Control of Volatile Organic Compounds

Dr. Wesam Al Madhoun

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 2,000F.


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 1000F.

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 50F 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 -
70F to less than -200F.
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 105F 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.

General Applicability of VOC Control Systems
Figures 5 and 6 summarize the general applicability of VOC
control systems.

These two charts apply to gas streams having total VOC
concentrations less than approximately 25% of the LEL.

If the concentrations are above this value, units such as
flares (not discussed) are used for control.

Control system applicability has been divided into two
separate groups: low VOC concentration and high VOC
concentration.
There is no generally accepted distinction between these two
groups.


For the purposes of Basic Concepts in Environmental
Sciences, total VOC concentrations less than 500 ppm are
considered low.


The low concentration group is further divided into three main
categories depending on the number of different VOC
compounds in the gas stream and the value of recovering
these compounds for re-use.
If there are a large number of separate VOC compounds, it is
usually not economically feasible to recover and reuse the
captured organics.

In this case, thermal or catalytic oxidizers are used to oxidize
the VOC compounds.

Adsorbers can also be used as independent control systems
or as preconcentrators for the oxidizers.

If there are a very limited number of VOC compounds (less
than or equal to 3), it is usually possible to use either
adsorbers or biological oxidation systems
It is necessary to confirm that the compounds can be
desorbed from regenerative-type adsorbers and that the
specific organics are not toxic to the microorganisms in
biological oxidation systems.

Both thermal and catalytic oxidizers can also be used for
these types of gas streams.

If recovery and reuse are necessary, an adsorber system is
generally used as the control technique.

Due to the low VOC concentrations, the cost of organic
compound recovery can be quite high.
The applicability of VOC control systems for high
concentration systems also depends, in part, on the number
of separate VOC compounds present in the gas stream and
the economic incentives for recovery and reuse.

Thermal oxidizers can be used in all cases in which recovery
and reuse are not desired or economically feasible.

Catalytic oxidizers can be used in these same situations if
there are no gas stream components that would poison,
mask, or foul the catalyst.

Adsorbers can also be used for this service as long as there
are environmentally acceptable means for disposal of the
collected organics.
If recovery and reuse are desired, either adsorbers or
condenser/refrigeration systems can be used.

These systems are limited to gas streams containing at most
three organic compounds due to the costs associated with
separating the recovered material into individual components.

If the process can reuse a multi-component organic stream,
both adsorbers and condenser/refrigeration systems can be
used without the costs of recovered material purification and
reprocessing.
There are a number of commercial VOC control systems that
fall outside the general pattern of applicability indicated in
Figures 5 and 6.


These figures provide a very general indication of the uses
and limitations of the five main types of VOC control systems.