Biofiltration of Air 1A

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    Critical Reviews in Biotechnology, 25:5372, 2005

    Copyrightc Taylor & Francis Inc.

    ISSN: 0738-8551 print / 1549-7801 online

    DOI: 10.1080/07388550590935814

    Biofiltration of Air: A RevieMarie-Caroline Delhomenie

    and Michele Heitz

    Chemical Engineering

    Department, Faculty of

    Engineering, Universite de

    Sherbrooke, Canada

    ABSTRACT In this paper we present a review of the existing air pollu

    control technologies (APCT), when used essentially for the eliminatio

    volatile organic compounds (VOC). The biotechnologies referred to, biosc

    bers, biotrickling filters and biofilters, are also described. A more detailed re

    of biofiltration is proposed, presenting the most recent and latest developm

    achieved in the field of bioprocessing. In particular, the influence of the fi

    bed, the polluted air flowrates, the pollutants, the pressure drop, bed m

    ture content, temperature, nutrients, pH and the microorganisms are revie

    Models of biofiltration are also presented.

    KEYWORDS biofiltration, air treatment, air pollution control, biotechnologies, voorganic compounds.

    CONTEXT

    The recent pollutant release inventories, published by various governm

    and environmental organizations, demonstrate that, since the beginning o

    20th century, emissions of atmospheric pollutants in North America have b

    in continual increase. Thus, in 2000 in Canada, some 41 Mt of pollutants ticulate matter, SOX, NOX, COXand volatile organic compoundsVOC)

    released to atmosphere, representing about 1.3 t/person living in Canada.

    industrial sector alone was responsible for 13% of these releases, which conta

    about 7% of VOC (Environnement Canada, 2000). On another scale, in 2

    the USA emitted some 150 Mt of pollutants (0.5 t/person), containing 10

    of VOC, mostly produced and released by the industries (US Environme

    Protection Agency, 2003).

    Most VOC emitted to the atmosphere are likely to be harmful to hu

    health (generating nausea, headaches, irritation and affecting the nervous

    breathing systems, initiating cancers, etc.), and they also contribute to substa

    damage on fauna and flora (Barnes, 1998). In addition to their toxic effVOC families, such as the chlorofluorocarbons (CFCs), present characteristi

    greenhouse effect gases. Some VOC (freons, halons,etc.) are directly involve

    the degradation of the stratospheric ozone layer, the natural filter for ultrav

    radiation, whereas other VOC, combined with NOX, are precursors for

    tropospheric ozone layer formation, which causes the urban smog visible ab

    large agglomerations (Barnes, 1998):

    Sunlight+ VOC+NOX + air/O2 photosmog

    Address correspondence to MicheleHeitz, Chemical EngineeringDepartment, Faculty of Engineering,Universite de Sherbrooke, Sherbrooke,QC, J1K 2R1, Canada. E-mail:[email protected]

    53

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    All of this data illustrate the fact that technological

    short-term depollution solutions must be developed

    and applied to reduce the amplitude of these emissions.

    Concerning the VOC emissions problem, existing de-

    pollution measures are of three orders:

    1. to ban the utilization of certain VOC in industrial

    processes (case for the benzene and freons);

    2. to review and modify existing processes to reducetheir associated VOC emissions and to make them

    less polluting (by installation of recycling systems,

    for example);

    3. to install depollution systems downstream of the

    emitting sites.

    This latter category of depollution solutions will form

    the subject of the remainder of this work. A brief review

    of the air pollution control technologies (APCT), as

    applied to VOC reduction, will be presented. Then,

    among the various proposed control technologies, theapplicable biotechnologies will be principally discussed,

    with the emphasis placed largely on the application of

    biofiltration.

    DEPOLLUTION TECHNOLOGIES

    Due both to the diversity and to the quantities of

    VOC released into the atmosphere, a variety of APCT

    have been developed. The operating process for all of

    these APCT involves either one or several physico-

    chemical air/contaminant separation steps. The main

    differences between the APCT are related to the treat-

    ment of pollutants, following the separation procedure

    for their recovery (recycling) or destruction.

    The main APCT giving rise to recovery and recycling

    of VOC are the following:

    phase transfer technologies: adsorption and absorp-

    tion. VOC concentration technologies: condensation, cry-

    ocondensation and membrane processes. These tech-

    nologies permit the extraction of VOC from the ini-

    tial gas phase, and to then concentrate them.

    Processes leading to the partial or total elimination of

    VOC involve the use of more or less drastic oxidative

    ways:

    combustion processes: incineration and catalytic

    oxidation.

    chemical or photochemical oxidation technologies. biotechnologies: biotrickling filter, bioscrubber, and

    biofilter.

    Table 1 presents some characteristics of the main

    APCT, as applied to the VOC elimination (Hermia

    and Vigneron, 1993; Ruddy and Carroll, 1993; van

    der Vaart et al., 1994; Huang et al., 1997; Crocker and

    Schnelle, 1998; Goralski et al., 1998; Sylvester et al.,

    1998; Hurashima and Chang, 2000; Degreve et al., 2001;

    Wang et al., 2001).

    The choice of a well-adapted process depends on the

    operating conditions (flow rate, VOC concentrations,

    temperature, humidity, etc.) and on the pollutants

    physico-chemical characteristics (solubility, phase tran-

    sition points, biodegradability level, inflammability,

    etc.) (Crocker and Schnelle, 1998). Figure 1 presents

    the application limits (flow rateVOC concentration)

    of the different APCT (Juteau, 1997; Crocker and

    Schnelle, 1998; Devinny et al., 1999).

    As indicated in Table 1 and Figure 1, biological pro-

    cesses constitute pertinent ways for the elimination of

    biodegradable VOC (alcohols, ketones, aldehydes, aro-

    matic compounds,etc.) emitted at low to moderate con-

    centrations (1 ppm to 1000 ppm) (Devinny and Hodge,

    1995; Kim, 2004). The industries mainly concerned

    with depollution biotechnologies are chemistry, petro-

    chemistry, pulp and paper, metallurgy, mining and en-

    ergy production (Bailey and Ollis, 1986; Robert and

    Pilon, 2000).

    In the following sections, bioprocesses (bioscrub-

    ber, biotrickling filter and biofilter) are generally de-

    scribed, with a more detailed section dedicated to

    biofiltration.

    THE BIOTECHNOLOGIES

    The particular interest of these biotechnologies is that

    they do not utilize energy other than the capacity of

    microorganisms to metabolize a wide range of VOC:

    biocatalytic oxidation of pollutants. The catalysts areheterotrophic microbial strains (bacteria, fungi) that are

    able to utilize VOC in two ways:

    contaminants, oxidized in the course of the catabolic

    pathway (respiratory chain) are a source of energy; contaminants are also a source of available carbon for

    the anabolic processes, such as cell growth.

    M.-C. Delhomenie and M. Heitz 54

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    TABLE 1 Characteristics, advantages and drawbacks of the main APCT applied to VOC elimination.

    Technology Principle and characteristics Performances and limitations Costs/(m3 h1) air

    Adsorption Transfer of VOC to a porous

    solid phase, fixed or fluidized

    Materials: activated carbons,

    zeolites and polymers

    Ex.: Activated carbon adsorbs

    1030% VOC on a weight basis

    Doubled installations:adsorptiondesorption cycles

    Operating temperature

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    TABLE 1 Characteristics, advantages and drawbacks of the main APCT applied to VOC elimination.(Continued)

    Technology Principle and characteristics Performances and limitations Costs/(m3 h1) air

    Membranes Separation of gas mixtures

    through semi-permeables

    membranes

    Materials: polymers (hollow

    fibers, silicones), porous

    ceramics

    Gas flow compressed beforemembrane separation

    Conversion: 5098%

    VOC are concentrated 5100

    times, and valorization (recycle)

    possible

    Selective membranes, resistant

    to halogenated VOC

    But . . . Pressure drop

    High operating pressures

    Membrane cleaning required

    Not available

    UV/photochemical

    oxidation

    Complete oxidation by

    oxygenated oxidizers (O3,

    H2O2), and initiated by UV

    radiation

    Possible utilization of

    photocatalysts (TiO2, FexOy,etc.)

    Operating temperature:

    ambient

    Conversion: 9098%

    Moderate energetic costs

    But . . .

    Inadequate for halogenated

    VOC

    Deposit of oxidation

    by-products on the catalysts

    surface (cleaning)

    Complex systems

    Not available

    Biotechnologies(detailed later)

    Biocatalytic oxidation of VOC 3 configurations: biofilters

    (most frequent), biotrickling

    filters and bioscrubbers

    Biocatalysts: microorganisms

    (bacteria, fungi)

    30 s < Residence time < several

    min

    Operating temperature:

    2040C

    Filter-bed life time: 35 years

    Conversion: 8095% Moderate installation and

    operating costs

    Low maintenance

    But . . .

    Strict control of biological

    parameters (pH temperature,

    moisture level, nutrients,etc.)

    Large spaces required for

    biofilters

    Pressure drop problems

    Investment: US $1070 Operation: US $310

    The products of the biological reactions engaged inthese bioreactors are essentially: carbon dioxide, water,

    inorganic byproducts (e.g. HCl, SOX) related to the

    presence of heteroatoms in the VOC squeleton (Cl, S,

    N, etc.), new cellular matter, and organic byproducts

    (metabolites such as exopolymers). Biooxidations are

    exothermic reactions (some kcal/mol VOC oxidized),

    thus the associated heat release is also a biodegradation

    reaction product (Scriban, 1993).

    The effective useof biocatalysts requires strict control

    of their environment, normally the biological growth

    medium. There are some critical parameters that arecommon to the 3 types of bioreactors: (a) temperature

    (optimum between 20 and 35C for a mesophilic mi-

    croflora) (Leson and Winer, 1991; Swanson and Loehr,

    1997), (b) pH (optimum at about 7) (Leson and Winer,

    1991; Leson, 1998), (c) moisture content in the growth

    medium, and (d) availability of essential, non-carbon

    nutrients (N, P, K, S and micronutrients).

    The main differences between the three bioreactorscome from their design and mode of operation: mi-

    croorganisms conditioning, respective disposal of fluid

    phases (gas and liquid), presence or absence of station-

    ary solid phases. Table 2 presents the technical charac-

    teristics of the three bioprocesses.

    THE BIOSCRUBBER

    The bioscrubber, as represented in Figure 2, con-

    sists of two subunits: 1) an absorption tower and

    2) a bioreactor. In the absorption unit, input gaseouscontaminants are transferred to a dispersed liquid phase

    (aerosol). Gas and liquid phases flow counter-currently

    within the column, which may contain a packing.

    Nevertheless, the addition of inert packing (structured

    ceramic for example) provides for increased transfer

    surface between the VOC and the aqueous phase

    (Kellner and Flauger, 1998). The washed gaseous phase

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    FIGURE 1 Application limits (flow rateVOC concentration) of different APCT, based on references of Crocker and Schnelle, Juteau, 1997, and Devinnyet al., 1998.

    is released at the top of the column whereas the sepa-

    rated contaminated liquid phase is pumped towards an

    agitated, aerated bioreactor. This reactor contains the

    degrading microbial strains suspended in the aqueousphase, and the nutrients essential for their growth and

    maintenance. Most of the presently operating bioscrub-

    bers are inoculated with activated sludge, derived from

    wastewater treatment plants, for example (Ottengraf,

    TABLE 2 The technical characteristics of bioscrubbers, biotrickling filters and biofilters.

    Bioprocess Microorganisms Liquid phase Depollution step

    Bioscrubber Suspended in the bioreactor,

    in the aqueous growth

    medium

    Mobile

    Continuously

    dispersed

    Recycled

    VOC/air separation wit

    the absorption column

    VOC oxidation in the

    aerated bioreactorBiotrickling filter Immobilized on the filtering

    material

    Mobile

    Continuous trickling

    over the filter bed

    Possible recycling

    In the filter bed

    In the biofilm

    Biofilter Immobilized on the filtering

    material

    Occasional bed

    irrigation with

    nutrient solutions

    In the filter bed

    In the biofilm

    1987). In some cases, bioreactors are directly i

    ulated with specific degrading strains. The resid

    times for aqueous solutions in bioreactors range

    tween 20 and 40 days. After a treatment step (filtratsedimentation of biomass), part of the waste solu

    may be recycled in the absorption unit while pa

    the sedimented biomass may be reintroduced into

    bioreactor.

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    FIGURE 2 Bioscrubber description.

    The advantages of bioscrubbers are as follows:

    operational stability and good control of the biolog-ical parameters (pH, nutrients);

    bioscrubbers do not generate high pressure drops

    (Rho, 2000); their installation does not require large spaces.

    However, the major limitations of bioscrubbers are:

    bioscrubbers are adapted to treat readily soluble

    VOC (alcohols, ketones), with low Henry coefficients

    (

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    the absorption step (Cox and Deshusses, 1998), the

    solubility specifications are less drastic than for bio-

    scrubbers (Henry coefficient

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    Filter Bed

    The filter bed constitutes the heart of the biofiltra-

    tion process because it provides the support for micro-

    bial growth. Bohn (Bohn, 1996) has established a list

    of characteristics that suitable filtering materials should

    present. The following criteria are among the more im-

    portant of the required specifications:

    1. a high specific surface area, which is favorable to

    microflora establishment and maintenance, and to

    gas/biofilm exchange;

    2. a high porosity to facilitate gas convection and

    to promote the homogeneous distribution of gases

    throughout the bed;

    3. a good water retention capacity to avoid bed desic-

    cation;

    4. the presence and availability of intrinsic nutrients;

    5. the presence of a dense and diverse indigenous

    microflora.

    Peats, soils, composts, and at a smaller scale wood chips,

    are the most frequently employed basic materials in

    biofiltration, because they satisfy most of the required

    criteria, and they are widely available and at low cost.

    The main advantage of soils is that they offer a rich

    and varied microflora. However, they contain only a

    few intrinsic nutrients, they present low specific surface

    areas and they generate high pressure drops (Swanson

    and Loehr, 1997).

    Peat is also an interesting material because it containshigh amounts of organic matter, it presents high specific

    surface area, a good water holding capacity and a good

    permeability.However, peat contains neither high levels

    of mineral nutrients nor a dense indigenous ecosystem.

    Composts are the materials that are most frequently

    employed for a variety of reasons. They offer a dense

    and varied microbial system, a good water holding ca-

    pacity, a good air permeability, and they contain large

    amounts of intrinsic nutrients. Moreover, their utiliza-

    tion in biofilters constitutes a recycling and effective

    way for utilization of residual organic matters, such asthe residues and activated sludge of wastewater treat-

    ment plants, forest products (branches, leaves, barks),

    domestic residues, etc. (Alexander, 1999) However, com-

    posts are often less stable than soils or peats because they

    tend to break down and to become compacted, leading

    to pressure drop increases, due, among other reasons,

    to their high water holding capacity.

    Some authors have studied biofiltration on wood

    chips or barks (Smet et al., 1996a; Smet et al., 1999;

    Hong and Park, 2004), but they have shown that per-

    formances obtained with such filtering materials are less

    satisfactory than those obtained with compost or peat.

    This has been explained by the low pH-buffering capac-

    ity, the low specific surface areas and the low nutrient

    content of such materials. Despite these deficiencies,

    wood barks are still widely used in biofiltration as struc-tural materials, in association with peat or compost.

    Indeed, to prevent bed crushing and compaction,

    most authors employ materials that provide the bed

    with good structure maintenance and rigidity, which

    delays the clogging phenomena and increases the bed

    lifetimes: wood chips or barks (Oh and Choi,2000; Luo,

    2001; Mareket al., 2001), perlite (Weigneret al., 2001;

    Woertzet al., 2002), vermiculite (Krishnayyaet al., 1999;

    Pineda et al., 2000), ceramic (Cardenas-Gonzalez et al.,

    1999), glass beads (Zilli et al., 2000), polyurethane foam

    (Moe and Irvine, 2000; Woertzet al., 2002), polystyrene(Ottengraf, 1986; Arulneyam and Swaminathan, 2000),

    lava rock (Chitwood and Devinny, 2001), etc. More re-

    cently, Ibrahim et al., 2001, prepared a bed composed of

    activated sludge, immobilized in gel beads, and Marek

    et al., 1999, have utilized beds of activated carbon or mi-

    croorganisms immobilized in calcium-alginate beads.

    Christen et al., 2002, and Sene et al., 2002, developed

    a sugarcane-bagasse-based bed, for the treatment of

    ethanol and benzene.

    Some bed structuring agents also present interest-

    ing chemical characteristics such as pH buffering ca-pacity (limestone, for example) (Smet et al., 1996b),

    or general adsorbing capacity (activated carbon). Or-

    ganic materials such as composts, soils or peats present

    only small adsorption capacities: Acuna et al., 1999,

    determined a value for the adsorption coefficient of

    toluene on peat as 0.137 mg g1 of peat, Tang and

    Hwang, 1997, reported partition coefficients for toluene

    of 1.43 mg g1 of compost, 2.00 mg g1 of diatoma-

    ceous earth, and 0.89 mg g1 of chaff. Beds contain-

    ing activated carbon (granulated or powdered) pro-

    vide adsorption coefficients for toluene some 10 to20 times greater: 50.6 mg g1 of granulated activated

    carbon (Tang and Hwang, 1997), and 0.287 g g1 of

    powdered activated carbon (Marek et al., 1999). Thus,

    the addition of activated carbon leads to (1) improve-

    ments of the degrading capacity of biofilters (Webster

    et al., 1995; Abumaizaret al., 1998), (2) elimination of

    hydrophobic compounds, which naturally tend to be

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    more recalcitrant to biofiltration (Cardenas-Gonzalez,

    1999), and (3) to better control loading variations (flow

    rate or VOC concentration fluctuations) (Mason et al.,

    2000).

    Flow Rate

    The air flow rate, Q, and the empty bed residence

    time (EBRT), , defined as: = Vbed

    Q (Vbed, is the bedvolume), are parameters that have significant impact

    on the biodegradation performance (Elmrini et al.,

    2004). Indeed, two physico-chemical mechanisms may

    limit the overall elimination efficiency of a biofilter

    (Ottengraf, 1986): the pollutants diffusion transfer from

    gas phase to biofilm, and the biodegradation reaction.

    Depending on both the flow rate and the VOC concen-

    tration, the VOC degradation process is limited by ei-

    ther one of these mechanisms, or both simultaneously.

    Figure 5 presents the characteristic-time scales of the

    various physical, chemical and biological processes oc-curring in a biofilter (Kisselet al., 1984; Picioreanuet al.,

    1999). From this time-scale chart, it appears that dif-

    fusion mechanisms are slower than the biological re-

    actions. Thus, to improve biofiltration performance,

    the EBRT should be greater than the time required

    for diffusion processes, which is the case for low op-

    erating flow rates. Most of the authors studying vari-

    able flow rates have effectively verified that long EBRT

    give rise to better VOC removal efficiencies (Jorioet al.,

    1999; Christen et al., 2002; Delhomenie et al., 2002a;

    Martin et al., 2002; Yoon and Park, 2002). However,

    FIGURE 5 The characteristic times of the main mechanisms taking place in a biofilter, based on references of Picioreanuet al., and Kisselet al., 1989.

    the application of long EBRT requires larger filter

    volumes.

    On the contrary, when flow rates are too high,

    tact times between microorganisms and gases are

    short so that the biodegradation reaction canno

    completed. Moreover, when the input air velocity i

    high, the water contained in the filter bed is strippe

    the gas flow, which tends to desiccate the biofilte

    most of the operated biofilters, the EBRT ranges f15 seconds to several minutes. The EBRT value also

    pends on other operating conditions such as the V

    concentration, the VOC biodegradability level and

    available bed volumes.

    Pollutants

    As previously mentioned, the overall biofiltratio

    ficiency and the pollutants biodegradability level

    on the following microscopic processes: the VOC t

    fer rate from gas phase to biofilm, and the Vbiodegradation rate. The magnitude of both param

    depends on the operating conditions (flow rate, tem

    ature, pH, moisture content, etc.), but also on the

    and concentration of pollutants presented. The

    taminants absorption in the biofilm is governed by

    Henrys law, which correlates the VOC vapor pres

    with its solubility in water. The reversible adsorptio

    pollutant on the particle surface is described by an e

    librium isotherm (linear, Langmuir, Freundlich,

    Mass transport in the biofilm is described by mo

    ular diffusion in an aqueous phase (Ficks law).

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    biodegradation rate is related to the microbial strains

    established in the filter bed, and to the concentration

    and chemical configuration of the VOC.

    In this way, the removal of slightly soluble com-

    pounds, introduced at low concentrations, is limited

    by their transfer rate into the biofilm. In contrast, sol-

    uble compounds, introduced at higher concentrations,

    are easily absorbed into the biofilm, but the biodegrada-

    tion rate then tends to limit their removal rate. Takinginto account these parameters, the oxygenated hydro-

    carbons (alcohols > aldehydes, ketones > ethers) are

    more readily biodegraded than the linear alkanes, fol-

    lowed by the aromatic hydrocarbons. The very short

    chain alkanes, such as methane, and the branched com-

    pounds, are more recalcitrant, and the halogenated hy-

    drocarbons (chlorinated) are the most recalcitrant of

    VOC.

    Further, VOC concentrations introduced beyond a

    toxicity threshold value tend to inhibit the microbial

    growth and activity. The existence of such thresholdconcentrations has been proved, at the laboratory-scale,

    by Tang et al., 1996, with triethylamine, by Jorio et al.,

    2000, with styrene and by Krailas et al., 2000, with

    methanol. Generally, VOC concentrations do not ex-

    ceed 5 g m3 in biofilters inlet gas flow (1000 ppmv

    methane equivalent).

    Finally, even though most laboratory studies con-

    sider single substrates or restricted mixtures of VOC,

    large scale gas effluents contain, in fact, more or less

    defined, and sometimes variable mixtures of pollutants.

    However, authors working with VOC mixtures havedemonstrated that the simultaneous presence of several

    compounds can:

    have either no effect or they improve the removal

    efficiency of single pollutants. This is the case for

    the elimination of some recalcitrant compounds that

    requires cometabolic oxidation pathways.a For exam-

    ple, the trichloroethylene degradation is induced by

    the addition of toluene (Ergas et al., 1993; Cox et al.,

    1998), propane or methane (Watwood and Sukesan,

    1995) in the gas mixture. create interference within the metabolic processes of

    each pollutant. Deshusses et al., 1999, reported that

    the presence of ethylacetate in the gas flow has an in-

    hibitory effect on toluene degradation. Oh et al.,1994,

    showed mutual inhibition processes occurring within

    aThe VOC-degrading enzymes are activated only in the presence of aprimary substrate.

    BTEX mixtures: competitive inhibition between ben-

    zene and toluene, benzene and toluene degradation

    inhibited by the p-xylene cometabolism. Deshusses,

    1997, also illustrated strong mutual inhibitions oc-

    curring in a mixture containing hexane, acetone,

    propanol, methylisobutylketone, and methylethylke-

    tone. Other studies proved that, in some cases, the

    observed inhibitions resulted from an accumulation

    of inhibitory intermediate metabolites in the micro-bial growth medium (Leon et al., 1999; Yu et al., 2001).

    Diauxyb has also been observed as a consequence of

    the interactions between compounds (Webster and

    Devinny, 1998). This phenomenon was illustrated by

    Mohseni and Allen, 2000, who concluded that, in a

    mixture of methanol and -pinene, methanol, a hy-

    drophilic and easily biodegradable compound, was

    consumed prior to the hydrophobic and recalcitrant

    -pinene.

    Pressure Drop

    The bed pressure drop is an important biofiltration

    parameter because it is taken into account in the op-

    erating costs. Thus, Leson et al., 1995, reported that a

    pressure drop increase from 4 to 25 cm of water led

    to an increase in energetic needs from 7 to 27 kW,

    within only 6 months. The pressure drops recorded in

    most of biofiltration systems do not exceed some cm of

    water/m. Several factors influence the pressure drop

    level through the porous filter bed: filter bed charac-

    teristics, flow rate, moisture content, biomass density,

    etc.

    Among the organic materials that constitute the

    biofilter beds, soils are the least air permeable, and

    thus give rise to high pressure drops, followed by com-

    posts, then peats, and wood chips (Kennes and Thalasso,

    1998). Moreover, filter beds that contain small parti-

    cles offer high specific surface areas, thus favoring the

    microbial activity (Oude Luttighuis, 1998; Kent et al.,

    2000), but also constitute a greater resistance to gas flow,

    which is even further increased when biomass grows in

    bed porosities (Bailey and Ollis, 1986; Allen and Yang,

    1991). Even though larger particles favor the gas flow

    through the bed (lower pressure drop), they offer less

    surface sites for the oxidation reaction, and thus can

    lead to lower elimination performances (Delhomenie

    bSome compounds, that are easier to degrade, or for example provide

    more reaction energy, are sometimes preferred by microorganisms.

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    et al., 2002b). As a compromise, Ottengraf, 1986, have

    suggested the addition of 35 mm polystyrene beads

    to the bed, and Williams and Miller, 1992, concluded

    that beds should contain at least 60% particles with a

    size greater than 4 mm. As suggested by Eitner and

    Gethke, 1987, and Leson and Winer, 1991, most re-

    searchers have utilized particles of diameters greater

    than the threshold value of 4 mm (Corsi and Seed,

    1995; Oude Luttighuis, 1998; Ortiz, 1998; Cardenas-Gonzalez et al., 1999; Delhomenie et al., 2001a).

    Overall biofilters dimensions also significantly in-

    fluence the bed pressure drop: under the weight

    of the overlying layers, the whole bed tends to be

    crushed and compacted, which affects its air perme-

    ability. Usually, filter bed volumes range from 10 to

    3000 m3, with heights ranging from 0.5 to 2 m. In

    some cases, bed configurations are also multi-staged or

    modular.

    The impact of the gas flow rate on the pressure drop

    is also important. Several authors have proved that thehigher the superficial gas velocity, the more significant

    is the pressure drop. Phillips et al., 1995, proposed a

    correlation between the pressure drop (P) and the air

    superficial velocity (u), inspired by the Kozeny-Carman

    relationship: P = a ub, where 1 < a < 1.9, and b

    depends on the filtering material properties and the gas

    flow regime (2

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    Thus, Delhomenie et al., 2004, have determined that,

    in a biofilter treating high concentrations of pollutant,

    evaporation and stripping can cause water losses up

    to 70 g of water per day per kg filter bed. Van Lith

    et al., 1997 developed a calculation procedure to eval-

    uate the bed drying rate and proposed moisture con-

    trol methods. In biofilters, the systematic humidifica-

    tion of the inlet gas stream permits the maintenance

    of a minimum moisture content, but Abumaizaret al.,1998, and Devinny et al., 1999, suggest operating an

    occasional, manual irrigation of the bed when water

    losses are

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    element after carbon and oxygen), have been devel-

    oped and experimentally validated (Kinney et al., 1998;

    Alonsoet al., 2001; Delhomenie et al., 2001a).

    Nutrients supply is performed either in the solid

    form, directly inserted into the filter bed (Gribbins and

    Loehr, 1998), or as mineral salts dissolved in aqueous

    solutions, the most frequently used method. Given the

    wide range of elements and compounds influencing the

    microbial behavior, the optimization of nutrient solu-tions delivered to filter beds is a large subject of study.

    Wu et al., 1999, reviewed the most common nutrient

    solutions adapted for biofilter use. The most utilized

    salts are: KH2PO4, NaxH(3x)PO4,KNO3,(NH4)2SO4,

    NH4Cl, NH4HCO3, CaCl2, MgSO4, MnSO4, FeSO4,

    Na2MoO4, and vitamins (B1, etc.).

    The pH has a similar influence on the biofiltration

    efficiency than temperature: there exists an optimum

    range of pH, and beyond this interval microbial ac-

    tivity is severely affected. Most of the microorganisms

    in biofilters are neutrophilic: their optimum pH is 7.Thus, for BTEX, Lu et al., 2002, have observed maxi-

    mum degradation rates for pH between 7.5 and 8.0, and

    Lee et al., 2002, at around 7.0. Veiga et al., 1999, have also

    proved that for pH values ranging between 3.5 and 7.0,

    the alkylbenzenes degradation performance is increased

    with pH, while Arnold et al., 1997, stated that styrene

    elimination was improved within a neutral medium.

    Moreover, pollutants that contain heteroatoms (S, Cl,

    N) are converted into acid products, which tends to

    reduce the pH (Devinny and Hodge, 1995; Christen

    et al., 2002), affect the microorganisms, and cause cor-rosion problems in downstream conducts (Webster and

    Devinny, 1998).

    Kennes and Thalasso, 1998, report that, among the

    organic materials employed in biofilters, soils present

    the best intrinsic pH buffering capacity, followed by

    composts and wood-chips (Smet et al., 1996a). Peats are

    naturally acidic (pH 3.04.0), with low buffering ca-

    pacity. To maintain the pH constant at around 7.0, some

    authors insert buffer materials into their filter beds: cal-

    cium carbonate (Ottengraf, 1986; Smet et al., 1996b;

    Krishnayya et al., 1999), dolomite (Smet et al., 1999),oyster shells (Ergaset al., 1995; Morgenrothet al., 1996;

    Cardenas-Gonzalez et al., 1999). The pH regulation is

    also performed via bed irrigation with nutrient solu-

    tions that contain pH-buffers: Ca(OH)2 (Acuna et al.,

    1996), NaOH (Zilli et al., 1996), NaHPO4, NaHCO3(Tang et al., 1996), urea (Wu et al., 1999; Delhomenie

    et al., 2001b).

    Microorganisms

    Microorganisms are the catalysts of pollu

    biodegradation. They are essential for the opera

    of the bioprocess. During the elimination of V

    heterotrophic microorganismsd are predominant, m

    often being bacteria or fungi. The bed inocula

    depends on both the nature of the filtering mate

    and the VOC biodegradability level. Many authorsfer taking advantage of the ecosystems indigenou

    the beds (Mohseni and Allen, 2000; Delhomenie e

    2001b; Delhomenieet al., 2002a;). After an acclima

    tion period, the most resistant populations are natu

    selected and a microbial hierarchy is established in

    bed. In many other cases (materials with low biom

    density, recalcitrant VOC, reduction of acclimatiza

    period), researchers inoculate the beds with conso

    extracted from sewage sludge, for example, or strain

    rived from either commercial sources or isolated f

    previously operated biofilters. Table 3 presents somthe strains employed in biofilters, either as inocul

    or as materials isolated from operating systems.

    In terms of biomass density, a biofilter contain

    tween 106 and 1010 cfue of bacteria and actinomyc

    per gram of bed (Ottengraf, 1986; Websteret al., 1

    Krailas et al., 2000), and some 103 to 106 cfu of f

    per g (Ottengraf, 1986; Tahraoui et al., 1994). La

    Pedersenet al., 1997, and Delhomenieet al., 2001a,

    reported that, in biofilters, the degrading species re

    sent between 1 and 15% of the total populations.

    Models

    The design and application of large-scale biofi

    requires the development of tools to evaluate th

    fluence of the main operational parameters (flow

    concentrations, nutrient effects, etc.). Studies perfor

    at the laboratory and pilot scales provide experime

    results that contribute to the understanding of c

    plex biofiltration mechanisms and that also suppor

    development of process models, which are themse

    very useful tools for both performance extrapola

    and prediction.Since the beginnings of air biofiltration, progress

    been realized in the field of biofiltration mode

    and numerous models now exist, describing both

    steady-state and the transient behaviors of bioreac

    dTheir sources of carbon and energy are the organic compounds.ecfu: colony forming units.

    65 Biofiltration o

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    TABLE 3 Microorganisms identified during the degradation of VOC by biofiltration.

    Pollutants Microorganisms References

    Benzene Pseudomonassp. Seneet al., 2002

    Benzene Alcaligenes xylosoxidans Yeom and Daugulis, 2001

    Benzene Cladosporium sphaeraspermum, Qiet al., 2002

    Exophiala lecanii-corni,

    Phanerochaete chrysosporium

    BTX

    Phanerochaete chrysosporium Ohet al., 1998Butylacetate Cladosporium resinae,

    C. sphaeraspermum,

    Exophiala lecanii-corni,

    Mucor rouxi,

    Phanerochaete chrysosporium

    Qiet al., 2002

    Chlorobenzene Pseudomonassp. Seignezet al., 2001

    Dichloromethane Pseudomonas putida Ergaset al., 1996

    Dichloromethane Hyphomicrobiumsp. Dikset al., 1994

    Dimethyl sulfide Hyphomicrobium Smetet al., 1999

    Ethanol Candida utilis Christenet al., 2002

    Ethylacetate Rhodococcus fascians Hwanget al., 2002

    Ethylbenzene Cladosporium resinae,

    C. sphaeraspermum,Exophiala lecanii-corni,

    Phanerochaete chrysosporium

    Qiet al., 2002

    Ethylene Mycobacteriumsp. Deheyderet al., 1997

    Methylethylketone Alcaligenes denitrificans,

    Geotrichum candidum,

    Fusiarum oxysporum

    Agathoset al., 1997

    Methylethylketone Cladosporium resinae,

    C. sphaeraspermum,

    Exophiala lecanii-corni

    Qiet al., 2002

    Methylethylketone Rhodococcussp. Amanullahet al., 2000

    Methylisobutylketone Cladosporium resinae,

    C. sphaeraspermum,

    Exophiala lecanii-corni,Phanerochaete chrysosporium

    Qiet al., 2002

    Methyl-tertbutyl-ether Pseudomonas aeruginosa Dupasquieret al., 2002

    Pentane Pseudomonas aeruginosa Dupasquieret al., 2002

    Phenol Pseudomonas putida Zilliet al., 1996

    -pinene Aspergillussp. Diehlet al., 2000

    -pinene Pseudomonas fluorescens,

    Alcaligenes xylosoxidans

    Kleinheinzet al., 1999

    Styrene C. sphaeraspermum,

    Exophiala lecanii-corni

    Qiet al., 2002

    Styrene Tsukamurella, Pseudomonas,

    Sphingomonas, Xanthomonas

    Arnoldet al., 1997

    Styrene Exophiala jeanselmei Coxet al., 1997

    TEX+ Bacillus sp.,Pseudomonassp.,

    Trichosporon beigelei

    Veigaet al., 1999

    Toluene Acetinobactersp. Mareket al., 1999

    Toluene Pseudomonas putida Parket al., 2002; Ergaset al., 1996;

    Villaverde and Fernandez, 1997

    Toluene Pseudomonas pseudoalcaligenes Oh and Choi, 2000

    Toluene Exophiala lecanii-corni Woertzet al., 2001

    Toluene Scedosporium apiospermum Garcia-Penaet al., 2001

    M.-C. Delhomenie and M. Heitz 66

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    TABLE 3 Microorganisms identified during the degradation of VOC by biofiltration.(Continued)

    Pollutants Microorganisms References

    Toluene Corynebacterium jeikeium,

    C. nitrilophilus, Turicella oritidis,

    Pseudomonas mendocina,

    Sphingobacterium thalphophilum,

    Micrococcus lutens

    Strausset al., 2000

    Toluene Cladophalophoriasp. Woertzet al., 2002

    Trichloroethane Pseudomonas putida Ergaset al., 1993Trichloroethylene Pseudomonas putida Coxet al., 1998; Ergas et al.,

    Xylene Pseudomonas pseudoalcaligenes Oh and Choi, 2000

    Benzene, Toluene, Xylene.+Toluene, Ethylbenzene, Xylene.

    Biofilters are three-phase biological reactors involving

    complex, physical, chemical and biological phenom-

    ena: interfacial transfers, diffusion, convection, disper-

    sion, sorption equilibriums, degradation and microbial

    kinetics, etc. The differences between the various models

    proposed in the literature depend on the assumptionsstated by the authors to establish the mass balances and

    equations for the different phases considered.

    Ottengraf and van den Oever, 1983, proposed the

    first model for air biofiltration, by describing the

    steady-state performance. In this model, the cases of

    zero and first order degradation kinetics were presented,

    and associated with a substrate mass equilibrium at a

    unique gas/biofilm interface. This model, analytically

    solvable, is still widely used to describe biofilter perfor-

    mance (Zilliet al., 1996; Metriset al., 1999; Pinedaet al.,

    2000; Delhomenie et al., 2002a; Park et al., 2004). Topredict steady-state biofilter effectiveness, Shareefdeen

    et al., 1993, proposed another model by introducing

    oxygen limitation and substrate inhibition in the ki-

    netic expressions. Deshusses and Hamer, 1993, as well

    as Baltzis et al., 1997, developed models for steady-state

    biofilters treating mixtures of pollutants, through con-

    sidering either Monod or Haldane degradation kinetics.

    Even though they provide satisfying descriptions of the

    steady-state performance, most of these models reduce

    the real three-phase problem to a simplified two-phase

    problem involving a unique gas/biofilm interface, andwithout other flow models than the ideal plug flow one.

    Dealing with the transient behavior of biofilters led

    most of the authors to consider more complex sys-

    tems. Hodge and Devinny, 1995, for example, con-

    sidered axial dispersion in the plug flow reactor, and

    introduced a mass transfer term between the gas and

    biofilm/solid phases. Shareefdeen and Baltzis, 1994,

    proposed a three-phase development, taking into

    count adsorption of the pollutant at the gas/solid

    terface. This model also considered oxygen limita

    and substrate inhibition. Amanullah et al., 1999,

    posed a three-phase model derived from Shareefd

    and Baltzis, 1994, combining adsorption and axialpersion phenomena. In their transient model, Tang

    Hwang, 1997, established mass balances that took

    account the heterogeneity of the packing material

    sorption phenomena on the pellets, and they prop

    a complex generalized form of the Monod expres

    for substrate biodegradation. Deshusseset al., 1995,

    Zarook et al., 1997, suggested transient models for

    biofiltration of mixtures of pollutants, with kineti

    teractions between the pollutants. All of these trans

    regime models describe complex mechanisms betw

    gas, solid and biofilm, and their solution by numcal methods requires the assumption that both bio

    thickness and biomass density remain constant

    ing biofilter operation. To this end, it is assumed

    biomass growth is counterbalanced by death and m

    tenance (Metriset al., 1999). However, as mentione

    Morgan-Sagastume et al., 2001, and Delhomenie e

    2003, biomass tends to accumulate on the bed p

    surface, so that the biofilm thickness in biofilters

    reach several hundreds m after several weeks of

    eration (Pineda et al., 2000; Cohen, 2001). Cha

    of biofilm physionomy alter the transfer mechan(Alonsoet al., 1997; Wubkeret al., 1997) and tend t

    fect the overall performance (Delhomenie et al., 2

    Song and Kinney, 2002). Despite the recognized im

    tance of the clogging problems in biofilters, up to d

    only one transient model has been presented in th

    erature to describe the consequence of biomass gro

    on biofiltration performance (Song and Kinney, 20

    67 Biofiltration o

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    CONCLUSION

    In this paper, the existing air pollution control tech-

    nologies (APCT) applied for the removal of volatile

    organic compounds have been reviewed. The main

    APCT (adsorption, absorption, incineration, etc.) have

    been briefly presented. Among them, the emerging

    biotechnologies: bioscrubbers, biotrickling filters and

    biofilters, have been described. The emphasis of this re-

    view focused on biofiltration and presented the recent

    and latest developments that concern biofilters. Details

    of the main physical, chemical and biological parame-

    ters governing this bioprocess have been presented: fil-

    ter bed, flowrate, pollutants (nature and concentration),

    pressure drop, moisture content, temperature, nutrients

    and pH, microorganisms, and models.

    ACKNOWLEDGMENTS

    The authors are indebted to the Natural Science and

    Engineering Research Council of Canada (NSERC) for

    their financial support. They also wish to acknowledge

    Dr. P. G. Lanigan for text revision.

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