ASSIGNMENT

CMT 674
THE BENEFITS OF CATALYTIC PROCESSES
PREPARED BY:
KHAIRUN NIESA BINTI ABDULLAH
2013633154 (AS245 6M)
PREPARED FOR:
AP DR RUSNAH HAJI SAMSUDDIN
SUBMISSION DATE: 29TH APRIL 2016

TABLE OF CONTENT

TITLE

PAGES

1.0 INTRODUCTION
1.1 Catalysis
1.2 Catalysts provide alternative reaction pathways
1.3 Role of Catalysts
1.4 Type of catalysts

2.0 LITERATURE REVIEW

2.1 Catalysis in industry
2.1.1 Heterogeneous catalysts
2.1.2 Zeolites
2.2 Area of application
2.2.1 Petrochemical
2.2.2 Palm oil biorefining

3.0 CONTENT
3.1 Petrochemical industries
3.2 Palm-oil biorefinery

10

4.0 DISCCUSION

14

5.0 CONCLUSION

16

6.0 RECOMMENDATION

16

7.0 REFERENCES

17

1.0 INTRODUCTION
1.1 Catalysis
Catalysis is an acceleration or retardation of the rate of a chemical reaction,
brought about by the addition of a substance (the catalyst ) to the reaction
medium. The catalyst, usually present in small amounts, is not consumed in the
reaction. Catalysis is also a modification and especially increase in the rate of a
chemical reaction induced by material unchanged chemically at the end of the
reaction. Catalysts are substances that speed up a reaction but which are not
consumed by it and do not appear in the net reaction equation.
Catalysis today is almost always associated with rate acceleration, and is very
important in industry because rate acceleration usually means that a chemical
compound can be made more cheaply and cleanly. It is hard to envision what
modern society would be like without its use of myriad chemicals, polymers, and
pharmaceuticals, most of which are prepared industrially by catalytic chemistry.
In addition, catalysts affect the forward and reverse rates equally; this means that
catalysts have no effect on the equilibrium constant and thus on the composition
of the equilibrium state. Thus a catalyst (in this case, sulfuric acid) can be used to
speed up a reversible reaction such as ester formation or its reverse, ester
hydrolysis:

The catalyst has no effect on the equilibrium constant or the direction of the
reaction. The direction can be controlled by adding or removing water (Le
Chtelier principle).

1.2 Catalysts provide alternative reaction pathways

Catalysts function by allowing the reaction to take place through an alternative
mechanism that requires a smaller activation energy. This change is brought about
by a specific interaction between the catalyst and the reaction components. Recall
that the rate constant of a reaction is an exponential function of the activation
energy, so even a modest reduction of Ea can yield an impressive increase in the
rate. The rate of reaction refers to the amount of reactant consumed or product
formed per unit of time at a given temperature and pressure. Generally speaking,
the rate of reaction goes up as the temperature of the reaction is raised. This is
related to the fact that most reactants have to "climb" over one or more energy
barriers to reach the product stage. This can be likened to one's climbing a hill.
The taller the hill, the more energy one expends in reaching its top. Reactants
must become energetic enough to "reach" the top of an energy barrier if a reaction
is to occur. Raising the reaction temperature ultimately imparts more energy to
the reactants, creating a greater probability that more of them will be energetic
enough to traverse the barrier, and this results in a faster rate.
1.3 Role of Catalysts
First of all, a catalyst does not change the energetic characteristics of the reactants
and products and the barriers between them. It instead finds an alternate reaction
pathway that bridges reactants and products, and one that has lower (and thus
easier-to-traverse) energy barriers. An alternate pathway means a faster reaction
rate. Although a catalyst can itself be considered a reactant, it is regenerated,
unchanged, at a later stage in the catalytic process. The regenerated catalyst can
then be used to catalyze another like reaction. Thus, in principle, only a very
small amount of catalyst is needed to generate copious amounts of product. This
is desirable, as many catalysts that are used industrially are very expensive.

1.4 Types of catalyst

Catalysts are conventionally divided into two categories: homogeneous and
heterogeneous. Enzymes, natural biological catalysts, are often included in the
former group, but because they share some properties of both but exhibit some
very special properties of their own, they are treated here as a third category.

1.5 Examples of catalytic reactions

Type

Reaction
Phase(s)
homogeneous gas

Reaction

Catalyst
chlorine atom
sulfuric acid

Fischer esterification

aluminum
chloride
rhodium salts
+1
iron
transition metals
such at Pt and
Pd

Friedel-Crafts
acylation

heterogeneousgas-solid

ozone oxygen
alcohol + acid
ester
arene + acid
chloride ketone
methanol + CO
acetic acid
3H 2 + N 2 2NH 3

Name of
Process/Reaction
ozone depletion

zeolite

catalytic cracking

liquid
liquid
liquid

gas-liquid- alkene +
solid
H 2 alkane
crude oil
gasoline
waste water +
liquid-solid H 2 O 2 (O 2 )
clean water
starch Dwater
glucose
cellulose Dwater
glucose
gas-solid

enzyme

Monsanto process
Haber process
catalytic
hydrogenation

titanium dioxide photocatalysis

-Glucosidase

hydrolysis

-Glucosidase

hydrolysis

2.0 LITERATURE REVIEW

2.1 Catalysis in industry
Much fundamental and applied research is done by industrial companies and
university research laboratories to find out how catalysts work and to improve
their effectiveness. If catalytic activity can be improved, it may be possible to
lower the temperature and/or the pressure at which the process operates and thus
save fuel which is one of the major costs in a large-scale chemical process.

Further, it may be possible to reduce the amount of reactants that are wasted
forming unwanted by-products.
If the catalyst is in the same phase as the reactants, it is referred to as
a homogeneous catalyst. A heterogeneous catalyst on the other hand is in a
different phase to the reactants and products, and is often favoured in industry,
being easily separated from the products, although it is often less specific and
allows side reactions to occur.
2.1.1 Heterogeneous catalysis
The most common examples of heterogeneous catalysis in industry
involve the reactions of gases being passed over the surface of a solid,
often a metal, a metal oxide or a zeolite

Process

Catalyst

Making ammonia

Iron

Making synthesis gas (carbon

monoxide and hydrogen)

Nickel

Catalytic cracking of gas oil

Zeolite

Reforming of naphtha

Platinum and
rhenium on
alumina

Making epoxyethane

Silver on alumina

Making sulfuric acid

Vanadium(V)
oxide on silica

Making nitric acid

Platinum and
rhodium

Equation

Produces:
a gas (e.g. ethene, propene)
a liquid (e.g.petrol)
a residue (e.g. fuel oil)

Table 1 Examples of industrial processes using heterogeneous catalysis.

2.1.2

Zeolites
The ability of the zeolite to adsorb some molecules and to reject others
gives it the ability to act as a molecular sieve. For example, in the
manufacture of ethanol from ethene or from biomass, an aqueous

solution of ethanol is produced, in which there is 4% water still present

even after repeated distillations. Further purification of ethanol
requires the use of a zeolite which absorbs the water preferentially.
Table 2 gives examples of industrial processes involving zeolites (The
essential chemical industry, n.d )
Process

Catalyst

Catalytic cracking of gas oil

Zeolite

Reforming of naphtha

Platinum and
rhenium on zeolite

Disproportionation of
methylbenzene

Zeolite

Dealkylation of
methylbenzene

Zeolites

Making cumene (1methylethyl)benzene<

Zeolite (ZSM-5)

Equation

Produces:
a gas (e.g. ethene, propene)
a liquid (e.g.petrol)
a residue (e.g. fuel oil)

Table 2 Examples of industrial processes using zeolites.

2.2 Area of application

Catalyst manufacturing was one of the earliest commercial application areas for
modern nanoscience methods. Important examples include sol-gel wash coat
processing for the fabrication of automobile catalytic converters and use of
zeolites with tailored framework structures for shape-selective chemical and fuel
processing (Evelyn et al., 2011).
2.2.1

Petrochemical
Zeolites have ceased to be minerals merely displayed in museums, and
have become a commercial and scientific success-story since their
large-scale utilization in industry. It all started with the use of synthetic
zeolites in oil refining and petrochemicals. The rest is now part of

industrial history: it is a case study of breakthrough and incremental

innovation (Moulijn et.al., 2001) and a model of interplay between
science and technology, from very fundamental academic research and
industrial curiosity to efficient large scale production of zeolites and
their deployment in catalytic- or adsorbent based processes.
This contribution is not another updated compilation of zeolite-based
processes found in oil refining and petrochemistry; many reviews exist
already (Guisnet et.al.,2005) and point to further and more detailed
studies. In particular, the two volume contribution of Marcilly is a
compulsory reading for the serious beginner for the depth and the
breadth of its coverage; moreover, it gives a unique perspective by a
seasoned practitioner acquainted with both fundamental and applied
aspects of zeolites and other acidbase catalytic processes.Zeolites
have so far been extensively used in the petroleum industry and could
still play an important role in the major challenges ahead of us. These
are the exploitation of non-conventional petroleum resources (tar
sands, heavy crude oil and oil shales), nonpetroleum,resources like gas
and coal and valorization of biomass for our petrochemicals production
and fuel supply (Vermeiren & Gilson, 2009).
2.2.2

Palm-oil refining
Lipases (triacyl glycerol hydrolases E.C.3.1.1.3) catalyst the hydrolysis
of triglycerides at the oil/water interface, but their ability to form ester
bonds under reverse hydrolytic conditions enables them to catalyst
various

other

types

of

reactions

such

as

esterification,

transesterification, polymerization and lactonization. The high

selectivity and mild conditions associated with lipase-mediated
transformations have made them very attractive for the synthesis of a
wide range of natural products, pharmaceuticals, fine chemicals, food
ingredients (Schreier, 1997) and bio-lubricants (Drm et al., 2004).
For example, lipases are employed to obtain polyunsaturated fatty
acids (PUFAs) which are then used along with mono- and diglycerides
for the synthesis of nutraceuticals and pharmaceuticals such as
anticholesterolemics, anti-inflammatories and thrombolytics (Gill and

Valivety, 1997; Belarbi et al., 2000). The main reason for the use of
lipases is the growing interest and demand for products prepared by
natural and environmentally compatible means. As a consequence of
their versatility in application, lipases are regarded as enzymes of high
commercial potential. Lipase catalysed esterification in organic
solvents presents challenges, which if dealt with successfully, can
result in the generation of a number of useful compounds. Both the
range of substrates with which lipases react and the range of reactions
catalysed are probably far wider than those of any other enzyme
studied to date (Divakar & Manohar, 2007).

3.0 CONTENT
3.1 Petrochemical industries
Refining and petrochemicals are the industries where zeolites are by far the most
frequently used for adsorption and catalysis. The earliest application goes back to
the end of the fifties, after the discovery by the company Linde of the synthesis of
the A-type zeolite that capable of separating normal and branched paraffins. The
second, and certainly the most significant event was the introduction of X and Ytype zeolites in catalytic cracking at the beginning of the sixties, which generated
some deep technological changes in the process and substantial gains in gasoline
yield. The first use of shape selectivity properties for zeolites dates back to 1968
with selective hydrocracking on erionite for normal paraffins of gasoline cuts.
Over the last 40 years, zeolites were introduced first in refining, and then in
petrochemicals, and now hold what may be considered a key position.
The development of crude oil refining and the use of new processes to satisfy the
increase in demand for gasoline has provided refinery off-gases and other
hydrocarbons that are now used as the main source of industrial organic
compounds, and the term petrochemicals arose to describe this evolution of the
chemical industry.

For example, in the early years following the development of the Haber- Bosch
process for the manufacture of ammonia, both ammonia and methanol were
manufactured from synthesis gas derived from coal. This was eventually replaced
by a naphtha-like fraction from the refining of crude oil, and much of the World
capacity for methanol and ammonia is now derived from natural gas. In general,
refinery feeds have now replaced coal for the production of synthesis gas almost
entirely, and both ammonia and methanol can rightly be regarded as
petrochemicals. Such is the scale of modern refining, together with the increased
demand for petrochemical products such as plastics, fibers, and rubber,
petrochemical complexes are now frequently closely linked to refineries. For
example, of the 666 million tonnes of naphtha produced in 1997, up to 40% were
used in the steam crackers and aromatics units that provided feeds for
petrochemical production.
Many chemicals are made using continuously operating refinery-like processes,
often with several reaction steps in sequence, and the products must be produced
to tight chemical specifications. Some of the oxidation,
hydrogenation/dehydrogenation reactions developed more than 80 years ago are
still being used, although efficiency and selectivity have been greatly improved
by the use of better catalysts and equipment. About 1914 the volume of gasoline
sold exceeded the demand for kerosene. Consequently thermal cracking processes
were introduced, since these resulted in an increase in the gasoline yield from
crude oil. However, cracking produced large volumes of low-molecular-weight
gases, which at first were used as fuel.
The almost worthless gas did, however, contain significant volumes of olefins,
which were eventually to become the aliphatic building blocks used in producing
high-octane gasoline and, later, petrochemicals. (Lloyd, 2011)

3.2 Palm-oil biodiesel

The production of liquid transportation fuel from renewable resources has been
expanding worldwide because of the depletion of petroleum reserves and growing
concerns about greenhouse gas emission. There have been numerous efforts to
produce biofuels, but most methods have been focused on single-component fuels
such as ethanol, butanol, and narrowly distributed C5AC10 hydrocarbons for use
in gasoline engines (Olcay et.al.,2010). Recently, synthesis of biofuels that can be
used in diesel engines using cascade catalytic processes and sugars as a starting

material have also been successfully demonstrated (Serrano et.al.,2011).

Triglycerides, which are the main components in animal fats and vegetable oils,
are also widely considered to be renewable resources for the production of diesel
biofuels, because it is easy to convert them into liquid transportation fuels. For
example, transesterification of triglycerides into fatty acid methyl esters (FAMEs)
is the most common way of transforming vegetable oils into transportation fuels
(Kim et al., 2014).
Biofuels offer number of advantages over the fossil fuels in terms of (a)
availability of renewable sources; (b) representing CO2 cycle in combustion; (c)
environmentally friendly; and (d) biodegradable and sustainable (Puppan, 2002).
Plant oils have recently got attention due to their environmental benefits and
renewable resources. They have the potential to substitute for the petroleum fuels
in the near future (Demirbas,2003). In petroleum refineries, the different types of
fuels are obtained through fractionation of crude oil by distillation and subsequent
processing of different fractions of crude oil in the downstream processes. In a
typical biorefinery, liquid product from biomass processing and plant oil could be
processed to produce biofuels using appropriate technologies. However, there are
number of economic barriers to replace the petroleum-based technology suitable
for processing of renewable resources in a biorefinery (Miller and Jackson, 2004).
Plant oil-based fuels are more expensive than petroleum fuels (Demirbas, 2003).
One of the factors contributing to the biofuels price is the cost, availability and
sustainable supply of the feedstocks.
There are number of catalytic processes in a typical biorefinery which are
needed for the conversion of renewable feedstocks into the desired biofuels.
These are two types of processing sections: (1) solid feedstock processing plant
and (2) liquid feedstock processing plant. Solid feedstock processing plant
includes biomass gasification, pyrolysis and liquefaction followed by catalytic
upgrading. Liquid feedstock processing plant includes transesterification process
and catalytic cracking of palm oil. The right choice of catalysts, reactors and
downstream separation processes are some of the important issues to be
addressed by the researchers. The design operation and control of reactor is one
of the challenges in a catalytic biorenewable process. The reactions involving
biomass or plant oil are generally carried out in multiphase reactors. This includes

fluidized bed reactor, entrained flow reactor, trickle bed reactor, fixed bed reactor,
slurry phase reactor and bubbling bed reactor to facilitate adequate contact
between fluid phases and catalyst. In these reactors, the mass and heat transfer
effects to be incorporated for better control and operation of the reactors (Miller
and Jackson, 2004). The integration between process
and reactor operation with the catalyst design is one of the difficult tasks to make
the overall process to be successful in a biorefinery.
A reactor must be designed with consideration of mass and heat transfer as well
as residence time and flow patterns so that the catalyst performs to its highest
efficiency (Miller and Jackson,2004).
3.2.1

Catalytic process in biorefinery

Pyrolysis
Pyrolysis of biomass is the direct thermal decomposition of the organic
matrix in the absence of oxygen, or is partially combusted in a limited
oxygen supply, to produce a gas mixture (containing mainly carbon
oxides, some methane and higher gaseous hydrocarbons in minor
quantities), a carbon rich solid residue (char and coke) and liquid oil
(bio-oil) (Demirbas, 2001; Yaman, 2004). Low temperature (450550
C), high heating rate and short gas residence time of biomass pyrolysis
could result in maximum yield of liquid product (bio-oil) (Zhang et al.,
2005).
The pyrolysis liquids are complex mixtures of oxygenated aliphatic
and aromatic compounds (Meier and Faix, 1998). High temperature
(500850 C), low heating rate and long gas residence time of biomass
pyrolysis are required to maximize the yield of fuel gas (Chen et al.,
2003). The pyrolysis gas contains CO2, CO, CH4, H2, C2H6, C2H4,
minor amounts of higher gaseous organics and water vapour
(Klass,1998). For highly cellulosic biomass feedstocks, the liquid
fraction usually contains acids, alcohols, aldehydes, ketones, esters,
heterocyclic derivatives and phenolic compounds (Klass, 1998)and
(Chew & Bhatia, 2008).

4.0 DISCUSSION
Almost all chemical industries using catalyst in their processes. Since the catalyst function by
allowing the reaction to take place through an alternative mechanism that requires a smaller
activation energy. This change is brought about by a specific interaction between the catalyst
and the reaction components. For example,the production of biofuels in a palm oil and oil
palm biomass-based biorefinery. The catalytic technology plays an important role in the
different conversion processes in a biorefinery for the production of liquid as well as gaseous
biofuels. The development of the catalysts and catalytic processes are essential in the
biorefinery with the capability and flexibility to adjust and optimize performance in response
to the changes in feedstock and market demands. The development of catalysts that facilitate
highly selective conversion of substrate to desired products is one of the challenges
encountered by biorefinery (Miller and Jackson, 2004). The thermally stable, effective and
cost effective catalysts with high selectivity towards desired products are required
(Westermann et al., 2007).
The catalytic processes in biorefinery are pyrolysis. Pyrolysis of biomass is the direct thermal
decomposition of the organic matrix in the absence of oxygen, or is partially combusted in a
limited oxygen supply, to produce a gas mixture (containing mainly carbon oxides, some
methane and higher gaseous hydrocarbons in minor quantities), a carbon rich solid residue
(char and coke) and liquid oil (bio-oil) (Demirbas, 2001; Yaman, 2004). Bio-oil (known as
pyrolysis liquid) generally consists of two phases: an aqueous phase containing a wide
variety of low molecular weight oxygenated organic compounds (such as acetic acid,
methanol, acetone), a non-aqueous phase containing oxygenated compounds (such as
aliphatic alcohols, carbonyls, acids, phenols, cresols, benzenedioles, guaiacol and their
alkylated derivatives), aromatic hydrocarbons which are single ring aromatic compounds
(such as benzene, toluene, indene and alkylated derivatives) and polycyclic aromatic
hydrocarbons (PAHs) (such as naphthalene, fluorene and phenanthrene and alkylated
derivatives) (Bridgwater, 1994; Williams and Nugranad,2000). Fast pyrolysis is regarded as
one of the promising technologies for the production of liquid bio-oils. It is an effective
biomass conversion process with high liquid yield, as much as 7080% and a high ratio of
fuel to feed (Demirbas, 2001).

Catalysis plays important role in enhancing the yield of bio-oil. The oil produced contains
less amounts of oxygen content with a higher H/C ratio than the original feedstock. Further
comparison of the H/C ratio with conventional fuels indicates that the H/C ratio of the oil is
very similar to those of light petroleum products (H/C = 1.51.9). The usage of catalysts in
the pyrolysis process helps in improving the yield and quality of gas. Some inorganic salts,
such as chlorides, carbonates and chromates, exhibit beneficial effect on the pyrolysis
reaction rate (Ni et al., 2006).
Biodiesel, produced from transesterification of vegetable oils or animal fats, is used in
compressionignition (diesel) engines. Homogenous alkali and acid catalysts have been
widely studied, whereas heterogeneous catalysts such as zeolites, hydrotalcites, oxides, calumina, appears to be promising catalysts for transesterification of vegetable oil. There are
number of solid heterogeneous catalysts reported for acid-catalyzed as well as alkalicatalyzed transesterification processes. However, these catalysts have lower activity
compared to homogeneous catalysts besides their cost and life.

5.0 CONCLUSION

The global demand for palm-oil biodiesel, petrochemical, pharmaceuticals, fertilizer

product are increasing rapidly and therefore the capacities of refining and petrochemicals
will continue to grow for many years to come. Refining and petrochemicals are mature
industries that are constantly changing. For the last three decades, refining schemes have
indeed evolved considerably. They continue to change to adapt to numerous constraints
which are not likely to decrease in the foreseeable future, and which are due to the need
to limit consumption of petroleum products (in particular CO2-related issues), to have
greater respect for the Environment and minimize refining costs.
In this context, catalysts have an important role to play in order to fulfill the global
demand in various chemical industries.

6.0 RECOMMENDATION
I think a new catalyst should be discover in order to fulfill the demand of catalyst in
various chemical industries.

7.0 REFERENCES
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