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1. Introduction

1.1 Volatile Organic Compounds

Volatile Organic compounds (VOCs) are chemicals, which evaporate readily or are gases
at room temperature and pressure. Many physical and chemical properties of VOCs have been
given in Appendix A. They are important pollutants in indoor air (Yu, 2007; Wang,
2007). Compared to outdoors, higher concentrations of VOCs can be found indoors (Wang,
2007) where there is limited ventilation. The U.S. Environmental Protection Agency (EPA) Total
Exposure Assessment Methodology (TEAM) studies revealed that indoor VOC levels were
typically 2 to 5 times higher than outdoor concentrations (U.S. EPA, 2009; Birnie, 2006).
Minnesota Department of Health (2009) listed a variety of factors that affect levels of
VOCs in an indoor environment. These are volume of air in the room/building, the rate at which
the VOC is off-gassed, the building ventilation rate, outdoor concentration, and the time spent by
people in the affected environment. List of VOCs defined as priority polutants by the USEPA are
grouped in appendix –B.
Biological treatment for removing VOCs from gas streams has been accepted in Europe
and Japan as an effective technique to treat VOCs and odor-containing industrial exhaust (Fouhy
1992; Leson and Winer 1991). In the United States, it was until recently still considered a new
and untested technology (Fouhy 1992; Bohn 1992), but has since been receiving increasing
attention because of its effectiveness and low costs (Swanson and Loehr 1997).

1.2 Sources of VOCs

Fossil fuel deposits, including oil sands, are natural sources of volatile organic
compound, as are volcanoes, vegetation and bacteria. Trees also emit different volatile organic
compounds. For example, deciduous trees emit great amounts of the compound isoprene during a
hot day; coniferous trees emit the volatile organic compound pinene day and night.
Man-made volatile organic compound emissions come from transportation, solvent use,
industrial processes and gasoline evaporation. Gasoline evaporation can occur when vehicles are

being filled at service stations or when transfers of gasoline are made. Others are released when
oil-based paints are applied or cleaning solvents are used.
Common VOCs include acetone, benzene, ethylene glycol, formaldehyde, methylene
chloride, perchhlorothylene, toluene, xylene, and 1, 3- butadiene. Acetaldehyde, a component of
Environmental Tobacco Smoke (ETS) is one of the organic compounds that accumulate in
rooms. Xu and Shiraishi (1999) and Tang (2004) recognized it as key indoor air pollutant.
VOCs may come from gaseous emissions of household chemicals and products (U.S. EPA,
2009). There are thousands of different VOCs produced and present in our daily lives
(Minnesota Department of Health, 2009). These include those coming from cleaning and
degreasing agents, pesticides, air fresheners, toilet bowl deodorants, environmental tobacco
smoke (second hand smoke), furniture and building materials (e.g. wood products, adhesives,
carpeting, paints, varnishes, vinyl floors, moth balls, solvents, gasoline, newspaper, upholstery
fabrics, sealing caulks), cosmetics, fuel oil, vehicle exhaust, cooking, photocopying, etc. (U.S.
EPA, 2009; Minnesota Department of Health, 2009).

1.3 Health effects of VOCs

The risk of health effects from inhaling any chemical depends on how much is in the air,
how long and how often a person breathes it in. Scientists look at short-term (acute) exposures as
hours to days or long-term (chronic) exposures as years to even lifetime.
Breathing low levels of VOCs for long periods of time may increase some people‟s risk
of health problems. Several studies suggest that exposure to VOCs may make symptoms worse
in people who have asthma or are particularly sensitive to chemicals. Each chemical has its own
toxicity and potential for causing different health effects. Common symptoms of exposure to
VOCs include:

1.3.1 Short-Term (Acute) to high levels of VOCs

 Eye, nose and throat irritation

 Headaches
 Nausea / Vomiting

 Dizziness
 Worsening of asthma symptoms

1.3.2 Long-Term (Chronic) to high levels of VOCs

Increased risk of:

 Cancer
 Liver damage
 Kidney damage
 Central Nervous System damage

1.4 Environmental impact of volatile organic compounds

Volatile Organic Compounds (VOCs) are of serious environmental concern because of the
harmful or offensive properties that they exhibit in varying degrees. These include:
 Harmful effects on natural ecosystems through toxicity, carcinogenicity and other
adverse physiological effects.
 Damage to materials.
 Contribution to photochemical ozone creation at ground level with consequent harmful
 Destruction of stratospheric ozone.
 Contribution to global climate change
 Sensory effects such as malodour.

1.4.1 Adverse physiological effects

Many volatile organic compounds (VOCs) are directly harmful to health on a broad
spectrum of acuteness, and include irritation to skin and mucous membranes; various toxic and
neurological effects; carcinogenicity, teratogenicity and mutagenicity. Some, such as Methane
and Ethylene, are simple asphyxiants. VOCs also have an indirect effect on human health via the

formation of photochemical oxidants such as ozone. (DEVELOPMENT OF NATIONAL

1.4.2 Damage to materials

Some volatile organic compounds (VOCs) have the potential to cause damage to
materials close to their point of discharge, for example as a consequence of oxidising or
corrosive properties. VOCs also indirectly contribute to damage to materials through the
formation of ozone. Ozone is a highly reactive oxidizing agent and can attack natural and
synthetic rubber, textiles, and resins such as those used in surface coatings. Through attack on
protective coatings, ozone damage can lead to accelerate building decay.
PLANTS, CPCB, September 2008)

1.4.3 Photochemical oxidant production

Photochemical oxidant results from the reactions that occur between VOCs and oxides of
Nitrogen (NOx) in the presence of sunlight. Photochemical oxidants include ozone, peroxyacyl
nitrates, peroxides etc. These compounds can affect human health and are harmful to plants and
materials. They enhance environmental harmfulness of NO by oxidising it to NO2.
The ability of a VOC to contribute to the formation of photochemical oxidants may be
expressed by its photochemical Ozone Creation Potential (POCP) factors.
(United Nations Economic commission for Europe (1990), Derwent and Richardson

1.4.4 Stratospheric ozone depletion

Concern over the effect of CFCs and other man-made chemicals on the concentration of
ozone in the stratosphere led to the Montreal Protocol and subsequent amendments.
 Methane has both natural and anthropogenic sources and affects both tropospheric and
stratospheric ozone.

 Non-methane hydrocarbons - play a direct role in troposphere chemistry and an indirect
role in stratospheric chemistry.
Chlorine-containing Substances - e.g.CH3Cl, CHF2Cl, CH3CCl3, - these gases also act as a
source of CIOx. CIOx is an important intermediate in the breakdown of ozone in the

1.4.5 Global warming

Almost all VOCs have potential to contribute directly to global warming by absorbing
infrared radiation from the earth‟s surface. In general the more complex a VOC, the greater its
ability to absorb infrared radiation, however, most VOCs have a very short atmospheric lifetime
and are broken down by atmospheric reactions. Generally speaking the exceptions to this rule are
the saturated light hydrocarbons and halogenated compounds. VOCs also contribute indirectly to
global warming through the change in concentration of Ozone, which is a potent greenhouse gas.
The global warming potential (GWP) of a substance is a measure of the extra amount of heat that
is trapped in the atmosphere when one kilogram of the substance is released instantaneously into
it, relative to the case when 1kg Carbon dioxide is released. GWPs are calculated using computer
models, which incorporate the radiative heat balance of the atmosphere and the chemical kinetics
of all the substances involved.
Recently a paper has been published (Derwent, 1994) in which GWPs have been derived
using a continuous source instead of an instantaneous one. The GWPs are very similar to those
from the references using instantaneous one. (Ramaswamy et al., 1991 and Shine et al., 1990)
sources so we have taken the average of all three references. Where values in the more recent
IPCC report, Climate Change 1994, supersede these, the more recent values have been used.

1.5 Categorization Method for level of Volatile Organic Compounds

A decision tree approach was used to judge VOC‟s against a number of selection criteria,
which determine the category. Three categories were used which are termed as „High‟,
„Medium‟ and „Low‟ in descending impact. As can be seen, VOC‟s are first judged according to
criteria based on human health effects, then on other factors viz. POCP / ODP / GWP.

PLANTS, CENTRAL POLLUTION CONTROL BOARD (Ministry of Environment & Forests,
Govt. of India) Parivesh Bhawan, East Arjun Nagar, Delhi – 110 032 ,September 2008)
The three categories are summarized as follows:
High: IARC Group 1 or 2A OR Confirmed Mutagen or Teratogen OR MSI classification
Extremely Toxic OR Very High Inhalation Toxicity (TLV value < 5 ppm).
Medium: IARC Group 2B OR MSI classification Highly Toxic or High Inhalation
Toxicity (TLV Value > 5ppm & < 50 ppm) OR POCP >85 OR GWP >10 OR ODP >0.2.
Low: IARC Group 3 / 4 and not toxic as per MSI rules and POCP < 85 AND GWP < 10
AND ODP <0.2
The classification for toxicity as given under MSI Rules (Manufacture, Storage and
Import of Hazardous Chemicals) Rules 1989, as promulgated by the Ministry of Environment &
Forests, Government of India, is as given below: Table 1.2

Table 1.1 Classification of Toxicity

Category Oral LD50 Dermal LD50 LC50
(mg/Kg) (mg/Kg) (mg/L)
Extremely Toxic <5 <40 <0.5
Highly Toxic >5-50 >40-200 >0.5-2.0
Toxic >50-200 >200-2000 >2-10

1.6 VOC Emission Control Technologies In Petrochemical Industries

Emissions of VOC‟s /organic HAP‟s may occur from multiple sources but the following are the
major sources:
 Process Vents
 Storage Vessels and Transfer operations
 Components (Fugitive emissions)

Various types of control technologies used for treatment of VOC/HAP emissions are:
 Combustion Devices (Incinerators/Flares/Heaters)
 Recovery/Recapture Devices (Condensers / Adsorbers etc.)

 Specific techniques for transfer racks/storage emissions

1.6.1 Combustion Control Devices

Combustion control devices include incinerators, flares, boilers, and process heaters.
Combustion control devices operate on the principle that any VOC heated to a high enough
temperature in the presence of sufficient oxygen will oxidize to carbon dioxide and water. The
theoretical combustion temperature varies due to different VOC‟s are oxidised at different
temperatures, depending on their properties. A consistent VOC destruction efficiency can usually
be achieved in combustion devices regardless of the amount and type of VOC in the vent stream.
Scrubbers can be used downstream of combustion control devices (other than flares) to treat
halogenated streams.
Scrubbers reduce emission of halogens and hydrogen halides, such as chlorine and
hydrogen chloride, formed during combustion. (DEVELOPMENT OF NATIONAL EMISSION

1.6.2 Thermal Incinerators

Thermal incinerators are usually refractory-lined chambers containing a burner (or set of
burners). An efficient thermal incinerator provides (i) high temperature inside the chamber
enough to completely oxidize the VOC‟s (ii) proper turbulence of combustion products, air, and
the process vent streams, and (iii) adequate residence time to allow for complete oxidation of
VOC‟s. All thermal incinerators operate using excess air to ensure a sufficient supply of oxygen.
Thermal incinerators can achieve at least 98 percent destruction for most VOC‟s, for
example vent streams with VOC concentrations below 1,000 ppmv, all new thermal incinerators
can achieve outlet concentration of 20 ppmv or lower. Thermal incinerators are technically
feasible control options for most vent streams. Excessive fluctuations in flow rate may prevent
the use of a thermal incinerator in such situations a flare could be used. (DEVELOPMENT OF

1.6.3 Catalytic Incinerators

Catalytic incinerators operate at lower temperatures than thermal incinerators because

some VOC‟s are oxidized at lower temperatures in the presence of a catalyst. The vent stream is
preheated in a mixing chamber, and oxidation takes place on a catalyst bed like. Like the thermal
incinerators, heat can be recovered from the exiting gas stream.
Catalytic incinerators can achieve overall VOC destruction efficiencies of 95 to over 98
percent. The efficiency depends on temperature, oxygen content, catalyst activity, and the
characteristics and concentration of the VOC. Catalytic incinerators are typically used for vent
streams with stable flow rates and stable concentrations. They cannot be used on vent streams
that poison or block the catalyst reactive sites, or on vent streams with high inlet concentrations

1.6.4 Industrial boilers and process heaters

Industrial boilers and process heaters combust VOC‟s by incorporating the vent stream
into the inlet fuel or by feeding the vent stream into the boiler or heater through a separate
burner. Industrial boilers are used to produce steam. When boiler fire natural gas, forced-or
natural-draft burners mix the incoming fuel and combustion air. A VOC-containing vent stream
can be added to this mixture or it can be fed into boiler through a separate burner. The majority
of industrial boilers used in the chemical industry are of water tube design, where hot
combustion gases contact the outside of heat transfer tubes, which contain hot water and steam.
Process heaters are used to raise the temperature of process streams using a similar tube design,
where the process fluids are contained in the tubes. Heat recovery from the exiting gas stream is
achievable for both industrial boilers and process heaters.
Boilers and process heaters can achieve efficiencies of at least 98 percent. They can be
used to reduce VOC emissions from any vent streams that will not reduce the performance or
reliability of the boiler or process heater. For example, the varying flow rate and organic content
of some vent streams can lead to explosive mixtures or flame instability. Boilers and process

heaters are most applicable where the potential exists for heat recovery from the combustion of
the vent stream.
Vent stream with a high VOC concentration and high flow rate can provide enough
equivalent heat value to act as a substitute for fuel. Because boilers and process heaters cannot
tolerate wide fluctuations in the fuel supply, they are not widely used to reduce VOC emission
from batch operations and other non-contiguous vent streams. Vent streams with sulphur or
halogenated compounds are not usually combusted in boilers or process heaters because these

1.6.5 Flares

Flaring is an open combustion process in which the oxygen necessary for combustion is
provided by the air around the flame. High combustion efficiency in a flare is governed by flame
temperature, residence time of the organic compound in the combustion zone, turbulent mixing
to complete the oxidation reaction, and the amount of available oxygen. Steam-assisted elevated
flares are the most common type used in the chemical industry. The high flow rate of the vent
stream into the flare requires more combustion air than diffusion of the surrounding air to the
flame can supply. Steam injection nozzles are added to increase gas turbulence.
Flares can achieve 98 percent destruction efficiencies. Flares are most applicable to vent
streams with wide flammability limits, low auto-ignition temperatures, and high heat contents.
Flares can be designed to control both normal process releases and emergency upsets. Flares can
be used to control almost any VOC stream and can handle fluctuations in VOC concentration,
flow rate, heat content, moisture content, and inert content. Flaring is appropriate for continuous,
batch, and variable flow vent streams. However, halogenated or sulphur-containing vent streams
are usually not flared because they can corrode the flare tip or cause the formation of acid gases
or sulphur dioxide. The EPA provisions do not allow vent streams above a specified halogen
content to be routed to a flare. (DEVELOPMENT OF NATIONAL EMISSION STANDARDS

1.6.6 Condensers

Condensation is a separation technique in which one or more volatile components are

separated from a vapor mixture through saturation followed by a phase change. Condensation
can be achieved by lowering the temperature at a constant pressure, and refrigeration can be used
to obtain the lower temperatures needed for compounds with lower boiling points.
Surface condensers and direct contact condensers are the two most commonly used types.
In surface condensers, heat transfer occurs through tubes or plates in the condenser. Thus, the
coolant fluid does not contact the vent stream, which allows for reuse of the coolant fluid.
Furthermore, the VOC‟s can be directly recovered from the gas stream. A shell-and-tube
condenser, which circulates the coolant fluid on the tube side. Direct contact condensers spray
the coolant directly into the vent stream. Therefore, the coolant cannot be reused directly and
VOC‟s cannot be recovered without further processing.
Condensers may be used to recover raw materials and/or products. The removal
efficiencies of condensers range from 50 to 95 percent, and the efficiency is dependent upon the
vent stream flow rate, concentration, temperature, moisture content, and physical properties.
Condensers are more economically feasible for streams with higher condensation temperatures.
Vent streams with high concentrations of non-condensable will require a condenser with a larger

1.6.7 Adsorption

Adsorption is a mass-transfer operation where the gas-phase (adsorbate) is captured on

the solid phase (adsorbent) by physical or chemical means. A physically adsorbed molecule is
easily removed from the adsorbent, whereas, the removal of chemisorbed molecule is difficult to
The most common industrial adsorption systems use activated carbon as the adsorbent.
Activated carbon captures organic vapours by physical adsorption. Since oxygenated adsorbents
selectively capture water vapours, they are not suitable for high-moisture process vent streams.
Activated carbon beds are regenerated with steam or nitrogen, which release the captured

vapours. A typical fixed-bed, regenerative carbon adsorption system. When one bed is saturated,
the vent stream is routed to an alternate bed while the saturated carbon bed is regenerated. The
steam-laden vapours from regeneration are sent to a condenser and then to a VOC recovery
system to separate the VOC‟s from the condensed steam.
Continuous VOC removal efficiencies of more than 95 percent are achievable using
adsorption. The VOC removal efficiency of an adsorption unit depends on the vent stream
characteristics, the physical properties of the compounds in the vent stream and of the adsorbent,
and the condition of the bed. Carbon adsorption is not recommended for vent streams with high
VOC concentrations, high or low molecular weight compounds, mixtures of high and low
boiling VOC‟s, or vent streams with high moisture content. (DEVELOPMENT OF NATIONAL

1.6.8 Absorption

Absorption is the selective transfer of one or more components of a gas mixture (solute)
into a liquid solvent. Devices based on absorption principles include spray towers, venturi and
wet impingement scrubbers, packed columns, and plate columns. Spray towers have the least
effective mass transfer capability and are generally restricted to particulate matter removal and
control of high-solubility gases. Venturi scrubbers are also limited to particulate matter and high
solubility gases. Therefore, VOC control by gas absorption is limited to packed or plate columns.
Absorption, or scrubbing, is often used to separate gaseous streams containing high
concentrations of organics,especially water-soluble compounds such as methanol,ethanol,
isopropanol, butanol, acetone and formaldehyde. It is widely used to abate VOC/HAP emissions
during natural gas purification and coke byproduct recovery. However, it is more commonly
used for controlling inorganic gases,such as HCl, than for VOCs/HAPs. (DEVELOPMENT OF
September 2008)

1.7 Selection of Model VOCs and Bacterial Species

Most of the commonly encountered VOCs are biodegradable. However, because of the
variability in structures and biological reactivity of the organic compounds, they are biodegraded
at different rates and under different conditions. Under aerobic conditions, the VOCs that can be
degraded rapidly include alcohols, aldehydes, ketones, ethers, esters, organic acids, amines, and
thiols. Aliphatic and aromatic hydrocarbons, phenols, and metheylene chloride generally are
degraded at a slower speed, while aliphatics degrade faster than aromatics such as toluene,
benzene, xylene, and styrene. Polyaromatic hydrocarbons and highly halogenated hydrocarbons,
such as trichloroethylene, trichloroethane, carbon tetrachloride, and pentachlorophenol, have the
slowest degradation rate among the VOCs (Bohn 1992). For highly halogenated hydrocarbons,
anaerobic biodegradation, such as reductive dehalogenation, is a successful alternative. (Parsons
et al, 1985)
For VOCs in gas streams, the reactions will be aerobic in most cases. One reason is that
the gas stream to be treated is usually air contaminated with relatively low concentrations of
VOCs. The 21 percent oxygen content of air means that establishing anaerobic conditions will be
difficult and costly. In addition, most of the key VOCs are best or only degraded under aerobic
conditions. This situation is particularly true for the petroleum hydrocarbons and alkane gases. A
large number of VOCs were available for study, it was decided that benzene, toluene, and p-
xylene (BTX) would be the model VOCs. BTX are the most frequently found aromatic
hydrocarbons in soil and groundwater at sites contaminated by petroleum products. A well-
studied aromatics-degrading bacterial species, Pseudomonas putida F1, was used as the model
biomass (Byung 2000)

2. Benzene, Toluene and Xylene (BTX)

In the petroleum refining and petrochemical industries, the acronym BTX refers to
mixtures of benzene, toluene, and the three xylene isomers, all of which are aromatic
hydrocarbons. The xylene isomers are distinguished by the designations ortho  ( o –), meta  (m –
), and para  ( p –) as indicated in the adjacent diagram. If ethyl benzene is included, the mixture is
sometimes referred to as BTEX.

Figure.2.1 Structural diagrams of the BTX

Source: BTX (chemistry)Wikipedia,

The BTX aromatics are very important petrochemical materials. Global consumption of
benzene, estimated at more than 40,000,000 tons in 2010, showed an unprecedented growth of
more than 3,000,000 tons from the level seen in 2009. Likewise, the para-xylene consumption
showed unprecedented growth in 2010, growing by 2,800,000 tons, and a full ten percent growth
from 2009(BTX chemistry, Wikipedia, ChemSystems report, 2011).Toluene is also a valuable
petrochemical for use as a solvent and intermediate in chemical manufacturing processes and as
a high octane gasoline component.

2.1 Properties of the BTX hydrocarbons
Table 2.1

benzene Toluene ethylebenzene p-xylene m-xylene o-xylene

C6H6 C7H8 C8H10 C8H10 C8H10 C8H10
Molecular 78.12 92.15 106.17 106.17 106.17 106.17
Boiling point 80.1 110.6 136.2 138.4 139.1 144.4
Melting point 5.5 -95.0 -95.0 13.3 -47.9 -25.2

Source: BTX (chemistry)Wikipedia,

The table above lists some of the properties of the BTX aromatic hydrocarbons, all of which are
liquids at typical room conditions.


3. Biofiltration

3.1 What is Biofiltration?

Biofiltration of off-gas containing VOCs is a relatively new application of bioprocess

engineering for the management of such waste gases. It utilizes microorganisms attached to a
porous support media for stabilization of VOCs and has potential application in a number of
Biofiltration is based on biological oxidation of VOCs using aerobic microorganisms,
immobilized on solid particles of bed media such as peat, compost, wood chips, polyurethane
foam, and their mixtures packed in a column. Biofilter is essentially a fixed-film bio-reactor that
provides a large contact area between the gas stream and the microorganisms supported on a
porous granular solid surface. These microorganisms exist both in the medium and the bio-film.
As the polluted gas stream passes through the medium, VOCs get partitioned into the bio-film
where biological oxidation occurs under aerobic conditions.
The main advantage of biofiltration is that the pollutants are not transferred from one
phase to the other phase but are converted into harmless end-products. Relatively low cost and
excellent operational stability are some other advantages of this process.
The Clean Air Act Amendments (CAAA) of 1990 proposed by the United States
Environmental Protection Agency (US-EPA) distinguishes 188 air pollutants based on their
inherent toxicity. One VOC of particular interest in toluene, which is used as a raw material for
the synthesis of compounds such as tri-nitro toluene (TNT), chloramine-T, saccharin and many
dyestuffs. Literature reports indicate that toluene causes serious adverse human health effects.
Even at low concentrations, toluene has been reported to be carcinogenic, causing damage to the
liver and kidney and paralyzing the central nervous system. Thus, the widespread use of toluene
in various industrial operations, its high vapor pressure (28.6 mmHg at 25 oC) and high polarity
characterized by its water solubility (0.53 g l-1 at 25 oC) warrants its removal before emission
into the natural environment.

Due to emission of VOCs at low concentration level and the large volume of emissions
from various industrial processes, conventional methods like adsorption, incineration and
condensation etc are uneconomical. Hence use of methods based on aerobic biodegradation in
biofilters has received attention. Several groups of researchers all over the world have studied the
behaviour and performance of such biofilters. Zilli studied removal of toluene and
styrene vapors through two identical biofilters packed with peat and glass beads.

3.2 VOC Biofiltration process

Increasing stringent environmental legislation is generating great interest in industry

towards the biological waste air treatment technique. All biological technologies rely on two
primary fundamental mechanisms-sorption and biodegradation. The biodegradation is done by
microorganisms, which are either supported on media or maintained in suspension. Supported
microorganisms are immobilized on organic media or inorganic structures, while suspended
microorganisms are maintained in a liquid phase such as activated sludge. In all instances, VOCs
and odour are biodegraded by microorganisms into carbon dioxide and water. Organic
compounds serve as the substrate or source of carbon and energy. These compounds provide the
food supply, which allows the microorganism to function and multiply.
Biological waste air treatment technology makes use of several types of bioreactors.
There are mainly four types of related biological treatment units: biofilter, biotrickling filter,
membrane bioreactor and bioscrubber. These systems have differences in their complexity,
process design, equipment dimensions and working parameters, but all of these operated based
on the same principle of biological removal.
The process of biological removal involves:

Figure 3.1 VOC Biofiltration process

Where, x is the amount of VOCs entering.
x1 is the amount of VOCs carried by the liquid
x2 is the amount of VOCs absorbed by the bacteria
x3 is the amount of VOCs coming out of the column unconverted

From the figure 3.1:

Percentage reduction of VOCs = [(x-x3)/x] %

3.2.1 Biofilters

Biofilters (BFs) are reactor in which polluted air stream is passed through a porous packed
bed on which a mixed culture of pollutant-degrading organisms is immobilized. Biofiltration
uses microorganisms fixed to a porous medium to break down pollutants present in an air stream.
The microorganisms grow in a biofilm on the surface of a medium or are suspended in the water
phase surrounding the medium particles. The filter-bed medium consists of relatively inert
substances like compost, peat, etc. which ensure large surface attachment areas and additional
nutrient supply. As air passes through the bed, the contaminants in the air phase sorb into the bio
film and onto the filter medium. The contaminants are biodegraded on biofilm.
Biofilters usually incorporate some form of water addition for control of moisture content
and addition of nutrients. In general, the gas stream is humidified before entering the bio filter
reactor. The overall effectiveness of a biofilter is largely governed by the properties and
characteristics of the support medium, which include porosity, degree of compaction, water
retention capabilities, and the ability to host microbial populations. Critical biofilter operational
and performance parameters include the microbial inoculums, pH, temperature, moisture and
nutrient content.

Figure 3.2 Schematic diagram of a biofilter unit (Prabhat

The contaminated off-gas is passed through a preconditioner for particulate removal and
humidification (if necessary). The conditioned gas stream is then passed from the bottom of a
filter bed of soil, peat, composted organic material (such as wood or lawn waste), activated
carbon, ceramic or plastic packing or other inert or semi-inert media. The media provides a
surface for microorganism‟s attachment and growth. The bed and air stream are kept moist to
encourage microbial activity. Humidification is generally the most influential parameter
affecting the sorptive capacity of a biofilter, especially at lower inlet concentration, where
Henry‟s Law controls mass-transfer rates within the biofilter. Nutrient could be mixed with the
packing material either before biofilter installation or after construction (Jantschak,
Groenestijn, Adler ,Devinny

3.2.2 Bio Trickling Filters

A biotrickling filter is a combination of a biofilter and a bioscrubber. The bacteria

responsible for decomposition are immobilised on a carrier or filter material. The filter material
consists of synthetic foam, lava or a structured plastic packing. The surface must have a structure
that allows biomass to bond to it effectively. The carrier material is constantly covered with
water. This means that water must be uniformly sprayed over the packing. The polluted
components absorb in the liquid film and are decomposed by the bacteria.

In order to feed the biomass, the required nutrients are added to the water. This water also
carries away excess sludge/biofilm, as well as decomposition products which may hinder the
biomass. The scrubbing liquid which is circulated over the packing must be checked for pH,
nutrients and salt concentration. The pH can be continuously measured and corrected. The
nutrients are constantly dosed and dosage is periodically checked via analyses. In order to keep
salt concentrations within acceptable limits, one section must be discharged and filled with fresh
water. This can take place on the basis of conductivity. To safeguard the process, a temperature
measurement can be taken for flue gases, if there is a likelihood of temperatures exceeding
required limits. This will help to spare the biotrickling filter.
In the biotrickling filter, the packing may become blocked due to strong growth in the
biofilm. This will lead to prefered flows, which will in-turn reduce efficiency and increase
pressure drop. If the blockage is too severe, the packing will have to be replaced. During
dimensioning it is important to set the load at a modest level in order to avoid such blockages.

Figure. 3.3 Biotrickling Filter

(Source: )

3.2.3 Membrane Bioreactors:

Membrane bioreactor (MBR) is the combination of a membrane process like

microfiltration or ultrafiltration with a suspended growth bioreactor.These are being increasingly
used for wastewater treatment that requires excellent effluent quality, e.g., water reuse or water
recycling (Judd, Liao et al.(2006), Yang et al.(2006), Judd and Wang et al.(2008)).
MBRs allow high concentrations of mixed liquor suspended solids (MLSS) and low production
of excess sludge, enable high removal efficiency of biological oxygen demand (BOD) and
chemical oxygen demand (COD), and reclamation. However, membrane fouling is a major
obstacle to the wide application of MBRs. Additionally, large-scale use of MBRs in wastewater
treatment will require a significant decrease in price of the membranes.

Fig 3.4 Mechanism of MBR

(source: )

3.2.4 Bio Scrubber:

A bioscrubber consists of a gas scrubber and a biological reactor. In the gas scrubber, to-
be-removed components are absorbed from the gas stream by the wash water. In the biological
reactor, the pollutants absorbed by the wash water are biologically degraded. The purified
scrubbing liquid is circulated to the scrubber, where it is able to reabsorb pollutants.

Figure 3.5(a) bioscrubber working Figure 3.5(b) diagram of bioscrubber


3.3 VOC Reduction

3.3.1 VOC reduction through bacteria
Some literature on reduction of BTX have been tabulated below in table 3.1
Table 3.1
Bacteria used % Reduction Filter media References

Benzene Halophiles or 250μmol/bottle Brine Soil Carla A.

halotolerants in 2.5 weeks at Nicholson
(Marinobacter spp.) room,2004

Toluene Mixed microbial 80 % and above Biofilters Singh
inoculum culture packed with,2005
obtained by sludge maize cob
from wastewater pieces
treatment plant.
BTX P.putida F1 28-40 % Fluidized bed Byung J Kim

3.3.2 Intermediates formed during oxidation of BTX

Intermediates of ethylbenzene and xylene :Benzene; Toluene(Dhada,2008)

Intermediates of benzene; Phenol;Hydroquinone;1, 4-benzoquinone, 2-hexanol;2-
methylcrotonaldehyde; 4-hydroxyl-3-methyl-2-butanone (Mo,2009)
Intermediates of toluene : Benzaldehyde ; Benzyl alcohol; Cresol; Benzoic acid; Phenol;
Benzene (Mo,2009)


4 Growth of Suspended Biomass

4.1 Luria Bertani Broth (LB)

For the preparation of Luria Bertani Broth nutrient solution (Carbon source included), 25
grams of LB media (M1245-500G) were suspended in 1000ml of distilled water and autoclaved
it for proper sterilization and store it properly.

4.2 Preparation of synthetic wastewater

A synthetic wastewater was prepared to provide nutrition to the bacteria. The composition of this
media is given in Table 4.1( Ambily, 2012).After mixing all the salts the solution was autoclaved
properly and stored.

Table 4.1 composition for preparation of synthetic wastewater

4.3 Acclimatization of Suspended Biomass

Figure. 4.1 Acclimatization of biomass

To acclimatize the biomass we took the wastewater sample ( IIT Kanpur Nursery site) in
a bottle fitted with impingers( Fig.4.1) and at first stage LB Broth was supplied to the biomass as
nutrition which contained carbon and other sources. The sample was aerated with the help of
impinger with a filter at inlet to retain the biomass of air. Gradually the bio mass was supplied
with synthetic wastewater (lacked carbon source) and toluene vapor and the LB broth was
reduced. Each time the biomass was centrifuged with 5000 rpm (REMI- R23) for 15 minutes
after the indication of death phase. The bacterial cells obtained through centrifugation were
washed in 0.1 M phosphate buffer, re-suspended in de-ionized water and centrifuged again. The
cells were then suspended in synthetic wastewater. The above procedure was followed
periodically to maintain the bacterial culture throughout the experiment. Finally the biomass was
supplied with synthetic wastewater as nutrient and toluene vapor as carbon source. Then at the
final stage 25% of the solution was replaced by the synthetic nutrition at certain time interval.
In regular time interval (15-30 min) the pH , absorbance (wavelength 560 nm) were monitored
through pH meter (MFRS. TOSNNIWAL INSTRUMENT, Cat No CL54) and
spectrophotometer (Wensar, V-5000) respectively.

Table 4.2 Proportion of mixing synthetic wastewater and LB broth

Synthetic wastewater (ml) LB(ml)

0 200
50 150
100 100
150 50
170 30

Replaced by 25% synthetic wastewater gradually

4.4 Calibration curve and growth of bacteria mass

After preparing LB broth and synthetic wastewater these were mixed together with the
above proportion (Table 4.2) in a succession and a small amount of bacteria was put into the
solution thus achieved. Small amount of toluene was flowed into the solution. 2-2.5 ml of this
solution was put into a clean cuvette. The absorbance of the sample was measured (Fig. 4.2) at
560 nm using a spectrophotometer. The sample was then filtered.
The absorbance of the filtered sample was measured. The difference between the two
values (Net OD) was calculated and related to the biomass in the liquid through a calibration
curve. The calibration curve was compared with various standards and it was observed that the
bacteria was mostly P.putida. The absorbance at 560 nm was measured periodically until its
value reached approximately one. The high value of absorbance was necessary to ensure a
sufficiently high concentration of cells present and, thus, accurate measurement of cell dry-
For calibration a sample of 105 ml was then collected. Then 5 ml of the sample was
measured for absorbance (Net OD) following the same procedure as described in the previous
paragraph. The rest of the 100-ml sample was filtered (Fig. 4.3) through a pre-weighed filter
paper (47-mm dia, 0.2-µm). The filter paper was then dried at 104 oC and weighed. The dry

weight of the biomass was calculated from the two measurements. Meanwhile, an additional 25
ml sample was collected from the flask, and a series of dilutions were made to the sample. The
Net OD of each sample was measured. Because the biomass concentration of the undiluted
sample was known, the biomass concentrations of the diluted samples were calculated from the
dilution ratios. All the measurements of cell absorbance and dry weight were performed in
duplicates to obtain average values. The sampling process was repeated twice as the biomass in
the flask reactor continuously grew.

Figure.4.2 Absorbance of sample Figure.4.3 Filtration of biomass

This calibration was repeated four times throughout this study. Figure 4.4 includes results
from all four sets of standards, which were consistent with each other over time. The growth of
biomass was monitored and various phases of growth had been observed (Fig. 4.5)

0.5 Batch 1 0.4 Batch 2

0.2 y = 0.0012x + 0.0034 0.2
0.1 R² = 1.0000 y = 0.0012x + 0.0025
0.1 R² = 1.0000
0 100 200 300 400 500 0
Biomass(mg/L) 0 100 200 300 400

1 Batch 3 1.5 Batch 4


0.6 1
0.4 y = 0.0012x + 0.0050
0.5 y = 0.0013x + 0.0102

0.2 R² = 0.9994 R² = 0.9991

0 200 400 600 800 0
0.00 200.00 400.00 600.00 800.001000.00

Figure. 4.4 Calibration curve for the samples over time

Toluene flow 125 ccm
Bacteria Concentration(mg/L)


150ml Synthetic media and

1500 50ml LB

20ml LB added

50ml culture media replaced

500 by 50ml Synthetic media

0 500 1000 1500 2000 2500 3000 3500 4000 4500

Figure 4.5 various stages of growth of biomass

4.5 Physical identification of bacteria
4.5.1 Preparation of Agar Plates

First 50 ml of LB (luria bertani) agar media was prepared. The substances needed for making
this media were:
a) 0.5 gm tryptone
b) 0.25 gm yeast extract
c) 0.5 gm NaCl
d) 0.75 gm agar

All these substances were mixed together to form a powder.50 ml of water was added
into the powder to form a solution. The solution in the beaker was then covered with a stirring
hot plate to boil for 1 min while stirring. The media was autoclaved for 30 min. Then the agar
was allowed to cool down. This procedure marked the end of preparation of agar media for the
bacteria. Then the agar was spreaded over Petri dish.

4.5.2 Streak Plate method

It is used for Isolation and culture of bacteria growing together in a specimen MATERIALS:
l. Mixed broth culture.
2. Nutrient agar plate


The inoculating loop was kept with flame until the wire glowed red. The loop was
allowed to cool and a loop-full of the suspension of sample was taken. The surface of the
nutrition plate was streaked with the loop carefully so not to cut into the agar. The loop was
flamed before streaking next section. Then the petri dish was covered and plate was inverted
over it. The loop was sterilized and the dish was labeled. Then the plate was incubated at 37oC
for 18-24 hours. The bacterial colonies were observed.

4.5.3 Gram staining

Step 1 – Preparation of Smear

Some of the material to be stained was suspended in a drop of water on a microscope slide, The
drop was spreaded to about the size of a nickel. Then the slide was allowed to air dried. Then it
was heated (Warm) gently to fix the smear
Step 2 - Applying the Primary Stain
The slide was flooded with Crystal Violet and allowed to stand for 1 min and rinsed with water
to remove excess stain
Step 3 - Applying the Mordant
The slide was flooded with Iodine solution and allowed to stand for 2 min and rinsed with water
to remove excess Iodine
Step 4 - Decolorization
Drip Decolorizer (80% Methanol +20% Acetone) across the slide about 5 sec .The effluent
should appear pale or clear and rinsed with water to remove excess alcohol
Step5 - Counterstaining
The slide was flooded with Safranin solution and allowed to stand for 2 min and rinsed with
water to remove excess stain. Then the plate was dried (blot dry) and observed through the lens
of microscope (1000x magnification) under Oil Immersion to identify shape and arrangement of

4.5.4 Physical observation through microscope

The figures (Fig. 4.6 and Fig.4.7) shows the type of mixed culture in the sample after observing
the shape and arrangement of bacteria
1) E-coli
2) Streptococcus
3) Pseudomonas putida
4) Rod shape bacteria in chain
5) Coccus

Figure 4.6 Microscopic view of mix culture sample Figure 4.7 Microscopic view of pseudomonas


5. Experiments

5.1 The experimental setup:

Figure 5.1 Schematic diagram of Setup for VOC reduction through attached growth of bacteria

5.2 Experiment to determine the rate of evaporation of toluene

Toluene was filled in a cylindrical beaker. Its height and radius was determined and thus,
volume was calculated. The decrease in height of the toluene over time was observed and values
were noted down. The rate of evaporation was determined as per the below procedure.
A known amount of toluene was filled in the beaker (say 10 ml), height of the toluene in
the beaker was measured which came out to be 2.6cm.Thus, height for 10 ml of toluene=2.6 cm.

Volume of beaker π× r2×h=10 ml. Cross-sectional area of the beaker π× r2= (10 L)/ (26 m) =
(0.01 m3)/ (26 m) =0.00038 m2.The rate of evaporation of toluene was observed to be [1ml]/
[(0.00038 m2) (120 min)]=21.929 ml/m2/min (2hrs average)

5.3 Characteristics of blast furnace slag granules

10.17 C
29.16 Si
27.66 S
6.93 Ti
0.82 13.03 Cr
0.97 5.74 Mn
5.04 0.49 Fe
Figure5.2 Porous blast furnace slag granules Figure5.3 Energy Dispersive X-Ray(EDAX)
Analysis of slag granule

5.4 Experiment to determine the % void of various sized packing materials:

Table 5.1 Observations for determining the %void of various sized particles

Size of packing Material(ml) Void %

4.75 250 156.3 62.5
6. 250 166.7 56.7
10 250 160.3 64.1
12.5 250 157.9 63.2
16 250 166.7 66.7
20 250 154.4 61.8

Figure 5.4 Graph between percentage Void and Slag Granule

5.5 Experiment to determine the water holding capacity of various packings

Packings of various sizes (16 mm, 12.5 mm, 6.3 mm and 4 mm) of blast furnace slag
were taken separately. Each of these packings were filled in the column upto a height of 4 cm
one by one. A known amount of water was filled into the column through the inlet and the
residue was collected from the outlet at the bottom. Observations were tabulated in table.

Table 5.2 Observations to determine water holding capacity of various packings

Packing size Height of Inlet water Outlet water Water holdup

the packing
16 mm 4cm 240 ml 230 ml 10 ml
12.5 mm 4cm 260 ml 250 ml 10 ml
6.3 mm 4cm 260 ml 250 ml 10 ml
4 mm 4cm 320 ml 280 ml 40 ml

5.6 Experiment to perform blending of various sized packings

After determining the water holding capacity of each packing material, their blending
was performed. The aim was to achieve the highest water holding capacity by blending various
sized packing together. The observations were tabulated in table:

Table 5.3 Observations for performing blending of various sized packings

Blending Ratio Height Resultant height Water

(12.5+16) mm 1:1 4cm,4cm 7cm 40-30 ml
(16+12.5+5) 2:2:1 9.332cm,9.332cm,4.666cm 23.33 100 ml
(5+6) mm 3:2 9cm,6cm 14 cm 135 ml
(4+4.75+5)mm 1:1 9cm, 5cm,4cm 15cm 150ml

For different slag granule size the % void has been determined experimentally (Fig. 5.4). On the
basis of the above result (Table 5.3) the optimized blending proportion has been chosen to be
4mm +4.75 mm +5mm.


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Table A : Physical and Chemical Properties of VOCs

Name Benzene Toluene Ethyl o-Xylene m-Xylene p-Xylene Heptane Trichlo

benzene ro

Molecular C6H6 C7H8 C6H5C2H C8H10 C8H10 C8H10 C7H16 C2HCl3

Formula (C6H5C 5 (C6H4C2 (C6H4C2 (C6H4C2H6
H3) H6) H6) )
Molar 78.1118 92.14 106.167 106.167 106.167 106.167 100.21 131.390
Appearance Colourl Colourle Clear, Clear, Clear, Clear, Colourle Colourl
ess ss liquid colourles colourles colourles colourless ss liquid ess
liquid s liquid s liquid s liquid liquid liquid
Density 0.8786 0.8669 0.8665 0.87 0.861 0.86 0.684 1.46
Melting 5.5 °C −95 °C -95°C -24°C -48°C 13°C −90.61 −73 °C
Point °C
Boiling Point 80.1 °C 110.6 °C 136°C 144.4°C 139°C 138°C 98.42 °C 87.2 °C
Solubility in 1.79 0.515 0.15 insoluble insoluble Insoluble Immisci 1.280
Water (g/L) (25°C) (25°C) (20°C) ble (25°C)
Vapor 76 22 7 6 6 6.5 40 57.8
Pressure at
20°C (mm
Flash Point −11 °C 4.4 °C 15-20 °C 32 °C 25 °C 25 °C -4°C None
Thermodyna Phase Phase Phase Phase Phase Phase Phase Phase
mic Data behaviou behaviou behaviour behaviour behaviour behaviour behavio behavio
r r Solid, Solid, Solid, Solid, ur ur
Solid, Solid, liquid, gas liquid, gas liquid, gas liquid, gas Solid, Solid,
liquid, liquid, liquid, liquid,
gas gas gas gas
*Except mentioned otherwise, data are given for materials in their standard state (at 25 °C, 100kPa)


List of VOCs defined as priority polutants by the USEPA

Source: Treatment of Volatile Organic Compounds from Gas Streams Using a Three-Phase

Circulating-Bed Biofilm Reactor by Byung J. Kim, Haibo Yu, and Bruce E. Rittmann,April 2000

1 Acrolein 17 1,2-Dichloropropane

2 Acrylonitrile 18 1,3-Dichloropropylene

3 Benzene 19 Ethylbenzene

4 Bis (Chloromethyl) Ether 20 Methyl Bromide

5 Bromoform 21 Methyl Chloride

6 Carbon Tetrachloride 22 Methylene Chloride

7 Chlorobenzene 23 1,1,2,2-Tetrachloroethane

8 Chlorodibromomethane 24 Tetrachloroethylene

9 Chloroethane 25 Toluene

10 2-Chloroethyl vinyl Ether 26 1,2-Trans-Dichloroethylene

11 Chloroform 27 1,1,1-Trichloroethane

12 Dichlorobromomethane 28 1,1,2-Trichloroethane

13 Dichlorodifluoromethane 29 Trichloroethylene

14 1,1-Dichloroethane 30 Trichlorofluoromethane

15 1,2-Dichloroethane 31 Vinyl Chloride

16 1,1-Dichloroehtylene