ing (desorption) within cyclic adsorption/desorption beds.
and thereby improves the biofilter performance. Similar The authors reported that the cyclic adsorption/desorption
improvements in performance with GAC units tested un- beds unit successfully achieved its goal of stabilizing erratic
der fluctuating toluene loading patterns (8 h/d) have also loadings even with very sharp peaks in the inlet concentra-
recently been confirmed by other authors.[68] Moe et al.[69] tion. Moreover, the unit also buffered the fluctuating inlet
studied the effects of cycle length and fraction of time con- load and the biofilter had all the time a continuous stable
taminants (toluene - 1000 or 250 ppmv) are supplied on the flow, even during the starvation phase where no contami-
degree of load equalization achieved by passively operated nant was fed to the cyclic beds. From a practical applica-
GAC beds, by subjecting the GAC bed to different cyclic tion view-point, the adsorption column would be operated
loading conditions. under an extremely low residence time, or it would be op-
The authors concluded that “GAC columns can tem- erational only when high pollutant loads are encountered
porarily accumulate contaminants during intervals of high in the waste-gas stream.
influent concentration and desorb contaminants during in-
tervals of no loading, resulting in appreciable load equaliza-
Bioreactor + adsorption “polishing”
tion without the need for external regeneration by heating
or other means. Greater load equalization was achieved as GAC adsorption can also be used as a “polishing”,
the fraction of time toluene was loaded decreased and as post-treatment, process. Hansen[72] used a sequence of
the cycle length decreased”. Similarly, Nabatilan et al.[65] bioscrubber+adsorption filter to remove mixtures of hy-
installed a column packed with granular activated carbon, drogen sulphide and organo-sulphur compounds from a
prior to the biotreatment step, to achieve load equalization wastewater treatment plant. In this case the adsorption
for the biological treatment of toluene (250 ppmv). The unit acted as a “polishing” system. The bioscrubber was
results showed that load equalization can be achieved in operated at a pH of 8.5 to 9, and was able to remove a
GAC columns receiving intermittent pollutant loadings in maximum hydrogen sulphide concentration of 37 mg/m3,
combination with intermittent reduction of the air flow rate and some of the organo-sulphur compounds (concentra-
during pollutant non-loading intervals. tions less than 0.1 mg/m3) were treated adsorbed in the
However, the use of a single GAC bed, prior to a bio- second-stage adsorption unit.
logical system, also has its own disadvantages. The GAC
bed would lose its buffering capacity when it is exhausted,
UV pre-treatment + bioreactor
and the bioreactor would experience a starvation period
before the GAC column starts to breakthrough, which The presence of hydrophobic VOCs in waste-gases, at high
would eventually alter the long-term performance of the bi- loading rates, has shown to induce toxic and inhibitory
ological system.[70] Cai and Sorial[71] evaluated a dual-fixed effects for stand-alone bioreactors, such as biofilters and
adsorption system with a two-step adsorption and desorp- biotrickling filters. However, the stand-alone use of UV-
tion cycle, followed by a biotrickling filter, for dampening photoreactors for waste-gas treatment, depending on the
load fluctuations of a mixture of gas-phase toluene, styrene, chemical composition, is limited in application due to its
MEK and MIBK. For VOC loads less than 34 g/m3.h, the tendency to produce water soluble by-products that are
cyclic beds performed better and buffered the fluctuating of environmental concern. Keeping this in mind, when
inlet loads. a biofilter or a biotrickling filter are placed downstream
The performance of the integrated adsorption- of a UV-photoreactor, the by-products together with the
biotrickling filter system was improved, showing more non-treated air should presumably be removed readily by
than 99% removal efficiency for the VOCs, irrespective of the microorganisms present in the bioreactor. Less re-
the fluctuations in the inlet load. The authors also sug- search has, however, been done on such combinations, com-
gested that the two-step adsorption and desorption cycle pared to adsorption-bioreactor combinations for waste-gas
would act as a feeding source during starvation periods, treatment.
and also enhances the re-acclimation time for the biotrick- The combination of UV pre-treatment in a photoreac-
ling filter, while at the same time regenerate the adsorber tor and different bioreactor configurations has received
beds. Similarly, Aly Hassan and Sorial[70] also proposed only little attention recently among researchers. The first-
the utilization of dual GAC beds connected in series stage UV enhanced photooxidation step can be divided
and operated in flow-switching mode prior to a biotrick- in two groups: UV-photolysis and UV-photocatalysis. The
ling filter for the treatment of peak gas-phase concentra- efficiency of stand-alone UV-photolysis depends on the
molar absorptivity of the target gas-phase pollutant at the The authors compared the performance of the UV-
wavelength employed, the intensity of the UV light source, photolysis+biofilter system with that of a stand-alone
the initial concentrations of the different VOCs present in biofilter, and reported that the stand-alone biofilter was
the waste-gas, relative humidity and the concentration of able to reach a maximum elimination capacity of 15 g/m3.h,
added oxidants, if any.[22] In most of the lab-scale studies, while the biofilter combined with the photoreactor reached
UV-photolysis has been carried out using commercially a maximum elimination capacity of 20 g/m3.h. It was
available low-pressure mercury vapour lamps having peak suggested that the biofilter combined with a UV-photolysis
light intensity at 254 nm or 185 nm. reactor not only provides synergistic effects on the
On the other hand, UV-photocatalysis uses a suitable biofiltration process, in terms of enhanced capacity and
semi-conductor catalyst (mostly TiO2 ), to generate a pair effectiveness, but also can remove the water-soluble inter-
of conduction band electron and a valence band hole in the mediates formed from the first-stage photoreactor. Den
solid oxide lattice upon absorbing a photon with energy et al.[76] compared the performance of a biotrickling filter, a
greater than 3.2 eV, and the subsequent charge transfers at plug-flow photoreactor, and an integrated UV- biotrickling
the interface initiate various kind of redox reactions under filter system for the removal of TCE and PCE vapours.
well-controlled ambient conditions. Semi-conductors like The authors inoculated the granulated activated carbon
ZnO, WO3 , Fe-TiO2 and Sr-TiO2 have also been used to packed biotrickling filter with a mixed microbial consor-
carry out photo-induced redox reactions for the degrada- tium obtained from a chlorinated solvent contaminated
tion of VOCs in gas-phase. Photocatalytic reactors have site and performed experiments in the concentration
performed with higher efficiencies as stand-alone systems range of 25–350 ppmv for TCE and 5–45 ppmv for PCE,
than direct photolysis based photoreactors for the treat- respectively. The dominant organism was later identified as
ment of VOCs in gas-phase, but the advantages of coupling Pseudomonas strain. UV photoreactor experiments were
a photocatalytic reactor with a bioreactor has not been performed using a low-pressure mercury lamp, having a
fully explored by researchers. power output of 4 W (254 nm), a light intensity of 1.4
A combined UV photo-catalytic oxidation system as mW/cm2, and at gas-residence times of 6 to 36 s. The
a pre-treatment step followed by a biological waste-gas authors reported that the removal efficiencies of both TCE
treatment system offers the following advantages: (i) rapid and PCE were >99% in the combined UV+biotrickling
oxidation of a wide variety of recalcitrant compounds filter system, which was greater than either the stand-alone
to soluble and biodegradable form, (ii) ability to reduce biotrickling filter or the UV photoreactor system. On
high concentrations of pollutants to limits that can easily the other hand, the photooxidation products of TCE
be handled in a biological system,[73] (iii) versatility to and PCE, identified as phosgene, dichloroacetyl chloride,
handle unexpected variations in pollutant loading rate, trichloroacetyl chloride, carbon monoxide and hydrochlo-
(iv) no pressure drop and clogging related operational ric acid, were completely removed in the second-stage
difficulties, and (v) photo-oxidation step can also be used biotrickling filter that occurred by a combination of
as a post-treatment or “polishing” step when bioreactor hydrolysis, adsorption and microbial degradation.
performance is limited or inhibited. The presence of adsorbents like GAC in biological sys-
The use of a UV/bioreactor combination (Figure 8) has tems can help adsorbing highly adsorbable intermedi-
been reported in a few studies and synergistic effects in ates, resulting in enhanced microbial biodegradation of
pollutant removal have been observed.[74,75] Mohseni and slowly or poorly biodegradable compounds. Moussavi and
Zhao[75] combined an annular photoreactor and a biofilter Mohseni[77] showed that UV photolysis can be used as a
for the treatment of o-xylene vapour. The first-stage pho- first-stage system followed by a biofilter for the removal of
toreactor was fitted with an ozone producing low-pressure a mixture of VOCs, toluene and o-xylene, from polluted air.
mercury lamp that has its peak light intensity at 254 nm (97 In that study, a series of 7 experimental runs was conducted,
W/m2), and the photoreactor was subjected to o-xylene including acclimation to the biofilter, under the following
concentrations varying between 0.06 and 0.22 g/m3 at a test conditions: gas-residence time in the photoreactor- 0.57
gas-residence time of 0.5 and 1.2 s, respectively. The authors and 1.5 s, empty bed residence time in the biofilter- 30 and
observed a maximum elimination capacity of 200 g/m3.h 45 s, toluene concentration- 44.7 to 121.4 ppm, o-xylene
in the stand-alone UV photoreactor, despite subjecting it concentration- 29.8 to 132.7 ppm, and UV fluence- 6 to 12
to high loads of o-xylene (1300 g/m3.h) and attributed the mJ/cm2. The authors reported that, for inlet loading rates
lower removal to the fact that the process of direct photoly- up to 48 g toluene/m3.h and 46 g o-xylene/m3.h, the UV
sis was photon limited and there were not enough photons photoreactor+biofilter showed a near complete removal
with high energy to break down the organic molecules. for both the VOCs, while the stand-alone biofilter yielded
Later, the UV photoreactor was combined with a biofilter smaller elimination capacity values (<25 g/m3.h) for both
packed with wood chips and yard waste compost, and ex- the tested VOCs.
periments were performed continuously for about 70 days, The authors reported that the stand-alone biofilter did
at empty bed residence times of 35 and 75 s in the biofilter, not perform well due to the severe inhibitory effects of
and inlet o-xylene loads varying between 2 and 22 g/m3.h. xylene on toluene removal, while still higher elimination
934 Rene et al.
Fig. 9. Comparison of elimination capacity in the stand-alone photocatalytic reactor, the continuous stirred tank bioreactor, and the
combined process, for dichloromethane removal from gas-phase.
capacities could be reached in the combined UV Besides, under well-optimized conditions, the authors
photoreactor+biofilter as it did not reach a plateau over report that toluene removal efficiencies as high as 96.7%
the range of inlet toluene and o-xylene loadings tested. could be attained in the integrated system, at an empty
Besides, the biofilter was able to completely remove the in- bed residence time of 121.3 s in the biofilter, for inlet
termediates formed from toluene and o-xylene oxidation in concentrations varying between 210 and 500 mg/m3. The
the photoreactor (acetaldehyde, formaldehyde, propanal, authors also reported that the intermediate organic prod-
glycolaldehyde and benzyl alcohol), and the ozone gener- ucts of toluene oxidation, namely benzaldehyde, benzene,
ated from the photoreactor enhanced the degradation of benzal methanol, formaldehyde, vinyl methyl ketone and
these VOCs and helped to control excess biomass growth methyl glyoxal formed in the photocatalytic unit, were sub-
in the biofilter. sequently converted to CO2 and H2 O in the biofilter.
The authors also reported that relatively low concen- For practical purposes and in order to save operational
trations of ozone can be removed in the biofilter and its costs, it is advisable to use the UV pre-treatment step
presence did not affect the activity of VOC degrading mi- only when absolutely required. The UV lamps can be
croorganisms in the biofilter. The authors stressed the im- energized/turned–ON when the pollutant concentration
portance of this integrated system as follows: the presence is high, i.e., during unexpected load fluctuations, with the
of a UV pre-treatment stage is more beneficial in cases help of online sensors. The UV-operated photocatalytic re-
where the contaminant loadings become high and reaches actor can then serve as a load equalization system by bring-
beyond the level that is completely removed in the biologi- ing down the pollutant loads to levels easily treatable in the
cal system. bioreactor. In a recent study performed in our laboratory, a
Wei et al.[78] operated a bench scale photocatalytic oxida- photocatalytic reactor and a continuous stirred tank biore-
tion unit, where N-doped TiO2 /zeolite was used as the cat- actor (CSTB) were coupled to handle a 7-h shock-load of
alyst, combined with a biofilter, inoculated with activated dichloromethane vapour. The first-stage annular type pho-
sludge from a wastewater treatment plant and operated at tocatalytic reactor, coated in the inner side of the annular
an empty bed residence time of 40.4 to 121.3 s, for the space with commercially available TiO2 +poly vinyl alco-
removal of gas-phase toluene. The N-doped TiO2 /zeolite hol, was operated at a gas-residence time of 55.2 s, and
in the photoreactor was exposed to a luminous source illuminated with a 50 W UV light source.
composed of a 4 W UV-lamp, and a 4 W Visible lamp The second-stage CSTB was inoculated with Hypomi-
placed in axial position. The authors compared the per- crobium spp., and was operated at a residence time of 120
formance of the photoreactor under different operating s. It was observed that, when the inlet load was increased
conditions: pure TiO2 +UV, N-doped TiO2 +UV, N-doped from low (70 g/m3.h) to exceedingly high load of 1056
TiO2 +Visible light, and N-doped TiO2 +UV+Visible light, g/m3.h, the photocatalytic reactor was able to eliminate
in order to ascertain the photoactivity and found that nearly 70% of the load, thereby saving the second-stage
the N-doped TiO2 with UV and the N-doped TiO2 with CSTB from severe shock-load that would otherwise in-
UV+Visible light showed higher purification efficiency (> hibit bacterial activity, and affect its long-term performance
50%), at toluene concentrations of 290 mg/m3, and oper- (non published data). As summarized in Figure 9, the per-
ated at a gas-residence time of 4.5 s. formance of the integrated system was higher than the
Fig. 10. Schematic of a two-stage bioreactor (first-stage biotrickling filter and a second-stage biofilter for H2 S and VOC removal from
waste-gases).
standalone performance of the photocatalytic reactor and Bioreactor/bioreactor combinations

the CSTB.
Sometimes a combination of two biological techniques can
I
be used, especially when the waste-gas contains mixtures of
The Langmuir-Henshelwood (L-H) type rate equation
pollutants with different physicochemical characteristics or
is most commonly used to express gas-solid phase reac-
different biodegradation rates. In this case, the first-stage
tions in plug-flow type photocatalytic reactors.[20, 78] In this
biological reactor would be designed and operated in such
kinetic model, it is assumed that the gas-phase pollutant
a way that it would serve as the primary system responsible
mass transfer is not the limiting step, and the effect of in-
for removing some of the gas-phase pollutants, while the
termediate products is negligible. The values of k and K are
second-stage system would remove the non-treated pollu-
estimated from the following rate equation:
tants from the first-stage, as well as other specific pollutants
present in gas-phase. Standefer and Willingham[79] used a
ln (Ci n /Cout ) kK(V/Q)
= − K, combination of a bioscrubber and a biofilter to handle
(Ci n − Cout ) (Ci n − Cout ) 60000 m3 gas/h containing nitrogen compounds, glycols,
ln (Ci n /Cout ) 1 alcohols and aldehydes with a gas residence time below one
by plotting vs .
(Ci n − Cout ) (Ci n − Cout ) second. Their studies showed a removal efficiency >92%
for readily soluble compounds, while removal efficiencies
In bioreactors, the biodegradation rate of the gas-phase ranged between 70 and 95% for other compounds.
pollutant can be estimated from the simple Michaelis- In this case, the second-stage biofilter was used as a “pol-
Menten or Monod equation that takes the form: ishing” step. Another rather common situation is the co-
treatment of hydrogen sulphide and VOCs. In such case,
1 Ks 1 1 the pH of the biofilm would drop when hydrogen sul-
= × + phide is converted to sulphuric acid, which inhibits the
R Vm Cln Vm
biological activity of most VOC degraders in a bioreactor.
(Ci n −Cout ) Acidification-related problems may sometimes also include
where, Cln = ln(C i n /Cout ) an acid attack on the organic packing media, channelling
The values of Vm and Ks can be calculated from the linear in some site specific areas and filter bed compaction. Cox
relationship between C1ln and R1 . et al.[80] reported the long-term performance (10 month
936 Rene et al.
period) of a biotrickling filter (EBRT: 24 s) treating a mix- bioreactor during starvation periods. However, adsorption
ture of H2 S and VOCs from the Hyperion treatment plant. units can also be used as “polishing” units, when placed
About 25 to 35% of low concentrations of benzene, as a second-stage treatment process after a bioreactor.
toluene and chlorobenzene were removed, while other Another well known combination consists in using a
chlorinated VOCs could not be removed in the biotrickling scrubber as a pre-treatment step followed by a bioreactor.
filter. The low VOC removal was attributed to the presence Such a combination, known as a bioscrubber, is above all
of inhibitory concentrations of sulphate in the recycle suitable for relatively highly water-soluble pollutants.
liquid and the possible accumulation of metabolites other Photooxidation of volatile pollutants offers many ad-
than sulphate that inhibit VOC biodegradation. Emissions vantages, both as a stand-alone system and when com-
from pulp and paper industries contain hydrogen sul- bined with a bioreactor for waste-gas treatment. Our own
phide, methanol and α-pinene, representative inorganic, experience suggests, however, that the efficiency of using
hydrophilic, and hydrophobic organic pollutants.[81] A UV only (photolysis) is rather limited compared to a UV-
two-stage biological system (Figure 10) comprising a TiO2 system (photocatalysis). Under well-optimized con-
first-stage biofilter and a second-stage biotrickling filter ditions, photocatalytic reactors can effectively withstand
was proposed to treat this complex gas-phase pollutant short-term shock-loads and reduce pollutant loads to lev-
mixture. In that study, the biotrickling filter was inoculated els acceptable in a biological system, showing the potential
with autotrophic hydrogen sulphide degraders and an suitability of this technique as a pre-treatment step.
acid-tolerant yeast (Candida boidinii), while the biofilter Additionally, the water-soluble end-products from the
was inoculated with the fungus Ophiostoma stenoceras, photoreactor can afterwards effectively be removed in the
and experiments were performed at different inlet loading second-stage bioreactor without hindering the activity of
rates and process conditions. the microorganisms. However, depending on the nature
Hydrogen sulphide and methanol were removed in the and composition of the waste-gas, and the degree of
first-stage biotrickling filter with maximum elimination ca- treatment attained in the bioreactor, a photocatalytic
pacities of 45 and 894 g/m3.h, while α-pinene was removed reactor can be designed/modified to be used a pre- or
predominantly in the second-stage fungal biofilter with a post-treatment step. The combination of two bioreactors
maximum elimination capacity of 138 g/m3.h. The original in series can be recommended in the following situations:
idea was initially to remove H2 S in the first reactor, with (i) when the waste-gas contains a mixture of inorganic
medium acidification, and all the VOCs in the second reac- and organic pollutants; and some of their degradation
tor at constant pH. However, the acidipholic methanol de- end-products are highly acidic, the first-stage bioreactor
grader inoculated in the first reactor appeared to be highly can host a mixture of acid-tolerant microorganisms in
acid-tolerant, and methanol was easily removed in the first- order to eliminate those pollutants, and (ii) when two dif-
stage together with H2 S. ferent groups of pollutants need to be degraded, different
Chitwood and Devinny[82] evaluated the feasibility of microbial species can be maintained in each bioreactor that
using a two-stage biofilter for the treatment of H2 S, are specific for the given pollutants. In the latter situation,
air toxics and smog precursors. The first-stage acid-gas i.e., for waste-gas containing a mixture of hydrophilic
biofilter packed with lava rock contained acidophilic au- and hydrophobic compounds, the hydrophilic pollutants
totrophic bacteria to remove H2 S, while the second-stage can be treated in one bioreactor while the hydrophobic
wood chip biofilter removed other air toxics that in- substrates can be treated in the bioreactor with addition
cluded methanol, acetone, methylene chloride, chloro- of an organic phase such as silicone oil if needed.
form, toluene, xylene, ethylbenzene, methyl-tert-butyl-ether
(MTBE) and 2-methyl butane. However, they observed that
the first-stage AGB removed acetone and methanol com- Acknowledgments
pletely, while other VOCs were intermittently removed de-
pending on the concentrations, in addition to 99.6% re- The authors would like to acknowledge the financial sup-
moval of H2 S at an inlet loading rate of 0.057 g/m3.h. port of the Spanish Ministry of Foreign Affairs (project
A/024301/09), and European FEDER funds. ERR is also
Conclusions grateful to the Spanish Ministry of Science and Innovation
for his research contract (JCI-2008-3109).
The mechanism of pollutant removal in the most com-
monly used biological and non-biological waste-gas Nomenclature
treatment systems, and the advantages of combining
biological systems with physico/chemical systems were AOC = Assimilable organic compound
reviewed in this paper. An adsorption unit, when used AOPs = Advanced oxidation processes
as a pre-treatment step for a bioreactor, would handle BET = Branauer-Emett-Teller
dynamically varying pollutant loads acting as a buffering BOD = Biological oxygen demand
unit during shock-loads and as a feeding source to the BF = Biofilter
BTEX = Benzene, toluene, ethylbenzene and xy- R = VOC removal rate (g/m3.h)
lene V = Volume of the reactor or packed bed or
BTF = Biotrickling filter aqueous medium (m3)
COD = Chemical oxygen demand Vm = Maximum pollutant removal rate
CPR = Carbon dioxide production rate (g/m3.h)
CSTB = Continuous stirred tank bioreactor α = Constant of BET model
DCM = Dichloromethane
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Combined biological and physicochemical waste-gas

ELDON R. RENE, MARÍA C. VEIGA and CHRISTIAN KENNES

Introduction sions of pollutants to the atmosphere as they affect climate

(AOPs). This paper provides a general overview of some of

Absorption Chemical scrubbing

Fig. 1. Example of an absorption column: spray chamber.

band and an empty conduction band, and the energy dif-

Excitation Oxidation reaction

Fig. 3. Mechanism of photocatalytic oxidation.

carbon, and their ratios, BOD/COD and BOD/TOC,

Table 1. Photocatalytic oxidation products of gas-phase pollutants in photocatalytic reactors.

Fig. 4. Schematic of a biofilter.

pinocamphone, 3-hydroxyl-α-pinene, acetaldehyde, ace- Biological waste-gas treatment techniques

Fig. 5. Schematic of a biotrickling filter.

Fig. 6. Schematic of a bioscrubber with a scrubber and a bioreactor unit.

use of a non-biological pre-treatment step.

Pollutants ECmax (g/m3.h) Bioreactor configuration EBRT (s) References

Ethyl acetate 180 BF 180 [89]

standalone performance of the photocatalytic reactor and Bioreactor/bioreactor combinations

vironmental applications of semiconductor photocatalysis. Chem. 1991, 41, 1045–1054.

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