Catalytic

oxidation of
VOCs
Catálisis Heterogénea

Santiago Sánchez Gómez

Manuela Alejandra Rueda

Universidad de Antioquia
2020-1
 Introduction
A brief definition of VOCs
Volatile organic compounds (VOCs) usually refers to those organic compounds with low boiling
points (50 - 260 °C), or high atmospheric pressures. It means that VOCs easily evaporate at room
temperature. Typically these compounds are known to be solvents.

VOCs usually have less than twelve carbon atoms in their chain and contain other elements such as
oxygen, fluoride, chlorine, bromine, sulphur or nitrogen.
VOCs in industry (Why are they
bad?)
Rapid urbanization and industrialization
contribute to the growing emissions of VOCs
into the environment.

Emissions of VOCs can come from different

sources like: Food processing, petroleum
refineries, textile manufacturers, printers
and wood stoves, among others.

VOCs have been identified as responsible for

tropospheric ozone formation, ground
level smog formation, climate change,
decay of plants, toxicity of the
atmosphere, and carcinogenic effects in
humans.
VOCs in industry (Why are they
bad?)
Type and nature of VOCs depend on the source of emission.

The effect of VOCs on the atmosphere depends on the nature of VOCs, their concentration, and
emission sources.
Treatment of VOCs

The emission of VOCs can be controlled using methods based on recovery and destruction.

Recovery Methods Destruction Methods

VOCs CO2 + H2O
● Absorption
Disposal of VOCs and spent of solvent. ● Thermal oxidation
● Adsorption Incomplete combustion or incineration
High cost of adsorbents and their produces undesirable byproducts (CO and
regeneration. dioxins).
● Condensation ● Catalytic oxidation
Spent of coolants. Only for evaporative Low temperature operation and
solvents. formation of less noxious products.
● Membrane separation
Costly process and expensive operation.
Catalytic
Oxidation
Catalytic oxidation

Catalytic oxidation is one of the most effective and economically feasible techniques for the
oxidation of VOCs into CO2, water and other relatively less harmful compounds. It looks for the
complete destruction of VOCs rather than transferring it to another phase as in other techniques,
such as in condensation and adsorption.

❏ Catalyst
❏ Lower temperatures (250 - 500 °C)
❏ The product selectivity can be controlled
❏ Less noxious products

Some restrictions! It is most suitable for moderate flow rates and a low concentration of VOCs
(<0.5 vol %)
Catalytic oxidation
The catalyst

One of the main challenges of catalytic oxidation of VOCs is the selection of the proper catalysts.
Due to their wide variety and nature of the range of mixtures of VOCs, it is most often difficult to
identify the best possible catalyst.

A significant amount of investigations have

considered the design and synthesis of catalysts
for VOC oxidation.
The catalyst

In general, three fundamental types of catalysts are used in these processes:

❏ Noble metal catalysts

❏ Non-noble metal oxide catalysts

❏ Mixed metal catalysts

The catalyst

Noble metal catalysts (Rh, Pt, Pd, Au…)

Noble metals are attractive as catalysts due to their high efficiency for the removal of VOCs at
low temperatures. The most common support materials for the noble metal catalysts are ceramics
or metallic material in monolithic or honeycomb form.

➔ Superior activity
➔ Ease of regeneration
➔ Expensive and deactivated by sintering or poisoning
➔ They are not normally selective enough when alone
➔ Less stable in the presence of chloride compounds
The catalyst

Noble metal catalysts (Rh, Pt, Pd, Au…)

➔ Performance of these catalysts depends on the method of preparation, precursor type,

particle size, metal loading, concentration of the VOCs, reactor type, and the overall gas flow
rate.
The catalyst

Noble metal catalysts (Rh, Pt, Pd, Au…)

The catalytic combustion of toluene was used to

evaluate the catalytic activity of the developed
catalysts
The catalyst

Non-noble metal oxide catalysts (Fe, Co, Ni, Cr…)

This catalysts are a cheaper alternative to the noble metals. They possess excellent electron
mobilities and positive oxidation states. Can be either supported or unsupported metal oxides.

➔ Less active than the noble metal catalysts

➔ Low cost
➔ Thermal stability
➔ Resistance to poisoning

Other advantages include: long lifetime, masking tolerance, capability of regeneration, and the
availability of a range of metal oxides in different sizes and shapes.
The catalyst

Non-noble metal oxide catalysts (Fe, Co, Ni, Cr…)

➔ The supported catalysts show better activity and performance due to greater dispersion of the
active component. Support materials and the preparation methods are crucial in determining
the performance of metal-oxide catalysts (physicochemical properties of the active phase).
The catalyst

Non-noble metal oxide catalysts (Fe, Co, Ni, Cr…)

The catalyst

Mixed metals catalysts

The catalyst

How they “synthesize” the catalyst?

➔ Preparation
➔ Characterization
➔ Activity measurement
The catalyst

How they “synthesize” the catalyst?

The process (A schematic view
of the reactor)
Mechanistic proposals

Many factors, such as the catalyst elemental composition, the catalyst physicochemical properties,
the pollutant composition, and reaction conditions, can all drastically influence the surface
mechanisms taking place.

The mechanisms proposed for the complete catalytic oxidation of VOCs generally fall into three
main categories:

● Mars-van Krevelen model: Absorbed VOCs and lattice oxygen of the catalyst.

● Langmuir-Hinshelwood model: Absorbed VOCs and absorbed oxygen.

● Eley-Rideal model: Absorbed VOCs and oxygen in gas phase.

Mechanistic proposals

The validity of each model depends on catalyst property as well as the nature of the VOCs being
studied. The Mars-van Krevelen model has been commonly used for the kinetic modeling of
hydrocarbon oxidation reactions, especially over metal oxide materials.

Mars-van Krevelen model

This model assumes that the oxidation of the VOCs takes place in two steps: In the first step, the
adsorbed VOCs react with oxygen in the catalyst, leading to the reduction of the metal oxide. In
the second step, The reduced sites are then immediately reoxidized by the gas-phase oxygen
present in the feed.
Mechanistic proposals

Mars-van Krevelen model

Inside the reaction (Conditions
and thermodynamics)
“...the higher the molecular weight, the more difficult it is to oxidize VOCs.”

alcohols < aldehydes < aromatics < ketones < acetates < alkanes

At sufficiently high reaction temperatures, the catalytic oxidation mainly gives CO 2 and H2O
according to the following reaction:
Inside the reaction (Conditions
and thermodynamics)
The oxidation behavior of VOCs is influenced by reactant composition and reaction conditions, such
as:

● The role of water

● Promotion effect of ozone

● Mutual effect of miscellaneous VOCs

Inside the reaction (Conditions
and thermodynamics)
The role of water

The presence of water in catalytic oxidation of VOCs is very complex, depending on many factors,
such as catalyst component, VOC type, and reaction conditions.

Water vapor is found to act as an inhibitor for VOC deep oxidation, this is attributed to the
competitive adsorption of water molecules.
Inside the reaction (Conditions
and thermodynamics)
Promotion effect of ozone

The use of ozone in catalytic oxidation favors the conversions at lower temperatures, a case that
is not easy accomplished with molecular oxygen. The ozone induce the formation of active
oxygen species on the surface of catalysts, in other words, the ozone helps to reoxidize the
oxygen sites in the catalyst surface, and so continue with the cycle.
Inside the reaction (Conditions
and thermodynamics)
Mutual effect of miscellaneous VOCs

Industrial flue gas streams generally contain a mixture of VOCs with different physical and chemical
properties. The presence of other molecules usually inhibits the oxidation of VOCs, which is
attributed to the competition among various VOC pollutants and reaction intermediates for
adsorption sites.

The activity of the catalyst for the oxidation

of VOCs depends on the rate of redox reaction
on the surface:
Inside the reaction (Conditions
and thermodynamics)
Mutual effect of miscellaneous VOCs

The reducing site on the catalyst surface could be generated by each VOC involved:
Perspectives on catalytic
oxidation of VOC’s
Catalytic oxidation is one of the most promising technologies for VOCs removal. Despite the
progress of catalytic oxidation of VOCs, there’re still problems to solve, and that for now they’re
being studied and developed:

❏ Developing efficient catalysts with highly dispersed active phases.

❏ Designing highly active, universally applicable, and stable catalysts with strong resistance to
poisons.
❏ Demonstrating how bond cleavage and oxidation mechanisms of VOCs are influenced by
reaction conditions or times at the molecular level.
❏ Development and study of new supports, such as carbon nanotubes. Seeking to improve the
processes of adsorption and catalytic activity.
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