The improvement of the petroleum products can be due to the following:

I. Hydrogenation
II. Dehydration
III. Catalytic cracking
IV. Hydrocracking

I. Hydrogenation

Hydrogenation is a chemical reaction between molecular hydrogen (H2) and another compound
or element, usually in the presence of a catalyst such as nickel, palladium or platinum.
The process is commonly employed to reduce or saturate organic compounds. Hydrogenation
typically constitutes the addition of pairs of hydrogen atoms to a molecule, often an alkene.
Catalysts are required for the reaction to be usable; non-catalytic hydrogenation takes place only
at very high temperatures. Hydrogenation reduces double and triple bonds in hydrocarbons.
The following are the examples of hydrogenation reactions: (WIKIPEDIA)

Alkene: Ethene (C2H4) reacts with hydrogen at 150 ͦ C to produce ethane (C2H4).
C2H4 + H2 → C2H6
Cycloalkene: Cyclohexene (C6H10) converts into cyclohexane (C6H12) by reacting with
hydrogen in the presence of palladium (Pd) catalyst.

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C6H10 + H2 → C6H12
The catalysts most commonly used for hydrogenation reactions are the metals nickel, platinum,
and palladium and their oxides. For high-pressure hydrogenations, copper chromite and nickel
supported on kieselguhr (loose or porous diatomite) are extensively used.

II. Dehydration

Natural gas usually contains water, in liquid and/or vapor form, at source and/or as a result of
sweetening with an aqueous solution.
Operating experience proved that it is necessary to reduce and control the water content of gas to
ensure safe processing and transmission.
Reasons of Dehydration
a) To avoid hydrates formation that can plug valves fittings or even pipelines.
b) Water can condense in the pipeline, causing slug flow and possible erosion and corrosion.
c) Water vapor increases the volume and decreases the heating value of the gas.
d) Sales gas contracts and/or pipeline specifications.
The dehydration of the natural gas is accomplished by lowering the dew point temperature of the
gas at which water vapor will condense from the gas.
Dehydration Methods
There are several methods of dehydrating natural gas. The most common of these are;
i. Liquid desiccant (glycol) dehydration,
ii. Solid desiccant dehydration, and
iii. Refrigeration (i.e. cooling the gas).
The first two methods utilize mass transfer of the water molecule into a liquid solvent (glycol
solution) or a crystalline structure (dry desiccant).
The third method employs cooling to condense the water molecule to the liquid phase with the
subsequent injection of inhibitor to prevent hydrate formation
However, the choice of dehydration method is usually between glycol and solid desiccants

Glycol Dehydration:

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Absorption is the common technique, where the water vapor in the gas stream becomes absorbed
in a liquid solvent stream.
Several glycols such as Monoethylene glycol (MEG) have been found suitable for commercial
application.
Other glycols includes Diethylene glycol (DEG) and Triethylene glycol (TEG).

 Wet natural gas first typically enters an inlet separator to remove all liquid hydrocarbons
from the gas stream.
 Then the gas flows to an absorber (contactor) where it is contacted counter currently and
dried by the lean glycol.
 Glycol also absorbs volatile organic compounds (VOCs) that vaporize with the water in
the reboiler.
 Dry natural gas exiting the absorber passes through a gas/glycol heat exchanger and then
into the sales line.
 The wet or “rich” glycol exiting the absorber flows through a coil in the accumulator
where it is preheated by hot lean glycol.

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  After the glycol–glycol heat exchanger, the rich glycol enters the stripping column and
flows down the packed bed section into the reboiler

III. Catalytic cracking

Cracking; in petroleum refining, is the process by which heavy hydrocarbon molecules are
broken up into lighter molecules by means of heat and usually pressure and sometimes catalyst.
The original incentive to develop cracking processes arose from the need to increase gasoline
supplies and to increase the octane number of gasoline.
Moving down on the side streams of the distillation column, heavy gas oil constitutes the next
fraction in line.
Some generic conversion processes for the heavy distillates, such as heavy gas oil (consisting of
C20 to C25 hydrocarbons).
These processes, aimed at reducing the molecular size or the boiling point of gas oil compounds,
and involve thermal cracking or catalytic cracking.

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A mild thermal cracking process, called visbreaking, is applied to reduce the viscosity
of the feedstock, and it is more frequently applied to residual fractions, such as vacuum
distillation residue.
A more severe thermal cracking of heavy gas oil can be used to produce LPG and ethylene and
light and middle distillates from heavy gas oil.
A highly aromatic byproduct from thermal cracking is called ethylene tar.
Ethylene is an important petrochemical feedstock, while ethylene tar can be used as feedstock to
produce carbon blacks.
Catalytic cracking is more frequently used for conversion of heavy gas oil to gasoline.
Catalytic cracking is basically the same as thermal cracking, but it differs by the use of a catalyst.
The feedstocks for catalytic cracking can be any one (or blends) of the flowing:
 Straight gas oil
 vacuum gas oil
 atmospheric residuum and
 vacuum residuum.
If blends of the above feedstocks are employed, compatibility of the constituents of the blends
must be assured under reactor to conditions or excessive coke will be laid down on to the
catalyst.
In addition, there are several pretreatment options for the feedstocks for catalytic cracking units,
including:
i. Deasphalting to prevent excessive coking on catalyst surfaces
ii. Demetallation, i.e., removal of nickel, vanadium, and iron to prevent catalyst deactivation
iii. Use of a short residence time as a means of preparing the feedstock, and
iv. Hydrotreating or mild hydrocracking to prevent excessive coking in the fluid catalytic
cracking unit
There are three basic types of catalytic crackers:
i. Fluid bed
ii. Moving bed
iii. Fixed bed

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  The fixed-bed process was the first to be used commercially and uses a static bed of
catalyst in several reactors, which allows a continuous flow of feedstock to be
maintained.

Thus, the cycle of operations consists of:

 Flow of feedstock through the catalyst bed
 Discontinuance of feedstock flow and removal of coke from the catalyst by burning and
 Insertion of the reactor on-stream.
 The moving-bed process uses a reaction vessel in which cracking takes place and a kiln
in which the spent catalyst is regenerated, catalyst movement between the vessels is
provided by various means.
 The fluid-bed process differs from the fixed-bed and moving-bed processes insofar as the
powdered catalyst is circulated essentially as a fluid with the feedstock.
 Zeolites are the most common catalyst because of:
Higher activity:
 Ability to achieve higher conversion without over cracking.
 Permit short residence (reaction) time (good for riser cracking operations).
Higher selectivity:
 Produce higher gasoline yield for a given conversion.
 Produce gasoline containing more paraffins and aromatics.
 Produce more isobutene (higher ON).
 Lower coke yield (less catalyst fouling/deactivation) which means higher throughput at a
given conversion.
The high activity of zeolite cracking catalyst allows for shorter residence time.
Basic nitrogen compounds, iron, nickel, vanadium, and copper in the oil act as poisons to
cracking catalysts.
The nitrogen reacts with the acid centers on the catalyst and lowers its activity.
The metals deposit and accumulate on the catalyst and cause a reduction in throughput.
By increasing coke formation and decreasing the amount of coke burn-off per unit air.
This is due to the catalysis effect of the metal where the coke is converted to carbon dioxide
rather carbon monoxide.

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It is generally accepted that nickel has four times the effect on catalyst selectivity as vanadium
although nickel and vanadium deposits reduce the catalyst activity by occupying the catalyst’s
active sites.
The major effects are the promotion of the formation of gas and coke and reduce the gasoline
yield.
Metals removal processes can be used to reactivate the catalyst.
Catalytic cracking has a number of advantages over thermal cracking:
a) Gasoline produced by catalytic cracking has a higher octane number and consists largely
of iso-paraffins and aromatics.
b) The iso-paraffins and aromatic produced have high octane numbers and greater chemical
stability than mono-olefins and diolefins.
c) The olefins and diolefins are present in much greater quantities in gasoline produced by
thermal cracking processes.
d) Further, substantial quantities of olefin gases and smaller quantities of methane, ethane,
and ethylene are produced by catalytic cracking.
e) The olefin gases are suitable for polymer gasoline manufacture.
f) Sulfur compounds are changed in such a way that the sulfur content of gasoline produced
by catalytic cracking gasoline is lower than the sulfur content of gasoline
produced by thermal cracking.
g) Catalytic cracking produces less residuum and more of the useful gas oil constituents
than thermal cracking.
h) Finally, the process has considerable flexibility, permitting the manufacture of both
motor gasoline and aviation gasoline and a variation in the gas oil production to meet
changes in the fuel oil market.(BY ENG. WALID NOTICES, 2019)
IV. Hydrocracking
Hydrocrackingis a catalytic process that converts heavy oils to lighter fractions primarily by
means of aromatic saturation, cracking, and isomerization reactions in the presence of hydrogen.
It is one of two major conversion processes used in modern refining. The other process is Fluid
Catalytic Cracking (FCC), which is mainly used for gasoline production, while hydrocracking
plays a more versatile role, being equally flexible at producing middle distillates. Hydrocracking
has been widely accepted because of its capability to produce superior quality products: highest

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quality middle distillates; naphthas with high naphthene content for catalytic reformer feed; lube
oil base stocks; feedstock for FCC units and pyrolysis processes for ethylene production.
As shown in Table 1, hydrocracking is an extremely versatile process. It accepts a wide range of
feed stocks and produces a variety of products. The process is environment-friendly in that it
eliminates compounds from petroleum products that would otherwise end up as hazardous
sulphur and nitrogen oxides in the atmosphere. The exothermic reactions in hydrocracking result
in a low net requirement of fuel, and therefore gas emissions from the process are also low.

(VOLUME II / REFINING AND PETROCHEMICALS )

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References:
i. Hudlický, Miloš (1996). Reductions in Organic Chemistry. Washington, D.C.: American
Chemical Society. p. 429. ISBN 978-0-8412-3344-7.
ii. https://en.wikipedia.org/wiki/Hydrogenation#cite_note-1
iii. Handbook of Natural Gas Transmission and Processing By Saeid Mokhatab, William A.
Poe
iv. VOLUME II / REFINING AND PETROCHEMICALS