Control of Volatile Organic

Compounds
 Characteristics
• The majority of anthropogenic VOCs released into the
atmosphere are from transportation sources and industrial
processes utilizing solvents such as surface coating (paints),
printing (inks), and petrochemical processing (see Figure 1).
• VOCs are organic compounds that can volatilize and
participate in photochemical reactions when the gas
stream is released to the ambient air.

• Almost all of the organic compounds used as solvents

and as chemical feedstock are VOCs.

• A list of those few organic compounds that

are not considered to be VOCs is provided in Table 1.

• Other organic compounds are considered to be VOCs.

 Control Techniques
• The dominant source of VOC emissions is the vaporization of
organic compounds used in industrial processes.

• A variety of techniques can be used to reduce VOC emissions.

• Using material containing an inherently low quantity of VOC

compounds will reduce the release of VOCs.

• Also, the processes can be redesigned to reduce the quantities

that are lost as fugitive emissions.
• When these techniques are inapplicable or insufficient,
add-on control systems, such as the techniques listed
below, can be used:

• Thermal oxidation

• Catalytic oxidation

• Adsorption

• Condensation and refrigeration

• Biological oxidation
 Thermal Oxidation
• In a thermal oxidizer, the VOC-laden air stream is
heated to gas temperatures several hundred degrees
Fahrenheit above the autoignition temperatures of
the organic compounds that need to be oxidized.

• Due to these very high temperatures, thermal

oxidizers have refractory-lined combustion chambers
(also called fume incinerators), which increase their
weight and size considerably.

• A sketch of a thermal oxidizer is shown in Figure 1.

• The VOC-laden gas stream is held at this temperature
for residence times ranging from a fraction of a
second to more than two seconds.

• Temperatures of the exhaust gas from the refractory-

lined combustion chambers are often 1,000 to
2,000°F.

• Thermal oxidizers usually provide VOC destruction

efficiencies that exceed 95% and often exceed 99%.
• One of the main limitations of thermal oxidizers is the
large amount of fuel required to heat the gas stream to the
temperature necessary for high-efficiency VOC
destruction.

• Heat exchangers are used to recover some of this heat.

• The heat exchanger shown in Figure 1 is sometimes called

a recuperative heat exchanger.

• This type of heat exchanger has a heat recovery efficiency

ranging from 30 to 60% depending on the size of the unit.
• Some types of thermal oxidizers use large regenerative
beds for heat exchange.

• These beds have heat recovery efficiencies up to 95%.

• Due to the amount of heat that can be recovered and

returned to the inlet gas stream,

• these units, termed regenerative thermal oxidizers (RTOs)

require less fuel to maintain the combustion chamber at
the necessary temperature.
• Thermal oxidizers have the broadest applicability of all the
VOC control devices.

• They can be used for almost any VOC compound.

• Thermal oxidizers can also be used for gas streams having

VOC concentrations at the very low concentration range of
less than 10 ppm up to the very high concentrations
approaching 10,000 ppm.

• Thermal oxidizers are rarely used on gas streams having

VOC concentrations exceeding approximately 25% of the
lower explosive limit (LEL).
• This limit is imposed by safety constraints due to the
possibility that a short-term concentration spike would
exceed the LEL, and the gas stream would explode.

• The 25% LEL limit depends on the actual gas constituents

and usually is in the 10,000 to 20,000 ppm range.

• Thermal oxidizers handling VOC materials that contain

chlorine, fluorine, or bromine atoms generate HCl, Cl2, HF,
and HBr as additional reaction products during oxidation.

• A gaseous absorber (scrubber) is used as part of the air

pollution control system to collect these contaminants
prior to gas stream release to the atmosphere.
 Catalytic Oxidation
• Catalytic oxidizers operate at substantially lower temperatures
than thermal oxidizers.

• Due to the presence of the catalyst, oxidation reactions can be

performed at temperatures in the range of 500 to 1000°F.

• Common types of catalysts include noble metals (i.e. platinum

and palladium) and ceramic materials.

• VOC destruction by catalytic oxidizers usually exceeds 95% and

often exceeds 99%.

• A sketch of a catalytic oxidizer is shown in Figure 2.

• Due to the relatively low gas temperatures in the
combustion chamber, there is no need for a refractory
lining to protect the oxidizer shell.

• This minimizes the overall weight of catalytic oxidizers and

provides an option for mounting the units on roofs close to
the point of VOC generation.

• This placement can reduce the overall cost of the system by

limiting the distance the VOC-laden stream must be
transported in ductwork.
• Catalytic oxidizers are also applicable to a wide range of
VOC-laden streams;

• however, they cannot be used on sources that also

generate small quantities of catalyst poisons.

• Catalyst poisons are compounds that react chemically in an

irreversible manner with the catalyst.

• Common catalyst poisons include phosphorus, tin, and

zinc.
• Another potential operating problem associated with
catalytic oxidizers is their vulnerability to chemicals and/or
particulate matter that masks or fouls the surface of the
catalyst.

• (Masking is the reversible reaction of a chemical with the

catalyst and fouling is the coating of the catalyst with a
deposited material.)

• If the conditions are potentially severe, catalytic units are

not installed.

• As with thermal oxidizers, catalytic oxidizers should not

exceed 25% of the LEL, a value that is often equivalent to a
VOC concentration of 10,000 to 20,000 ppm.
 Adsorption
• Adsorption systems beds are generally used in the
following two quite different situations:

1- When the VOC-laden gas stream only contains one to three

organic solvent compounds, and it is economical to recover
and reuse these compounds, or

2- When the VOC-laden gas stream contains a large number

of organic compounds at low concentration, and it is
necessary to preconcentrate these organics prior to
thermal or catalytic oxidation.
• A flowchart for a multi-bed adsorber system used for
collection and recovery of organic solvent
compounds is shown in Figure 3.
• The VOC-laden gas is often cooled prior to entry into the
adsorption system because the effectiveness of adsorption
improves at cold temperatures.

• As the gas stream passes through the bed, the organic

compounds adsorb weakly onto the surfaces of the
activated carbon, zeolite, or organic polymer used as the
adsorbent.

• Essentially all of the commercially used adsorbents have a

very high surface area per gram of material.

• When the adsorbent is approaching saturation with organic

vapor, a bed is isolated from the gas stream and desorbed.
• Low-pressure steam or hot nitrogen gas is often used to
remove the weakly adsorbed organics.

• The concentrated stream from the desorption cycle is

treated to recover the organic compounds.

• After desorption, the adsorption bed is returned to service,

and another bed in the system is isolated and desorbed.
• An adsorption system used for preconcentration is smaller
than a system similar to the one in Figure 3 for solvent
recovery.

• In preconcentrator systems, the VOC-laden stream passes

through a rotary wheel containing zeolite or carbon-based
adsorbents.

• Approximately 75-90% of the wheel is in adsorption service

while the remaining portion of the adsorbent passes
through an area where the organics are desorbed into a
very small, moderately hot gas stream.
• The concentrated organic vapors are then transported to a
thermal or catalytic oxidizer for destruction.

• The preconcentration step substantially reduces the fuel

requirements for the thermal or catalytic oxidizer.
• Adsorption systems (in general) are usually limited to
sources generating organic compounds having a molecular
weight of more than 50 and less than approximately 200.

• The low molecular weight organics usually do not adsorb

sufficiently.

• The high molecular weight compounds adsorb so strongly

that is it is difficult to remove these materials from the
adsorbent during the desorption cycle.
• These molecular weights are provided as a guideline and
the suitability of an adsorption system for a particular
situation should be considered on a case-by-case basis.

• Adsorption systems can be used for a wide range of VOC

concentrations from less than 10 ppm to approximately
10,000 ppm.

• The upper concentration limit is due to the potential

explosion hazards when the total VOC concentration
exceeds 25% of the LEL.
• Adsorption systems are not recommended for gas
streams that contain particulate matter and/or high
moisture concentrations, because the particulate
matter and moisture compete with the gaseous
pollutants for pore space on the adsorbent material.

• The adsorption removal efficiency usually exceeds

95% and is often in the 98% to 99% range for both
solvent recovery and preconcentrator type systems.

• In both types of units, the removal efficiency

increases with reduced gas temperatures.
 Condensation, Refrigeration, and
Cryogenics
• Condensation, refrigeration, and cryogenic systems
remove organic vapor by making them condense on cold
surfaces.

• These cold conditions can be created by passing cold water

through an indirect heat exchanger, by spraying cold liquid
into an open chamber with the gas stream,

- by using a freon-based refrigerant to create very cold coils,

or by injecting cryogenic gases such as liquid nitrogen into
the gas stream.
• The concentration of VOCs is reduced to the level
equivalent to the vapor pressures of the compounds at the
operating temperature.

• Condensation and refrigeration systems are usually used

on high concentration, low gas flow rate sources.

• Typical applications include gasoline loading terminals and

chemical reaction vessels.

• The removal efficiencies attainable with this approach

depend strongly on the outlet gas temperature
• For cold-water-based condensation systems, the outlet gas
temperature is usually in the 40 to 50°F range,

- and the VOC removal efficiencies are in the 90 to 99% range

depending on the vapor pressures of the specific
compounds.

• For refrigerant and cryogenic systems, the removal

efficiencies can be considerably above 99%,

- due to the extremely low vapor pressures of essentially all

VOC compounds at the very low operating temperatures of
-70°F to less than -200°F.
• Condensation, refrigeration, and cryogenic systems
are usually used on gas streams that contain only
VOC compounds.

• High particulate concentrations are rare in the types

of applications that can usually apply this type of
VOC control system.

• However, if particulate matter is present, it could

accumulate on heat exchange surfaces and reduce
heat transfer efficiency.
 Biological Oxidation
• Biological systems are a relatively new control device in the
air pollution control field.

• VOCs can be removed by forcing them to absorb into an

aqueous liquid or moist media inoculated with
microorganisms that consume the dissolved and/or
adsorbed organic compounds.

• The control systems usually consist of an irrigated packed

bed that hosts the microorganisms (biofilters).

• A presaturator is often placed ahead of the biological

system to increase the gas stream relative humidity to more
than 95%.
• The gas stream temperatures are maintained at less than
approximately 105°F to avoid harming the organisms and to
prevent excessive moisture loss from the media.

• Biological oxidation systems are used primarily for very low

concentration VOC-laden streams.

• The VOC inlet concentrations are often less than 500 ppm and
sometimes less than 100 ppm.
• The overall VOC destruction efficiencies are often
above 95%.

• Biological oxidation systems are used for a wide

variety of organic compounds; however, there are
certain materials that are toxic to the organisms.

• In these cases, an alternative type of VOC control

system is needed.