Example -2

Oxidation of propene to propene oxide

Traditional route to propene oxide

Propene oxide is an important bulk chemical, used for making propylene glycol
(propane-1,2-diol), polyethers, glycerol (propane-1,2,3-triol), and other products.
catalytic process for oxidizing propene directly to propene oxide using molecular
oxygen would be very attractive.

Although this process is wasteful and polluting, it still accounts for 40% of the global
manufacture of propene oxide.
 Catalytic Alternatives – Two Processes
1. Styrene monomer propene oxide (SMPO) process - Shell and Lyondell

It is less polluting, but couples the epoxide production to that of styrene, a

huge-volume product.

2. ARCO/Oxirane process : uses a molybdenum catalyst. The t-butanol that

this generates as a by-product is then used as a gasoline additive
and a starting material for making methyl t-butyl ether (MTBE). The
disadvantages here are that Mo is a toxic heavy metal, and MTBE use is being
phased out in the US and Europe.
Styrene monomer propene oxide (SMPO) process
. ARCO/Oxirane process
 Sumitomo Chemical’s New PO-only Process

Using cumene, Sumitomo Chemical has established a cumene PO-only

process as a new PO production process.

1.Oxidation Process : Auto oxidation, without a catalyst

The oxidation reaction is an auto-oxidation reaction

that occurs without a catalyst, and the technology is
basically the same as phenol synthesis by the cumene
method.
 2. Epoxidation Process
This is a process where CMHP and propylene are reacted and α,α-dimethyl benzyl
alcohol (CMA) is obtained.

It is a fixed bed process that uses a Ti-silicon oxide catalyst developed by

Sumitomo Chemical

3. Hydrogenation Process

This is a process where cumene is reproduced from α,α-dimethyl benzyl alcohol

(CMA) and hydrogen.
 Epoxidation Catalyst

The most important thing in the construction of this process was the
development of the epoxidation catalyst.

since the cumene loss is large in epoxidation processes with conventional homogeneous
Mo catalysts and the like, the processes could not be set up economically.

Titanium based catalysts in combination with silica are known to exhibit a high level of
epoxidation activity, because they have a high dispersion of highly active
tetrahedral titanium in a highly hydrophobic crystalline silica matrix.

The epoxidation catalyst developed by Sumitomo Chemical is a silicon oxide catalyst that
contains Ti and has a mesoporous structure.

This mesoporous catalyst, which is prepared using a sol-gel process, was the first of its kind
in the world to be used industrially.
Main points for increasing the performance can be thought of as follows.
(1) The tetrahedral titanium, which is highly active in epoxidation reactions, is in the silica
matrix in a highly dispersed state.
(2) The meso – macro pores are precisely controlled so large molecules like CMHP can be
sufficiently diffused, and
(3) propylene affinity is increased by giving sufficient hydrophobic properties.

The Ti silicate catalyst (TS-1) known to be highly active in the hydrogen peroxide
method for PO synthesis has only has micropores of 5 – 6Å, and the reaction activity for large
molecules like CMHP was extremely low .

Important factors for effective Ti epoxidation catalyst Comparison between TS-1 catalyst and
Sumitomo Ti catalyst
XAFS , X-ray absorption fine structure (XAFS)

XAFS spectroscopy of Sumitomo Ti catalyst

 S-curve for research in catalysis.

Reasoning from a feedstock point of view, that is, fossil, biomass, and CO2, it
is reasonable to state that they are in different phases on the S-curve, the conversions of
fossil sources are in general mature and at the end of the curve. Kindly note that large
research efforts are still ongoing in that field, but improvements are small though
economically very relevant. The use of biomass is at the bottom of the S-curve. New insights
have emerged in recent years though the major breakthrough has not yet been made. The
use of CO2 is at the moment at its dawn. It is regarded as a potential source for carbon in
fuel and chemicals in the future, but its potential is not fully clear yet.
 Catalysis in a Nutshell

catalysis is the key to sustainability

It is about speeding up reactions and lowering activation barriers, not about changing
equilibria.

Catalysis is purely a kinetic and not a thermodynamic phenomenon.

A definition that is still valid today is

due to Ostwald (1895): “a catalyst
accelerates a chemical reaction
without affecting the position of the
equilibrium.” Ostwald recognized
catalysis as a ubiquitous
phenomenon that was to be
explained in terms of the laws of
physical chemistry.
Catalysis is a cycle in which reacting molecules bind to the catalyst, where they react to a
product that subsequently desorbs and leaves the catalyst available for the next reaction
sequence. Catalysis is thus a cycle of stoichiometric elementary reactions. Neither of these
steps can be called catalytic in itself. It is the cyclic combination of events from which the
catalyst emerges unchanged that makes the sequence catalytic. When different types of
catalysts are used, these steps can be very different even when the starting material and the
product are the same.
let us consider the catalytic oxidation of CO on a noble metal such as platinum (Pt)

Carbon monoxide adsorbs molecularly, while O2 dissociates. Adsorption is an exothermic

process that decreases the potential energy. Next, the adsorbed CO and O react on the
surface to produce CO2, which is weakly bound and desorbs into the gas phase,
leaving the surface free for the next reaction event.

Decreased activation energy accelerates the reaction tremendously

The activation energy Ea is an extremely important parameter in catalysis. It gives

the height of the energy barrier that the system must overcome for the reaction to
proceed. The higher the activation energy, the higher the sensitivity of k to temperature.
Typical values for Ea range from 2 kcal mol-1 to tens of kilocalories/mole. A
useful rule of thumb states that the reaction rate roughly doubles for every 10 oC
increase in temperature. Furthermore, when Ea is less than 5 kcal mol-1, we say
that the reaction is diffusion-controlled. This means that the reaction rate is limited
by how fast the molecules move toward one another. Conversely, when Ea is greater
than 5 kcal mol-1, we say that the reaction is chemically controlled.
Another important point to note is that the catalyst offers an energetically favorable pathway
not only for the forward reaction but also for the reverse one.

The forward reaction is known as the steam reforming of methane to produce synthesis gas
(CO + H2), which is an endothermic reaction carried out with nickel catalysts at high
temperature. The reverse reaction is the (exothermic) methanation reaction that is applied
to purify H2 from traces of CO or even to produce substitute natural gas from coal or
biomass. This reaction also utilizes nickel catalysts but at temperatures much lower than the
steam reforming.
 Catalysis is extremely important in the chemical industry

catalysts enable reactions to proceed faster so that smaller reactors as well as

milder conditions, that is, temperatures and pressures, can be employed. Thus,
costs to achieve the chemical conversion can be reduced.
However, even more important is the fact that catalysts allow enhancement of the
desired conversion, without increasing the rate of formation of undesired
products. In other words, selectivity of the conversion can be improved.
Therefore, more useful product can be produced per amount of feedstock,
limiting the production of waste as well as the need to separate targeted products
from waste produced by unselective reactions. The result is that costs can be
reduced, in terms of both investment and operating costs.
 CHEMICAL REACTORS

Generic flow diagram of a chemical process.

The subject of designing a chemical reactor for a given process might proceed as shown in the
following sequence of steps.
 Batch Reactor

 Reactors in which a certain quantity (batch) of reactants is loaded and the reaction is
thereafter performed “batch wise” with this quantity are called batch reactors.

 The batch reactor is often the most common reactor used in the laboratory in the initial
stage of catalyst development, especially for liquid phase reactions.

 Since in this reactor the unconverted reactants remain and the products are accumulating,
the composition in the reactor is changing with time.

 In industry, batch reactors are generally used most for (high value) smaller-scale
production of fine chemicals and pharmaceutics. To prevent undesired reactions during
startup (heating) of the reactor, it is often preferred to add one of the reactants or the
catalyst only once the reactor has reached the desired operating conditions.

 To assure good mixing of the reactants in the reactor, generally a batch reactor is equipped
with a mechanical stirrer, which will also help to suspend a solid catalyst in the reactor and
have an efficient heat exchange of the fluids in the reactor with the surroundings via a
cooled or heated wall.

 For reactors in which a larger heat supply or removal is required, often heat
exchanger coils are placed in the reactor in addition to heat exchange via the
reactor wall.
 Continuous Flow Reactors

1. Continuous Flow Stirred Tank Reactor (CSTR)

 A continuous flow stirred tank reactor, commonly simply referred to as a CSTR,

is often used in continuous processing in chemical industry. The design of such a reactor
can be identical to that of the batch reactor, a closed vessel with a stirrer mixing its
content, but in this case there is a continuous inlet and outlet stream.

 Bubble column reactors with optionally a suspended catalyst can often be described as a
CSTR reactor for the liquid phase, since in this case the gas is taking care of the mixing of
the liquid in the reactor.

 In continuous processes, the aim is to have a steady non-changing production

of a product.
2. Plug-Flow Reactor (PFR)

 The second type of continuous flow reactor is the PFR.

 This type of reactor is used most commonly in chemical industry in catalytic bulk
chemical and petrochemical processes. This reactor is often also referred to as a
tubular reactor.
 This reactor consists of a single or a bundle of tubes, either empty or packed with a
bed of catalyst through which the reactants are flowing continuously.
 The length of the reactor is typically much larger than the diameter, as a result there is
little mixing in the reactor. Therefore, a significant concentration (and possible
temperature) gradient will be present in the reactor from the inlet to the exit of the
reactor.
 Microengineering and Microtechnology
(One type of Modular Reactor)
 The progress in microtechnologies include novel micro-sized chemical apparatus like-
reactors, mixers, separators, heat-exchangers and analyzers, making possible the accurate
control of reaction conditions with respect to mixing, quenching and temperature profile.
 Microfabricated chemical systems have several advantages for chemical kinetic studies,
chemical synthesis and, more generally, for process development.
 Microdevices (reactors, mixer, heat exchangers, etc.) have advantages over conventional
devices in terms of (i) compactness and low capital cost, (ii) low energy consumption and
other operating expenses, (iii) short mixing time and well-defined mixing behavior, (iv)
narrow residence-time distribution and (v) performance independent of pressure and
temperature (vi) possible mass production at low cost (Vii) improved quality with reduced
waste production (iX) improved safety.
 The particular characteristics of the flow in microchannels, the behavior of fluids in
confined environments (micro spaces) and the high wall to volume ratio determine new
properties that are the bases for nonlinear effects and their use in process
intensification.
 Mode of Action of Catalysts

The suitability of a catalyst for an industrial process depends mainly on the following three
properties:
1. activity
2. selectivity
3. stability (deactivation behavior).

1. Activity

Activity is a measure of how fast one or more reactions proceed in the presence of the
catalyst. It can be defined in terms of kinetics. In a formal kinetic treatment, it is
appropriate to measure reaction rates in the temperature and concentration ranges that
will be present in the reactor.

The reaction rate r

Kinetic activities are derived from the fundamental rate laws

The temperature dependence of rate constants is given by the Arrhenius equation

 Hence there are three possibilities for expressing catalyst activity

Reaction rate
Rate constant k
activation energy Ea

Different catalysts are to be compared for a given reaction, the use of constant
concentration and temperature conditions is often difficult because each catalyst requires
it own optimal conditions. In this case, it is appropriate to use the initial reaction rates.

Another measure of catalyst activity is the turnover number (TON), which originates from the
field of enzymatic catalysis.
 Another measure of catalyst activity is the turnover number (TON)

The catalyst turnover number (TON) and the turnover frequency (TOF) are two important
quantities used for comparing catalyst efficiency.

In homogeneous catalysis, the TON is the number of cycles that a catalyst can run through
before it deactivates, i.e., the number of A molecules that one molecule of catalyst can
convert (or “turnover”) into B molecules. The TOF is simply TON/time, i.e., the number of A
molecules that one molecule of catalyst can convert into B molecules in one second,
minute, or hour.

For industrial applications the TON is in the range 106–107.

In heterogeneous catalysis, TON and TOF are often defined per active site, or per gram
catalyst. This is because one does not know exactly how many, “catalyst molecules”there are
on the surface.

In biocatalysis, the TON and TOF are defined by the rate measured when all the enzyme
molecules are complexed with a reactant, divided by the total enzyme concentration.

Always include the units of these values when discussing catalytic activity.
The TOF is simply TON/time, i.e., the number of A molecules that one molecule of catalyst
can convert into B molecules in one second, minute, or hour.

Heterogeneous Reaction

For most relevant industrial applications, the TOF is in the range 10-2–102 s-1 (enzymes
103 – 107 s-1).

Owing to competing reactions, the catalyst undergoes chemical changes, and its activity
becomes lower (catalyst deactivation). Thus, catalysts must be regenerated or eventually
replaced.
For comparative measurements, such as catalyst screening, determination of process
parameters, optimization of catalyst production conditions, and deactivation studies, the
following activity measures can be used:

 conversion under constant reaction conditions;

 space velocity for a given, constant conversion;
 space–time yield;
 temperature required for a given conversion.

Catalysts are often investigated in continuously operated test reactors, in which the
conversions attained at constant space velocity are compared (Product Conversion)

The space velocity is the volume flow rate V0(volume of fluid that is passing through a given
cross sectional area per unit time), relative to the catalyst mass m cat:
 Space–Time yield (STY)

The performance of a reactor is given relative to the catalyst mass or volume, so that
reactors of different size or construction can be compared with one another.

Determination of the temperature required for a given conversion is another method of

comparing catalysts. The best catalyst is the one that gives the desired conversion at a lower
temperature. This method cannot, however, be recommended since the kinetics are often
different at higher temperature, making misinterpretations likely. This method is better
suited to carrying out deactivation measurements on catalysts in pilot plants.
 2. Selectivity

The selectivity SP of a reaction is the fraction of the starting material that is converted to
the desired product P.

It is expressed by the ratio of the amount of desired product to the reacted quantity of a
reaction partner A and therefore gives information about the course of the reaction.
parallel and sequential reactions can also occur
 Selectivity in Catalyst demonstrated

There are various kinds of product selectivity. Chemical selectivity, or chemoselectivity,

denotes a situation where two different chemical reactions can occur, giving two

different products. Similarly, regioselectivity occurs when the same chemical reaction in

different regions of the molecule leads to different products. When a reaction gives two

(or more) diastereomers, the selectivity to each of these is called diastereoselectivity. In

the special case when two products are mirror-image diastereomers, or enantiomers, we

talk about enantioselectivity.

 Examples of selectivity of catalysts

 Over a silver catalyst, ethylene (ethene) is selectively converted into ethylene

oxide an important precursor in the manufacture of ethylene glycol which, in turn,
is required for the production of polyester fibres and antifreeze agents.
 Finely dispersed platinum, as in an auto-exhaust catalyst, selectively favours the total
combustion of ethylene.
 The oxidation of ethylene to acetaldehyde is best performed homogeneously in the
presence of aqueous palladium chloride and copper ions, this being
the essence of the industrial Wacker process.
Propene into different products
From a mixture of carbon monoxide and hydrogen, also known as ‘synthesis gas’ or ‘syn-
gas’, produced either by the older method of gasification of coal by steam (C + H2O → CO +
H2) or by the newer method of partial oxidation (2 CH4 + O2 ⇌ 2 CO + 4 H2 ) and ‘steam
reforming’ of methane from natural gas and (CH4 + H2O ⇌ CO + 3 H2), many commercially
important products can be prepared with high efficiency
A shape-selective catalyst, such as a synthetic zeolite with cylindrical pores
of about 5.5 Å in diameter, permits ready ingress of straight-chain reactant alkanes
(e.g. n-heptane) but not of branched isomers (e.g. 2-methylhexane). The acid centres lining
the pores can therefore catalyse the cracking of the n-heptane but not of the branched
hexane. For similar reasons, in the acid-catalysed disproportionation of toluene
to xylene and benzene, production of the pxylene is favoured.
 3. Stability

The chemical, thermal, and mechanical stability of a catalyst determines its lifetime in
industrial reactors. Catalyst stability is influenced by numerous factors, including
decomposition, coking, and poisoning. Catalyst deactivation can be followed by measuring
activity or selectivity as a function of time.
 Catalyst/Substrate Interactions and Sabatier Principle

The interaction between the catalyst and the substrates, intermediates, and products
is extremely important. If it is too weak, the substrate will drift away from the catalyst
and no reaction will take place. Conversely, if it is too strong, the substrate (or the
product) will never leave the catalyst, causing poisoning or inhibition,

Some catalyst/substrate interactions should be “just right”– not too weak and not too strong.
This qualitative concept is known as Sabatier’s principle
Reaction rate depends on the heat of adsorption

At first, as the heat of adsorption increases, the

reaction rate also increases. More
substrates bind to the catalyst and there is a
higher chance of reaction. When the heat
of adsorption is too strong, however, the
reaction rate starts to decrease, because now
the substrates (or products) do not leave the
catalyst. This type of plot is called a
volcano plot, and is quite common in catalysis.
 Catalyst Deactivation, Sintering, and Thermal Degradation

Catalytic intermediates (or the active sites) can lose or gain activity as the reaction
progresses, because catalysts are often sensitive to changes in acidity/basicity, temperature,
pressure, and phase composition. Moreover, as the conversion increases, products and by-
products can bind to the catalyst, thereby changing the preferred reaction pathway. Such
processes are known as deactivation, sintering, inhibition, or poisoning.

1. Catalyst Deactivation

This is a general term for a common situation in catalysis, where a catalyst becomes
less active as the reaction progresses.

An organometallic complex catalyst, for example, may dimerize or oligomerize, reducing

the concentration of active catalytic intermediates. Often, the activity depends on specific
ligating groups. If these are destroyed via side-reactions – e.g., due to pH changes,
oxidative degradation, increasing temperature, or the formation of additional phases – the
catalyst will deactivate.
 2. Catalyst Sintering and Thermal Degradation

Catalyst deactivation via thermal degradation or sintering is a common phenomenon

in heterogeneous catalysis.

At high temperatures, the support pore structure may collapse, and the size and shape of the
metal crystallites can change. This decreases the catalysts surface area and the number of
active sites

The temperature at which this happens varies, but many metals are already sensitive to
sintering at ~200 0C below their melting point

This can occur by two pathways: atom migration and crystallite migration. In atom migration,
metal atoms migrate from one crystallite to another via the surface or the gas phase. Smaller
crystals are more likely to lose atoms this way, because they have a higher surface area and
correspondingly a higher proportion of atoms at high-energy sites. Thus, the big clusters get
bigger and the small clusters become even smaller. Conversely, in the crystallite migration
model, entire metal crystallites migrate on the support surface, collide, and coalesce
Different aspects of catalyst sintering: a crystallite migration; b atom migration; c phase
transformation of the support at high temperatures.
 Sintering is a complex process .
 It depends on temperature, support composition, support porosity, type of active metal,
and surrounding atmosphere.
 At lower temperatures (typically ~600 0C for noble metals) the primary sintering
route is atom transfer from small metal particles via surface diffusion. Crystallite
migration becomes important at higher temperatures.
 Another type of sintering occurs when the crystal phases of the support itself transform.
This happens only at very high temperatures (typically above 1000 0C). Such
transformations collapse the pore structure, thereby reducing the surface area and
blocking access to active sites.
 3. Catalyst Inhibition

 Catalyst inhibition is traditionally associated with biocatalytic processes, but can also
apply to homogeneous and heterogeneous catalysis.

 A competitive inhibitor is any chemical species I which can bind to the same
site as the substrate, or to another site on the enzyme (an allosteric site).

 A noncompetitive inhibitor binds only at an allosteric site. This changes the

properties of the active site and stops or retards the catalytic activity. The structure
and shape of the enzyme change, reducing the “active enzyme”concentration and
decreasing νmax.
 4. Catalyst Poisoning

 When an inhibitor bonds irreversibly to the catalyst, we say that it “poisons”the catalyst.

 If there is enough poison, the catalytic cycle will grind to a halt.

 Like sintering and inhibition, poisoning depends on temperature and reaction conditions.
Poisons can be selective for a certain catalyst, or for certain reactions. Coke, sulfur, and
phosphorus are common poisons in automotive catalysis
Classification of Catalysts
Technical terms in different fields occasionally differ although they describe the
same thing.
Comparison of homogeneous and heterogeneous catalysts
The separability of homogeneous catalysts has been improved strongly by using
organometallic complexes that are soluble in both organic and aqueous phases. These can
readily be removed from the product stream at the reactor outlet by transferring them to the
aqueous phase. This two-phase method has already been used successfully in large-scale
industrial processes, for example, the Shell higher olefin process (SHOP) with nickel complex
catalysts
 Metal cluster catalysts.

Intermediate between homogeneous and heterogeneous catalysts

In many reactions that require several active centers of the catalyst, it is found
that heterogeneous catalysts are active, while homogeneous catalysts give zero
conversion. The reason is that crystallites on a metal surface exhibit several active centers,
while conventional soluble catalysts generally contain only one metal center.

 In contrast, metal clusters have several active centers or can form multielectron
systems. Metal clusters such as Rh6(CO)16, Rh4(CO)12, Ir4(CO)12, Ru3(CO)12, and more
complex structures have been successfully tested in carbonylation reactions. Rhodium
clusters catalyze the conversion of synthesis gas to ethylene glycol, albeit at very high
pressures up to now.

 With increasing size, the clusters become less soluble, and the precipitation of
extremely small particles from solution is possible, that is, a transition from
homogeneous to heterogeneous catalysis.
 Surface Area - Porous Catalyst

Gas reactions catalysed by solid materials occur at the exterior and interior surfaces of the
porous catalyst. The rate of product formation is a function of the available surface area and
so it follows that the greater the amount of surface area accessible to the reactants, the
larger the output.

 Metal catalysts are dispersed throughout the entire internal surface area of some
suitable porous support, such as high-area silica or γ-alumina, in order to create a large
specific surface area which is entirely accessible because of its open pore structure.
 Metal oxide and other catalysts often have a sufficiently high surface area and open pore
structure for them to be employed directly .
 Applications of Surface Area

 The prediction of catalyst poisoning. If, on continued use, the activity of a catalyst
declines more rapidly than any decrease in surface area, then poisoning is suspected.
Conversely, if a decrease in surface area is concomitant with reduced activity, then
thermal deactivation is indicated.
 provides a method of assessing the efficacy of catalyst supports and promoters. A
support or promoter may either increase the surface area available for adsorption
and subsequent reaction or it may increase the catalyst activity per unit surface area.
Hence, surface area measurement is an important expedient in predicting catalyst
performance and determining the role which the catalyst surface plays in any
heterogeneous gas reaction.
 Pore structure of the catalyst

Pore structure of the catalyst material or support, which, although contributing to the total
surface area, must be regarded as a separate factor.

 The distribution of pore sizes in a given catalyst preparation may be such that some of the
internal surface area is completely inaccessible to large reactant molecules and,
furthermore, may restrict the rate of conversion into products by impeding the diffusion
of reactants and products throughout the porous medium. Accordingly, it is necessary to
know something about the pore structure of a catalyst.

 Commercial catalysts usually have a high internal surface area. If this were not so, the
external surface, being quite small, would quickly become poisoned and the catalyst
would rapidly lose activity.
 Important techniques of probing porous solids generally and solid catalysts in
particular

 scattering and diffraction methods (involving neutrons, X-rays, electrons and

light);
 adsorption from the liquid phase;
 mercury porosimetry;
 fluid flow;
 thermoporometry;
 NMR techniques;
 high-resolution electron microscopy and
 positron annihilation spectroscopy.

kinetic diameter, σ, is defined as the intermolecular distance of closest approach of two

molecules of zero kinetic energy.
Nitrogen (at 77 K),(σ = 0.36) is generally considered to be most suitable adsorbate for
standard surface areas determinations: it is generally assumed that the BET monolayer is
close-packed (with the molecular area taken to be 0.162 nm2). A particular advantage in
the use of N2 is that its multilayer isotherm is not very sensitive to
differences in adsorbent structure.
 IUPAC classification of pore size

1) pores with widths not exceeding about 20 Å (02nm)are called micropores;

2) pores of widths between 20 (02nm) and 500 Å (05nm)are called mesopores;
3) pores with widths exceeding about 500 Å (0.05 μmor50nm) are called macropores.

The term nanoporous refers to a solid with pores less than about 500 Å (0.05 μmor50nm)

 In monolayer adsorption all the adsorbed molecules are in contact with the surface layer
of the adsorbent.
 In multilayer adsorption the adsorption space accommodates more than one layer of
molecules so that not all adsorbed molecules are in direct contact with the surface
layers of the adsorbent.
 In capillary condensation the residual pore space which remains after multilayer
adsorption has occurred is filled with condensate (a gas condenses to a liquid phase in a
pore at a pressure p less than the saturation pressure p∘ of the bulk liquid.)
separated from the gas phase by menisci (plural of meniscus). Capillary condensation is
often accompanied by hysteresis. Four distinct types of hysteresis loops are generally
encountered in adsorption on porous solids .

Porosity is defined as the ratio of pore volume to overall volume of the granule of particle
under investigation.
The six types of adsorption isotherms in the IUPAC classification.
Type Interpretation
This is characteristic of either a chemisorption isotherm (in which case the final upswing at high pressures
I may not be present) or physisorption on a material that has extremely fine pores (micropores)

This is characteristic of a material, which is not porous, or possibly macroporous, and has a high energy of
II adsorption
 This is characteristic of a material, which is not porous, or possibly macroporous, and has a low energy of
III adsorption

This is characteristic of a material, which contains mesoporosity and has a high energy of adsorption. These
IV often contain hysteresis attributed to the mesoporosity
 This is characteristic of a material, which contains mesoporosity and has a low energy of adsorption. These
V
often contain hysteresis attributed to the mesoporosity

This type of isotherm is attributed to several possibilities the most likely being, if the temperature is below
the adsorptive triple point, that the adsorbate is more like a solid forming a structured layer, i.e. epitaxial
growth. Other possible explanations include multiple pore sizes. If the steps are at the low pressure portion
VI
of the isotherm, then the steps may be due to two or more distinct energies of adsorption. If the steps are
at the high pressure part of the isotherm, then the steps might be due to sharp steps on the adsorbate
surface
The four principal types of hysteresis loops observed during adsorption of
gases on porous solids
Assessment of Porosity
Description of Isotherms
Type Interpretation
This is characteristic of either a chemisorption isotherm (in which case the final upswing at high pressures
I may not be present) or physisorption on a material that has extremely fine pores (micropores)

This is characteristic of a material, which is not porous, or possibly macroporous, and has a high energy of
II adsorption

This is characteristic of a material, which is not porous, or possibly macroporous, and has a low energy of
III adsorption

This is characteristic of a material, which contains mesoporosity and has a high energy of adsorption. These
IV often contain hysteresis attributed to the mesoporosity

This is characteristic of a material, which contains mesoporosity and has a low energy of adsorption. These
V
often contain hysteresis attributed to the mesoporosity

This type of isotherm is attributed to several possibilities the most likely being, if the temperature is below
the adsorptive triple point, that the adsorbate is more like a solid forming a structured layer, i.e. epitaxial
growth. Other possible explanations include multiple pore sizes. If the steps are at the low pressure portion
VI
of the isotherm, then the steps may be due to two or more distinct energies of adsorption. If the steps are
at the high pressure part of the isotherm, then the steps might be due to sharp steps on the adsorbate
surface
Comparison of homogeneous and heterogeneous catalytic reactions
 Brunauer–Emmett–Teller Isotherm

Assumptions on which the BET theory rests

1. The first layer of adsorbate is taken up with a fixed heat of adsorption (H1)
2. The second and subsequent layers are all characterized by heats of adsorption equal to
the latent heat of evaporation (HL)
3. By considering a dynamic equilibrium between each layer and the gas phase, the BET
equation is arrived at
Specific surface areas of catalysts and support materials
Causes of deactivation in large-scale industrial processes
 Barrett–Joyner–Halenda Method

The modified Kelvin equation based on a cylindrical pore model serves as the
basis for many methods applied for mesopore analysis. Below is the Kelvin equation

Here, γ is the surface tension of the liquid condensate and ν1 is its molar volume and rk
represents the radius of a hemispherical meniscus: it is also termed the Kelvin radius. If the
pores are in the form of a parallel-sided slits, the meniscus is cylindrical and for cylindrical
pores the radius rp is given by, rp = rk+t, where t is the thickness of the multilayer film due to
capillary condensation. This is the modified kelvin equation.

Capillary Condensation: A gas condenses to a liquid phase in a pore at a pressure p less than
the saturation pressure p∘ of the bulk liquid.
Ionic Liquids
Ionic liquids are defined as salts with melting points below 100 oC.

They have no (or exceedingly low) vapour pressure, so volatile organic reaction products can
be separated easily by distillation or under vacuum.

They are thermally stable and can be used over a wide temperature range compared with
conventional solvents and their properties can be readily adjusted by varying the anion and
cation.

Ionic liquids have been described as designer solvents , as these are made-up of two
components (i) cations and (ii) anions, which vary with different types of groups. Property of
ionic liquids depends on this group. Hence, the term “designer solvents” has been justified for
ionic liquids. The nature of the cations and anions has large influence on the properties of
these ionic liquids. The most employed ionic liquid anions are polyatomic inorganic species,
halogens, organic and perfluronited anions, such as [BF4 ], [PF6], [SbF6], [NO3]-, [AcO]-, Cl-, Br-.
The “green” behavior of ILs is controversial, because they have some drawbacks: ILs must be produced
without any undesired by-products because they cannot be purified by distillation. Moreover, if they become
contaminated as a solvent in a catalytical process, they must be disposed off.

The ionic liquids show excellent extraction capabilities and allow catalysts to be used in a biphasic system for
convenient recycling. For example, the hydrovinylation of styrene with ethene can be carried out successfully
using an ionic liquid and sc-CO2 as solvent. The ionic liquid dissolves the metal organic complex catalyst, and
sc-CO2 facilitates mass transfer and continuous processing.
 Manufacture of 6-aminopenicillanic acid, an antibiotic
intermediate

The original process involved protection of the carboxylate group in penicillin G by silylation; this reaction
also requires dimethyl aniline to remove the HCl produced during silylation

In the biocatalytic process, genetically engineered and immobilised penicillin amidase is used to
deacylate penicillin G directly.
Additional green benefits
Avoidance of dichloromethane solvent—water is used in the biocatalytic
process
• Energy savings—reaction carried out at 30°C as
against -50°C for the protection step
• Fewer safety problems—PCl5 also was used in the non-biocatalytic
process
 The BHC Ibuprofen Process
Ibuprofen functions by inhibiting cyclooxygenase (COX), an enzyme which participates in
the arachidonic acid cascade towards prostaglandin synthesis. Prostaglandins are
important mediators of inflammation and pain in the human body.(Non steroidal anti
inflammatory) After being approved for over-the-counter use, annual ibuprofen
prescriptions have grown to 20 million encompassing such brands as Advil, Motrin,
Nuprin, Rufen and Trendar
Traditional Method- Boots synthesis
Steps involved :Manufacture by Boots in 1962

1. Friedel-Crafts acylation of isobutylbenzene (1) using acetic anhydride as the acylating

agent in the presence of aluminum trichloride. Giving isobutylacetophenone (2)
2. 2 then undergoes a Darzens condensation reaction with an α-chloroenolate (formed
by reacting an α-chloroester with sodium ethoxide) to produce epoxide (3.)
3. When treated with aqueous acid, 3 undergoes decarboxylation and rearrangement to
produce aldehyde 4 which is converted into the oxime 5 using hydroxylamine.
4. The oxime product then spontaneously loses water to form nitrile 6 which produces
ibuprofen upon aqueous hydrolysis.
 BHC process for Ibuprofen

When the patent rights on ibuprofen expired, Boots teamed with the Hoechst Celanese
Corporation and formed the BHC consortium, developing a new process for making
ibuprofen.

They started from the same raw materials, but replaced the stoichiometric six-step process
with a three-step catalytic one

isobutylbenzene 1 undergoes a novel Friedel-Crafts acylation in the presence of catalytic

amounts of anhydrous hydrogen fluoride, which also functions as the solvent (thus
eliminating the need for a co-solvent).

2 undergoes heterogeneous catalytic hydrogenation over a solid Raney Nickel catalyst to

form the secondary alcohol 7

The final step constitutes a homogeneous catalysis involving carbonylation of 7 with

carbon monoxide in the presence of a soluble palladium catalyst to produce ibuprofen in
high yield after vacuum distillation.
 Difference between the two Process
1. Each of the six steps in the Boots process contained the use of stoichiometric reagent, with an
overall atom economy of 40 %
2. This means that more than half of the materials that entered the process were thrown away as
waste. For example, note the addition of hydroxylamine, NH2OH, in step 4: This group is used to
create the imine 5, which is then converted to the cyano derivative 6 and finally oxidized to give
the carboxylic acid product 7. Effectively, what happens is that the hydroxylamine is first added to
the molecule and then removed. This type of “roundabout synthesis”is precisely what green
chemistry tries to avoid.
BHC Process
1. Replaced the stoichiometric six-step process with a three-step catalytic one.
2. The overall atom economy of this new process was 77%, with acetic acid as the only by-product.
The consortium also developed methods for recovering and recycling the acetic acid, increasing
the atom utilization to 99%, and creating an essentially waste free synthesis. Using anhydrous HF
as both catalyst and solvent offers important advantages in reaction selectivity and waste
reduction, as the new route has also eliminated the large volumes of aqueous salt waste
associated with ibuprofen manufacture.
3. The BHC ibuprofen process is an innovative, efficient technology that has revolutionized bulk
pharmaceutical manufacture.
4. It avoids the large quantities of solvents and waste (especially aqueous salt waste
5. streams) associated with traditional stoichiometric reagent usage.
6. The anhydrous HF catalyst is recovered and recycled with efficiency greater than 99.9%. No other
solvent is needed in the process, simplifying product recovery and minimizing emissions. The new
ibuprofen process became a model for environmental excellence in
chemical technology, and BHC received the Kirkpatrick Achievement Award for “outstanding
advances in chemical engineering technology”in 1993, and the US Presidential Green Chemistry
Award in 1997.
Polymer supported Catalysis
 Supported Catalysis

Supported metal complexes have been studied for many years due to their potential for
combining the best attributes of both homogeneous and heterogeneous catalysts.

Homogeneous catalysts are anchored to inert supports in such a way that the ligand
sphere of metal is kept unchanged and the anchored catalyst is bathed by solvent and
reactants. Thus the introduction of heterogeneity to a homogeneous catalyst helps it to
retain its homogeneous character on a molecular basis but heterogeneous behaviour on
functional basis .

Driven by the favourable economic potentialities it is more advantageous if coordination

complexes are used as immobilized catalysts.

Anchored or supported catalysts may be defined as solid or heterogeneous catalysts in

which relatively small amounts of catalytically active species; most probably metals, are
deposited on the surface of largely inert, porous, and shaped support bodies, like
pellets, rings, extrudate and granules
 Advantages of anchoring a catalyst on a support

• Easy separation of the catalyst from the products of the reaction and thus its reuse.

• Cost effective as the anchored catalyst is only a fraction of the weight of the total
catalyst.

• Larger total active surface area for a given amount of active material in a supported
catalyst.

• Control over the selectivity if the support chosen is chemically inactive to the products
of the reaction.

• Manufacturing a catalyst of a desired shape and size, using a support of similar

dimensions. This is an important consideration in the process design as these
properties determine the packing density and pressure drop across the reactor.

• Optimizing catalytic performance by choosing the right pore size distribution and the
nature of the pores in the catalyst support.
Two main classes of solids are used for immobilization of complexes: organic polymers
such as polystyrene, polyvinyl benzene, or nafion and inorganic oxides like silica, alumina,
magnesia or zeolites, clays.

Organic polymers

• Polymers can be used as effective matrices for the active metal particles. The polymer
supports can be of three types.

• Highly cross – linked macro reticular resins of large surface area.

• Swellable lightly cross-linked micro porous resins.

• Soluble polymers where the reaction products are separated by membrane filtration or
precipitation of the polymer by the addition of a non-solvent.
 Ion-Exchange Resin

Ion exchange resins are polymer with functional groups capable of cation or anion exchange ability.

Cation exchange resins show acidic properties and catalyze acid-catalyzed reactions in the presence of
water. This point is one of the favourable features of cation exchange resins as compared
to many of the other solid acid catalysts which lose their activity in the presence of large amount of water.

One drawback of the cation exchange resins is a poor thermal stability.

The polymers degrade and the functional groups decompose at a high temperature, though resins
with relatively high thermal stability are synthesized. For common resins, the maximum reaction
temperature is 373 K.

Formation of poly (styrene-divinylbenzene)

macroreticular sulfonated polystyrene-divinylbenzene such as Amberlyst-15 and

Amberlyst-35 from Rohm and Haas.
Fundamental requirements of an ion-exchange resin are
• It must be sufficiently cross-linked to have little solubility

• Resin must be hydrophilic to permit the diffusion of ions.

• It should contain sufficient number of accessible ion exchange groups and must
be chemically stable.

• The swollen resin must be denser than water

 Shape-Selective Catalysis:
Zeolites

Zeolites - Crystalline, hydrated aluminosilicates, framework structure- based

on infinitely extending three dimensional network if SiO4 and AlO4 tetrahedra
linked to each other by sharing oxygen atoms.
Framework contains channels or interconnected voids which are occupied by
water molecules and alkali metal ions in order to balance the negative charge of
the framework.
Alkali metals when replaced by transition metal act as active sites for oxidation
Metal complexes which are smaller than the free diameter of the channels can be
encapsulated in the channels (Ship-in-a-bottle) {Herron-1999)
Tetrahedral atoms such as titanium can be isomorphically substituted to get the
framework species {Titanium Silicate-1(TS-1), Taramasso-1983}
Zeolites are water-containing crystalline aluminosilicates of natural or synthetic origin with highly ordered
structures
They consist of SiO4 and tetrahedra, which are interlinked through common oxygen atoms to give a 3D network
through which long channels run.

In the interior of these channels, which are characteristic of zeolites, are water molecules and mobile alkali metal
ions, which can be exchanged with other cations. These compensate for the excess negative charge in the
anionic framework resulting from the aluminum content. The interior of the pore system, with its atomic-scale
dimensions, is the catalytically active surface of the zeolites. The inner pore structure depends on the
composition, the zeolite type, and the cations.
The general formula of zeolites is

where MI and MII are preferentially alkali and alkaline earth metals. The indices x and y denote the oxide
variables and z is the number of molecules of water of hydration. The composition is characterized by the
Si/Al atomic ratio or by the molar ratio M

and the pore size of zeolites by the type (A, X, Y).

A well-known representative of the class of pentasil zeolites is ZSM-5 (from zeolite Socony Mobil no. 5).
H-ZSM-5 is the protonic type or H form of ZSM-5 (Exchange of the alkali metal ions in the channels with ammonium ions
followed by heating to 500–600 °C, which leads to cleavage of ammonia and leaves behind protons. )
 The advantages of Zeolites over conventional catalysts can be summarized as
follows
 Crystalline and therefore precisely defined arrangement of SiO4 and AlO4- tetrahedra. This results in good

reproducibility in production.

 Shape selectivity: only molecules that are smaller than the pore diameter of the zeolite undergo reaction.

 Controlled incorporation of acid centers in the intracrystalline surface is possible during synthesis and/or by subsequent

ion exchange.

 Above 300 °C pentasils and zeolite Y have acidities comparable to those of mineral acids.

 Catalytically active metal ions can be uniformly applied to the catalyst by ion exchange or impregnation. Subsequent

reduction to the metal is also possible.

 Zeolite catalysts are thermally stable up to 600 °C and can be regenerated by combustion of carbon deposits.

 They are well suited for carrying out reactions above 150 °C, which is of particular interest for reactions whose

thermodynamic equilibrium lies on the product side at high temperatures.

 The shape selectivity of zeolites is based on the interaction of reactants with the well-defined pore
system.

The accessibility of the pores for molecules is subject to definite geometric or steric restrictions. The shape

selectivity of zeolites is based on the interaction of reactants with the well-defined pore system. A distinction is made

between three variants, which can, however,

overlap:

 Reactant selectivity

 Product selectivity

 Restricted transition state selectivity

Shape selectivity of zeolites with examples of reactions. (a) Reactant selectivity: cleavage of hydrocarbons. (b)
Product selectivity: methylation of toluene. (c) Restricted transition state selectivity: disproportionation of m-xylene.

(a) Reactant selectivity: cleavage of hydrocarbons.

Reactant selectivity means that only starting materials of a certain size and shape can penetrate into the
interior of the zeolite pores and undergo reaction at the catalytically active sites. Starting material molecules
that are larger than the pore apertures cannot react. Hence, the term “molecular sieve” is justified.

ZSM-5 is used for shape-selective reactions. the ability of ZSM-5 to cleave unbranched and monomethyl-branched
alkanes
with retention of more highly branched and cyclic isomers is exploited industrially in the dewaxing process to lower the
solidification point of lubricants and in reforming processes to obtain high-octane gasolines
 Product selectivity: methylation of toluene.

Product selectivity arises when, corresponding to the cavity size of a zeolite, only products of a certain size and
shape that can exit from the pore system are formed. Well-known examples of product selectivity are the
methylation of toluene and the disproportionation of toluene on ZSM-5.
 Restricted transition state selectivity

This third form of shape selectivity depends on the fact that chemical reactions often proceed via intermediates.
Owing to the pore system, only those intermediates that have a geometrical fit to the zeolite cavities can be formed
during catalysis. This selectivity occurs preferentially when both monomolecular and bimolecular rearrangements are
possible. In practice, it is often difficult to distinguish restricted transition state selectivity from product selectivity.
 Zeolite catalysts are mainly used in refinery technology and
petrochemistry

Catalytic cracking (FCC): Here, heavy heating oil is converted to middle distillate and high-octane gasoline with
cerium- and lanthanum-doped Y zeolites. Advantages compared to conventional thermal cracking processes are
the better conversion yields and product quality, albeit at the expense of slightly less flexibility with regard to
starting materials.

Hydrocracking: In this environmentally friendly process, which operates in a closed system with 100% conversion
of heavy crude oil fractions, zeolite is used as a support for a hydrogenating component such as Pd. Bifunctional
catalysis is achieved in which the cracking activity of the acidic zeolite is combined with the hydrogenation activity
of the palladium.

Dewaxing process: In this industrial catalytic hydrocracking process, waxy C 16+ paraffins are cracked and partly
converted to aromatics.

Methanol to gasoline process (MTG) process: Methanol, produced from natural gas or coal, can be converted to
high-quality, aromatics-rich gasoline in a two-stage fixed- or trickle-bed process with H-ZSM-5 catalysts. In 1985,
the MTG process was commercialized in New Zealand, where Mobil built a 2300 m 3/day plant based on natural
gas, converted through synthesis gas into methanol. But in the mid-1990s, the MTG part was shut down and the
plant switched to methanol production due to the period of low oil prices.
 Advantages and disadvantages of biocatalysts and
enzymes
Advantages Disadvantages
Often low specific activity (Specific enzyme activity
Very high enantioselectivity (specific activity for short) is a measure of the purity
of an enzyme solution and is quoted as units/mg.)
Very high regioselectivity Instability at extremes of temperature and pH
Transformation under mild
Availability for selected reactions only
conditions
Long development times for new enzymes and
Solvent often water
processes
Sustainable development Enzymes often require complicated conditions
Co-substrates such as cofactors ( A cofactor is a
second substrate that must be
Green chemistry
introduced to activate the enzyme)

The greatest advantage of enzymes is their often unsurpassed selectivity, especially in the differentiation between
enantiomeric substrates when a pair of substrates has Gibbs free enthalpy difference of ΔGRS between the R-
enantiomer and the S-enantiomer of around 1–3 kJ mol-1. With the help of enzymes, sometimes enantioselectivities
of >99% ee can also be
achieved.
There are recognized six classes of enzyme-catalyzed reaction in systematic
nomenclature.
Name Reaction catalyzed

1. Oxidoreductase Oxidation–reduction reactions

Transfer of chemical group from one substrate to another or from one part of
2. Transferases
substrate to another

3. Hydrolases Hydrolysis reactions

Elimination of groups from adjacent atoms or addition of groups to double

4. Lyases
bonds

5. Isomerases Rearrangements (isomerizations)

6. Ligases Formation of bonds to groups with hydrolysis of ATP and so on

Outlook for the biocatalytic sector:

 Biocatalysis will increasingly be used for the production of bulk chemicals including fuels, polymers, and
other large-volume materials. Large chemical manufacturers (e.g., BASF, DuPont, Celanese, DSM, Dow
Corning, Lonza, and Evonik) have invested heavily in biocatalysis capabilities. In many cases,
bioprocesses can improve productivity, lower costs, and reduce waste streams.

 Biocatalysis includes both enzyme catalysis and biotransformation using whole

microorganisms.

 Biocatalysis is a dynamic area of research providing many chances for innovation.

 The quest for sustainable production (chemicals and energy) favors biocatalysis.

 Production of fine chemicals and active pharmaceutical ingredients will also continue to benefit from the
application of biocatalysis, in many cases as part of multistep synthetic process routes.

 There is an increasing demand for chirally pure pharmaceuticals, because racemic drugs
often have unwanted side effects.
 Catalyst Shapes and Production of Heterogeneous
Catalysts
Precipitated
catalysts
Bulk catalysts are mainly produced when the active components are cheap. Since the preferred method of
production is precipitation, they are also known as precipitated catalysts.

Precipitation is mainly used for the production of oxidic catalysts and also for the manufacture of pure support
materials. One or more components in the form of aqueous solutions are mixed and then coprecipitated as
hydroxides or carbonates. An amorphous or crystalline precipitate or a gel is obtained, which is washed
thoroughly until salt free. This is then followed by further steps: drying, shaping, calcination, and activation
 Hydrothermal
Synthesis

Zeolites are synthesized by mixing a silica source (the primary building units of the framework, i.e., SiO2), an
alumina source (origin of the framework charge), organic templates, mineralizing agents NaOH, and water to
form an
aluminosilicate gel. Templates of the NR4+ type are used, such as tetraalkylammonium hydroxide.
Alkylphosphonium cations (R4P+) and organic complexes can also be applied. Reactants are mixed according
to a synthesis recipe under continuous stirring to obtain a unique milky white gel.

The well-known oxidation catalyst TS1 is synthesized hydrothermally from, for example, tetraethyl orthotitanate,
tetraethyl orthosilicate (Si:Ti ratio is typically 30–50), tetrapropylammonium hydroxide, and water. The reaction is
carried out at 160–180 °C, followed by calcination at 550 °C. Keeping the Si:Ti ratio high ensures that the Ti atoms
occupy lattice sites with no near neighbor Ti atoms. This is a prerequisite for an active catalyst. The typical pore
size is of the order of 0.55 nm, thus endowing the catalyst with shape selectivity, but thereby restricting its use to
small substrates.
 Monolithic
Catalysts

A monolith is a structured support or a structured catalyst characterized by long parallel channels separated

by thin walls. There are two different types of monolithic structures: the coated and the integral monolith. The

coated monolith consists of a monolithic backbone and a layer that is coated onto the so-called washcoat. An

integral monolith is made completely of support material providing the mechanical and the catalytical

properties. Ceramic monoliths

are made of porous cordierite 2MgO·2Al2O3·5SiO2 or mullite 3Al2O3·SiO2 by extrusion or by corrugation. The

porosity of the monolith walls ranges from 15 up to 40%, caused by macropores with an average diameter of

a few micrometers.
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