Lecture 4

The chemical processes in oil re ning involve obtaining fuel derivatives from oil
distillation processes, which are adjusted according to the requirements of the
markets for the quantities produced. The types of fuel obtained depend on the type
of crude oil used, which is determined by the characteristics of the crude oil and the
chemical transformations during the re ning process, including distillation and
fractionation. For example, heavy hydrocarbons are converted into lighter fractions
through processes such as catalytic cracking, which separates the heavier
components of crude oil into various lighter fractions, such as gasoline, diesel, and
lique ed petroleum gas (LPG), to meet increasing demands. The re ning process
involves improving the quality of the lighter fractions through chemical treatments,
such as hydrogenation and catalytic alkylation, to enhance their properties and
increase their economic value.

One of the important re ning processes is

catalytic alkylation, which is used to produce liquid hydrocarbon derivatives with

high octane ratings, essential for gasoline production. This process involves the
reaction of ole ns, such as propylene or butylene, with isobutane in the presence of
a catalyst, such as sulfuric acid, to produce high-octane alkylate.
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 Polymerization accompanies ole n metathesis reactions, allowing for the utilization
of unreacted ole ns, thereby reducing the cost of high-priced ole ns. This reaction
occurs selectively at low ole n concentrations, as it depends on the availability of
ole ns before the formation of catalytic intermediates. The process can yield high-
value polymers due to precise control of reaction conditions, restricting
polymerization to certain ole n types possessing suitable reactivity. For instance,
tertiary ole nic ions are the most stable, in uencing the selectivity of alkene
reactions. Regarding the use of isobutane as a reactant, polymerization becomes
more feasible in the gas phase, allowing for the incorporation of these isobutane-
derived alkanes into gasoline due to their similar boiling points.

Another signi cant re ning process is catalytic isomerization, which converts

normal butane into isobutane, a key component in gasoline production. The process
typically utilizes solid acid catalysts, such as zeolites, operating under high pressure
for gas-phase reactions or at lower pressure for liquid-phase reactions. Generally,
this catalytic process operates at temperatures ranging from 80 to 150 degrees
Celsius.

The success of the catalytic process relies on the controlled formation of carbocation
intermediates, which necessitates precise control over ole n and isobutane
concentrations. This means that the catalytic process requires only small quantities
of ole ns and isobutane to initiate the formation of carbocation intermediates.
Additionally, the reaction also requires small amounts of alkene for its activation.

Cocatalysts, such as aluminum chloride, are essential for the continuous operation of
processes like catalytic reforming. In this process, the catalyst itself consists of a
reaction between aluminum chloride and small amounts of water present in the
environment.
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 Catalytic reforming aims to improve the properties of fuel derivatives, such as
gasoline and petrochemical feedstocks, to increase their octane rating and suitability
for various industrial applications. Typically conducted at pressures of 10-50
atmospheres and temperatures ranging from 450 to 550 degrees Celsius, catalytic
reforming is a highly exothermic reaction.

Proper management of coke formation is essential in such processes, often

requiring multiple reactors operating in series, with periodic regeneration to remove
accumulated coke deposits and avoid catalyst deactivation. This regeneration
typically involves a high-temperature gas stream to burn off the coke deposits,
followed by a water quench to prevent overheating. The success of this process
relies on several key chemical reactions, including:

A. Naphthene

B. Naphthene Dehydroisomerisation

C. Para ne Dehydrocyclisation

D. Para ne isomerisation
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E. Para ne Hydrocracking

F. Hydrodesuiphurisation

In the mentioned reactions, such as the isomerization of hexane to

methylpentane, paraf n isomerization, and paraf n hydrocracking, the temperatures
needed for effective catalysis are elevated. Thus, it's crucial to avoid excessive
temperature increases during these reactions to prevent the formation of unwanted
coke deposits. Excessive temperatures can lead to the generation of coke residues,
reducing the ef ciency of liquid-phase reactions. Therefore, proper temperature
control is essential to mitigate coke formation and maintain the desired reaction
outcomes.

Thermal Cracking Processes: These processes involve converting a portion of

heavy oil into gasoline. Heavy oil typically contains a high percentage of gasoline
compared to the demand for gasoline, thus various operations have been developed
to address this. The most important of these processes cover 81% of the total. With
advances in science, the "Tube and Tank Process," a small-scale thermal cracking
process, has become popular, despite the option of other high-temperature thermal
cracking operations. The catalyst plays a crucial role in uidized-bed and moving-
bed thermal cracking operations. The process occurs at temperatures ranging from
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375°C to a maximum of 455-565°C, depending on the desired gasoline yield.The
removal of the catalyst coincides with the deactivation process. The key reactions
include cyclization, polymerization, dehydrogenation, and cleavage. Branched-chain
alkanes are more prevalent in thermal cracking due to their ease of formation, which
differs from regular alkanes. Cycloalkanes undergo the same reactions as normal
alkanes under thermal cracking conditions. However, the formation of polymeric
deposits decreases their reactivity. The focus is mainly on maintaining the high
catalytic activity associated with the cyclic group, as it enhances the formation of
desired gasoline components.

Catalytic Thermal Cracking Processes: The purpose of these processes is to

produce superior-quality gasoline from heavy oil, as opposed to conventional thermal
cracking operations. There are two types of catalytic thermal cracking processes
employed in industrial applications:A. Fluid-bed: These processes utilize uidized
bed technology for cracking heavy oil into gasoline. B. Moving-bed: These processes
employ moving-bed technology to achieve the same goal.Catalytic cracking
accounts for 15% of total cracking operations, covering both uid-bed and moving-
bed technologies.

In catalytic cracking processes, there are typically two types of catalysts used:

A. Natural Clay Catalysts:

These usually consist of silica (81%) and alumina (17.5%), along with small
amounts of other materials. They are often obtained from various types of
naturally occurring clays.

B. Synthetic Catalysts:

These are manufactured using pure materials to achieve precise properties

tailored for speci c catalytic cracking applications. They often include
molecular sieves, which are synthetic materials with speci c structures of
aluminum silicates capable of trapping metal ions, typically sodium ions. Rare
earth elements, binders, and other materials are also mixed in to form the
catalysts mechanically.Mechanically, the chemical components are mixed to
form a homogeneous mixture, with the weight of the primary components
slightly less than their intended nal weight to account for the main reactions
of the cracking catalyst. Mechanically, the cracking catalysts are divided into
two categories: the primary catalyst cracking and the secondary catalyst
cracking. The former involves the formation of the principal reaction products,
while the latter involves the transformation of the primary reaction products
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 into secondary ones. This rearrangement is essential for the conversion of
undesired components, such as dehydrogenation of aromatic hydrocarbons,
among others.Hydrocracking Processes:Hydrocracking is the process of
enhancing the catalytic cracking of hydrocarbons by adding hydrogen.
Typically carried out at temperatures between 345°C and 415°C and
pressures ranging from 65 to 835 atm, this process accelerates the
conversion of ole ns produced here to desirable alkanes, making it a
signi cant technological advancement. Additionally, it prevents the deposition
of coke on catalyst surfaces. One distinctive feature of hydrocracking
catalysts is their ability to withstand high-temperature operation and control
the formation of undesirable components, allowing for ef cient catalyst
regeneration and control over the composition of the resulting products. Given
the high-temperature operation of hydrocracking processes, the catalysts
used in them require careful consideration for heating arrangement

Catalytic Polymerization Processes:

Gas streams produced from re ning operations, such as catalytic cracking

processes, can be converted into valuable gasoline with high octane ratings by
employing catalytic polymerization processes. These processes utilize catalysts such
as phosphoric acid, fullers earth, or copper and cadmium phosphates.

The catalytic polymerization process involves heating the feedstock mixture to

temperatures typically ranging from 135°C to 875°C at pressures of 14 to 11 kg/cm².
Gasoline is then produced through various reactions, such as alkylation, where low-
octane components from petroleum are replaced with higher-octane ones, resulting
in gasoline with signi cantly improved properties.

The discussion surrounding catalytic polymerization processes often revolves around

the diverse chemical reactions involved and the selection of suitable catalysts. These
catalysts are chosen based on factors such as their cost-effectiveness, compatibility
with the feedstock materials used, and their ability to regenerate catalysts ef ciently.
The importance of catalyst selection is paramount in optimizing these processes and
achieving desired outcomes.
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