HEIDE Y.

SISLES ENCH5-A

THERMAL OXIDATION PROCESS

Thermal Oxidation processes incorporating energy recovery techniques can be

used to destroy pollutants chemically. The term incineration will not used to describe
thermal oxidation because of its common association with municipal solid waste
incineration. In thermal oxidation process it is assumed that the pollutant is a gas or
vapour (although the theory can be used for the oxidation of limited amounts of liquid and
solid matter).
For there to be successful thermal oxidation, regulatory agencies require that the
following conditions must be satisfied:
1. The pollutant must reside in the hot region for some agreed amount of
residence time, typically 0.5 to 1.0 s.
2. The average temperatures in the hot region must be within certain limits,
typically 1050 to 1250 K for direct flame oxidizers and 700 K for catalytic
oxidizers.
3. The concentrations and mass emission rates of the exhaust products must be
within certain limits.
Specific values of the residence time and average oxidation temperature depend
on the pollutant being oxidized.
A principal drawback to thermal oxidizers is the generation of nitrogen oxides and
possibly new pollutants. Wether new pollutants will be generated by oxidation is difficult
to anticipate, although certain classes of waste streams are apt to produce certain type
of pollutants. For example, it can be anticipated that oxidizing chlorinated compounds
may produce an exhaust stream in which HCl or free chlorine are discharged to the
atmosphere unless steps are taken to adsorb or absorb them. Thus engineers must take
steps to ensure that thermal oxidizers are not new sources of pollution.
Thermal oxidization is a generic phrase and includes all thermal devices where air
and an auxiliary fuel are used to produce a region of high temperature in which pollutants
are oxidized. Thermal oxidizers can be divided as follows.
 Afterburners
 Direct-flame oxidizers with energy recovery
o Regenerative oxidizer
o Recuperative oxidizer
 Catalytic oxidizers
  AFTERBURNERS

Afterburners are elementary combustors that have low initial and maintenance
costs per cfm (cubic feet per minute) but high operating costs. Afterburners are attractive
for small installations when the pollutant mass flow rate is small and the composition apt
to vary with time. Oxidizers with heat recovery are attractive when the process gas stream
is large and continuous and when transferring the energy of the exhaust to the incoming
process gas stream is financially attractive. Thus per cfm treated, heat recovery oxidizers
have a high initial cost but minimal operating costs.
Process gas streams associated with the laminating, surface finishing and coating,
chemicals, and wood products industries are particularly difficult to control. Such streams
contain solid particles and high-molecular-weight hydrocarbons that produce sticky
condensates. Treating these process gas streams is particularly difficult and causes
serious operating and maintenance problems. If the process of raw materials cannot be
changed to prevent generating these pollutants, the only available remediation
technology is regenerative thermal direct flame oxidizers.
 REGENERATIVE OXIDIZER
 The characteristic feature of regenerative oxidizers are beds of ceramic material
through which flow both hot exhaust products for one period of time and the cool inlet
process gas stream for other periods of time. Thus the process gas stream flip-flops. The
heat-resistant material in the regenerative oxidizer bed, stores energy from hot gases
exiting the combustion chamber while another preheated regenerator releases heat to
the cold gases entering the combustion chamber. This switching of the gas flow between
regeneration beds is accomplished by large damper valves that alternately open and
close. As a result of this switching, a pulse of untreated waste gas always escapes to the
discharge side of the oxidizer and limits the overall oxidation efficiency to a maximum of
95%. Owing to the robust and large (1-in.) ceramic packing elements, regenerative
oxidizers can cope with gas streams containing sticky particulate matter or pollutants that
might condense on the cooled bed and may coat the packing for a time. The packed beds
are heated periodically to bake-out this particulate matter. If, however, the particulate
matter is not combustible, the porosity of the packing may decrease over time.
 RECUPERATIVE OXIDIZER

Recuperative oxidizers use high efficiency air-to-air heat exchangers to recover

energy. Heat is transferred from the hot exhaust to the cool incoming combustion air
through a conducting surface that separates the gases (i.e., shell-tube or plate heat
exchangers). Recuperative oxidizers tend to have lower capital costs than regenerative
oxidizers for volumetric flow rates less than 40,000 cfm, yet have higher operating costs
than regenerative oxidizers for all volumetric flow rates. Recuperative oxidizers are less
forgiving than regenerative oxidizers since the narrow gas passages become irreparably
fouled when handling dirty particulate-laden gas streams or gas streams containing
pollutants that are apt to condense. The overall pollutant destruction efficiency of
recuperative oxidizers is in general higher than in regenerative oxidizers. On the other
hand, the efficiency of heat recovery in recuperative oxidizers is generally lower than in
regenerative oxidizers. Recuperative oxidizers cannot be baked out as easily as
regenerative oxidizers.
  CATALYTIC OXIDIZER

Catalytic oxidizers contain catalytic surfaces that enable reactions to occur at lower
temperatures, typically 300 to 800 ˚F, than would be possible in the gas phase without
the catalyst. The catalyst is not consumed in a reaction; it is merely the active surface
agent that enables the chemical reaction to occur, whereas it would not occur, thermally.
A catalyst is composed of a ceramic or metal substrate with a high surface area-to-volume
ratio. On the surface of the substrate is a thin layer of catalytic material. Catalytic surfaces
may be deactivated by exposure to certain materials. Deactivation may be irreversible or
reversible.
1. Irreversible deactivation. Poisons such as phosphorus, bismuth, lead, arsenic,
antimony, mercury, iron oxides, tin, and silicon produce irreversible damage.
Catalytic surfaces can also be damaged permanently if the temperatures are too
high, causing the substrate or catalytic surface to sinter.
2. Reversible deactivation. Sulfur in a reducing environment, halogens, zinc, and
solid organic materials produce damage that may be corrected by washing with
detergent, acidic, or caustic fluids. It may be possible to remove organic materials
deposited (blinding) on a catalytic surface by baking or burning.
Catalytic oxidizers have low fuel costs because they operate at lower temperatures
than direct flame devices but are useful mainly when the composition of the process
gas steam is known and does not vary. Catalytic oxidizers are ideally suited for the
oxidation of volatile organic compounds (VOCs), but specially designed catalysts are
required for the oxidation of halogenated hydrocarbons. Gases containing chlorine
and sulphur can deactivate noble metal catalysts such as platinum or palladium. Lead,
arsenic, and phosphorus are generally considered poisons for most oxidation
catalysts. Because oxidation occurs at low temperature, catalytic oxidizers produce
minimal amounts of nitrogen oxides. Catalytic oxidizers can incorporate heat
exchangers to transfer energy from the exhaust stream to the incoming airstream.
 Regardless of the type of oxidizer, designing a chamber in which pollutants
reside for no less than a certain amount of time and achieve a certain minimum
temperature is similar to the design of any kind of reaction chamber (internal
combustion engines, jet engines, rocket engines, chemical reactors, steam boilers,
etc.). Governing the design are the conservation equations of mass, momentum, and
energy modified to include terms describing the formation and destruction of certain
combustion species.