AN ASSIGNMENT ON OIL REFINING

Submitted to Sir Mohsin

Submitted by Kiran Shahzadi
0056-BH-E-CHEM-18
Semester 8th
Dated: 08/05/2022
GCU LAHORE
_______________________________________________________________________

What is Crude Oil:

Petroleum or crude oil is a complex mixture of hydrocarbons and other chemicals. The
composition varies widely depending on where and how the petroleum was formed. In fact,
chemical analysis can be used to fingerprint the source of petroleum. However, raw
petroleum or crude oil has characteristic properties and composition.

Origin of Petroleum:
The origin of petroleum still has uncertainties despite the tremendous researches and
studies devoted to it rather than any other natural substance. There are two different
theories for the origin of petroleum; Organic and Inorganic origin.
Inorganic or Abiotic origin:
States that hydrogen and carbon came together under great temperature and pressure, far
below the earth’s surface and formed oil and gas where chemical reactions have occurred.
The oil and gas then seeped through porous rock to deposit in various natural underground
traps. It has also excluded the hypothesis that petroleum is a finite substance. There are
some different theories that describe the inorganic origin of petroleum which include:
Metal carbide theory:
Developed by a Russian chemist and states that the deposition of petroleum is controlled by
tectonic activities that occurred during the life of sedimentary rock. To explain his
observations, he has put forth "metal carbide theory". Metal carbides deep in Earth reacted
with water at high pressure and temperature to form acetylene which condenses to heavier
hydrocarbons.
Reaction equation is: Cac2+H2O= C2H2+Ca (OH)2
Volcanic theory:
Involves outgassing of the mantle via volcanic activity or eruption.
Earthquake theory:
Involves outgassing deep Earth's mantle via tectonic activities such as faults, and this is still
happening till now.
Organic origin:
It is the most widely accepted. The oil and gas are formed from remains of prehistoric plants
and animals. Remains of plants have been transformed to coal and animals to oil and gas.
These remains were settled into seas and accumulated at the ocean floor and buried under
several kilometres of sediments. Over a few million years, the layers of the organic material
were compressed under the weight of the sediments above them. The increase in pressure
and temperature with the absence of oxygen changed the mud, sand, slit or sediments into
rock and organic matter into Kerogen. After further burial and heating, the kerogen
transformed via cracking into petroleum and natural gas.[3]
Overwhelming evidences for organic origin of petroleum:

• Presence of brine (sea water) with petroleum.

• Petroleum is found only in association with sedimentary rocks. There is no
petroleum associated with igneous or metamorphic rocks.
• Polarized light passing through all petroleum resources undergoes a rotation that is
similar to all organic oils.
• Molecules in hydrocarbons are thought to be similar to that of the organic matter.
• The organic carbon found in plants is depleted into C13 due to photosynthesis
process. In dead organic matter, it is further depleted due to radioactive decaying.
The same depletion was found in petroleum and natural gas.

Conclusions:
The battle between organic and inorganic theories are still persistent till now. All the
supporters from both sides were struggling to prove their theory. According to organic
theory, petroleum is a finite substance formed from organisms decaying at several
kilometres below the ground surface. On the other side, Inorganic origin supporters
consider petroleum a self-regenerating substance produced by the Earth itself with the
assistance of chemical interactions occurring deep within the Earth. In other words, it is
assumed that petroleum is not a finite substance as oil and gas didn't not run out till now.
The most widely accepted one is the organic theory which defines the substantial conditions
for the formation of petroleum such as: saturated soil, absence of oxygen and high pressure
and temperature conditions. All these conditions contribute to the decay of organic matters
which then is transformed into kerogen forming a source rock.
Chemical Constitution and Classification of Crude Oil:
Crude oil is a complex liquid mixture made up of a vast number of hydrocarbon compounds
that consist mainly of carbon and hydrogen in differing proportions. In addition, small
amounts of organic compounds containing sulphur, oxygen, nitrogen and metals such as
vanadium, nickel, iron and copper are also present.

Hydrocarbons are generally divided into four groups:

(1) Paraffins,
(2) Olefins,
(3) Naphthenes
(4) Aromatics

Among these groups, paraffins, olefins, and naphthenes are sometimes called aliphatic
compounds, as different from aromatic compounds. The lightest hydrocarbon found as a
dissolved gas is methane (CH4), the main component of natural gas. Olefins are not usually
found in crude oils, but produced in a number of refining processes.
Paraffins:
General formula: CnH2n+2 (n is a whole number, usually from 1 to 20), straight or branched
chain molecules, can be gasses or liquids at room temperature depending upon the
molecule. For example, methane, ethane, propane, butane, isobutane, pentane, hexane

Olefins (also known as alkenes):

General formula: CnH2n (n is a whole number, usually from 1 to 20), linear or branched
chain molecules containing one carbon-carbon double-bond, can be liquid or gas. For
example: ethylene, butene, isobutene

Naphthenes (cycloalkanes):
General formula: CnH2n (n is a whole number usually from 1to 20), ringed structures with
one or more rings, rings contain only single bonds between the carbon atoms, typically
liquids at room temperature. For example: cyclohexane, methyl cyclopentane
Aromatics:
General formula: C6H5 - Y (Y is a longer, straight molecule that connects to the benzene
ring), ringed structures with one or more rings, rings contain six carbon atoms, with
alternating double and single bonds between the carbons, typically liquids. For examples
benzene, naphthalene

Crude oils from various origins contain different types of aromatic compounds in different
concentrations. Light petroleum fractions contain mono-aromatics, which have one benzene
ring with one or more of the hydrogen atoms substituted by another atom or alkyl groups.
Examples of these compounds are toluene and xylene.

More complex aromatic compounds consist of a number of benzene rings. These are known
as polynuclear aromatic compounds. They are found in the heavy petroleum cuts, and their
presence is undesirable because they cause catalyst deactivation and coke deposition during
processing, besides causing environmental problems when they are present in diesel and
fuel oils. Examples of polynuclear aromatic compounds are shown below.

Sulphur Compounds:
Crude oils contain sulphur heteroatoms in the form of elemental sulphur S, dissolved
hydrogen sulphide H2S, carbonyl sulphide COS, inorganic forms and most importantly
organic forms, in which sulfur atoms are positioned within the organic hydrocarbon
molecules.
Sulfur compounds lead to environmental pollution, decreases the life of machinery,
corrodes of pipes, machines and equipment, affecting the additives used for the purpose of
increasing the octane number, reduce the activity of Tetra Ethyl Lead (TEL) added to
gasoline. As a result, the engine metal will erode and leads to destruct the metallic parts.
Also, their emissions are very dangerous to human safety and environment. In addition,
these impurities cause catalyst poisoning and reduce the catalyst activity.
Sulfur containing constituents of crude oils vary from simple mercaptans, also known as
thiols, to sulphides and polycyclic sulphides (Mercaptans (R–SH), sulphides (R–S–R'),
disulphides (R–S–S–R'), Thiophenes)
Nitrogen Compounds:
Crude oils contain very low amounts of nitrogen compounds, less than 1%, The nitrogen
compounds in crude oils may be classified as basic or non-basic. Basic nitrogen compounds
consist of pyridines. The greater part of the nitrogen in crude oils is the non-basic nitrogen
compounds, which are generally of pyrrole types. The decomposition of nitrogen
compounds in catalytic cracking and hydrocracking processes forms ammonia and cyanides
that can cause corrosion.

Oxygen Compounds:
Less than 1% (found in organic compounds such as carbon dioxide, phenols, ketones,
carboxylic acids) occur in crude oils in varying amounts.
Metals Compounds:
Metallic compounds exist in all crude oil types in very small amounts. Their concentration
must be reduced to avoid operational problems and to prevent them from contaminating
the products. They cause poisoning to the catalysts used for hydro processing and cracking.

Asphaltenes and Resins Compounds:

Asphaltenes are dark brown friable solids. They are made up of condensed polynuclear
aromatic layers linked by saturated links. The presence of high amounts of asphaltenes in
crude oil can create tremendous problems in production because they tend to precipitate
inside the pores of rock formations, well heads and surface processing equipment.

What Is an Oil Refinery?

An oil refinery is an industrial plant that transforms, or refines crude oil into various usable
petroleum products such as diesel, gasoline and heating oils. Oil refineries essentially serve
as the second stage in the crude oil production process following the actual extraction of
crude oil up-stream, and refinery services are considered to be a down-stream segment of
the oil and gas industry.
An oil refinery or petroleum refinery is an industrial process plant where petroleum (crude
oil) is transformed and refined into useful products such as gasoline (petrol), diesel fuel,
asphalt base, fuel oils, heating oil, kerosene, liquefied petroleum gas and petroleum
naphtha.
Petrochemicals feedstock like ethylene and propylene can also be produced directly by
cracking crude oil without the need of using refined products of crude oil such as naphtha.
The crude oil feedstock has typically been processed by an oil production plant.
Oil refineries are typically large, sprawling industrial complexes with extensive piping
running throughout, carrying streams of fluids between large chemical processing units,
such as distillation columns. In many ways, oil refineries use much of the technology and can
be thought of, as types of chemical plants.
Since December 2008, the world’s largest oil refinery has been the Jamnagar Refinery
owned by Reliance Industries, located in Gujarat, India, with a processing capacity of 1.24
million barrels.

Detailed Schematic Diagram of the Refining Process:

Steps of Petroleum Refining:
Distillation:

• Atmospheric Distillation
• Vacuum Distillation
Catalytic Reforming
Hydrotreating Units
Cracking

• Fluid Catalyst Cracking Unit (FCCU)

• Hydrocracking
• Thermal Cracking

The Atmospheric Crude Distillation Unit:

In refining the crude oil, it is first broken up into those raw stocks that are the basis of the
finished products. This breakup of the crude is achieved by separating the oil into a series of
boiling point fractions which meet the distillation requirements and some of the properties
of the finished products. This is accomplished in the crude distillation units. Normally there
are two units that accomplish this splitting up function: an atmospheric unit and a vacuum
unit. The crude oil is first desalted (dissolved brine is removed by washing) and heated to a
predetermined temperature prior to its introduction into the atmospheric unit. This is
accomplished by heat exchange with hot products and finally by a direct fired heater. The
hot and partially vaporized crude is “flashed” in a trayed distillation tower. Here, the
vaporized portion of the crude oil feed moves up the tower and is selectively condensed by
cooled reflux streams moving down the tower. These condensates are taken off at various
parts of the tower according to their condensing temperature as distillate side streams. The
light oils not condensed in the tower are taken off at the top of the tower to be condensed
externally as the overhead product. The Un vaporized portion of the crude oil feed leaves
the bottom of the tower as the atmospheric residue. The unit operates at a small positive
pressure around 5–10 psig.
The Crude Vacuum Distillation Unit:
Further breakup of the crude is often required to meet the refinery’s product slate. This is
usually required to produce low-cost feed to cracking units or to produce the basic stocks
for lubricating oil production. To achieve this, the residue from the atmospheric unit is
distilled under sub atmospheric conditions in the crude vacuum distillation unit. This unit is
similar to the atmospheric unit in so much as the feed is heated by heat exchange with hot
products and then in a fired heater before entering the distillation tower. In this case,
however, the tower operates under reduced pressure (vacuum) conditions. These units
operate at overhead pressures as low as 10 mmHg. Under these conditions the hot residue
feed is partially vaporized on entering the tower. The hot vapours rise up the tower to be
successively condensed by a cooled internal reflux stream moving down the tower as was
the case in the atmospheric distillation unit. The condensed distillate streams are taken off
as side stream distillates.

The Catalytic Reformer Unit:

The purpose of the catalytic reformer plant is to upgrade low-octane naphtha to the high-
octane material suitable for blending into motor gasoline fuel. It achieves this by reforming
some of the hydrocarbons in the feed to hydrocarbons of high-octane value. Notably among
those reactions is the conversion of cycloparaffin content of the feed to aromatics. This
reaction also gives up hydrogen molecules which are subsequently used in the refinery’s
hydrotreating processes.
The Hydrotreating Units (de-sulfurization):
Most streams from the crude distillation units contain sulfur and other impurities such as
nitrogen and metals in some form or other. By far the most common of these impurities is
sulfur, and this is also the least tolerable of these impurities. Its presence certainly lowers
the quality of the finished products and, in the processing of the crude oil, its presence
invariably affects the performance of the refining processes. Hydrotreating the raw distillate
streams removes a significant amount of the sulfur impurity by reacting the sulfur molecules
with hydrogen to form hydrogen sulfide (H2S); this is then removed as a gas. Several types
of hydrotreaters are described in this book. The two most common types found are:

• Naphtha hydrotreating – once through or recycle hydrogen

• Diesel hydrotreating – recycle hydrogen
In naphtha hydrotreating the naphtha from the naphtha splitter is mixed with the hydrogen-
rich gas from the catalytic reformer unit and preheated to about 700-degree F by heat
exchange and a fired heater. On leaving the fired heater, the stream enters a reactor
containing a desulfurizing catalyst (often Co Mo – cobalt molybdenum – on an alumina
base). The sulfur components of the feed combine with the hydrogen to form H2S.

Diesel hydrotreating has very much the same process configuration as the naphtha unit. The
main difference is that this unit will almost invariably have a rich hydrogen stream recycle.
The recycle gas stream in these units is often treated for the removal of H2S before
returning to the reactors.
The Fluid Catalytic Cracking Unit (FCCU):
This cracking process is among the oldest in the oil industry. Although developed in the
mid-1920s, it first came into prominence during the Second World War as a source of high-
octane fuel for aircraft. The prominence of the fluid catalytic cracking unit (FCCU) was re-
established in the 1960s by two developments in the process. These were:

• The use of highly active and selective catalysts (Zeolites)

• The establishment of riser cracking techniques These two developments enabled the
process to produce higher yields of better-quality distillates from lower-quality
feedstocks.
The process consists of a reactor vessel and a regenerator vessel interconnected by transfer
lines to enable the flow of finely divided catalyst powder between them. The oil feed
(typically high-vacuum gas oil, HVGO, from the crude vacuum unit) is introduced to the very
hot regenerated catalyst stream leaving the regenerator en route to the reactor. Cracking
occurs in the riser inlet to the reactor due to the contact of the oil with the hot catalyst. The
catalyst and oil are very dispersed in the riser so that contact between them is very high
exposing a large portion of the oil to the hot catalyst. The cracking is completed in the
catalyst fluid bed in the reactor vessel. The catalyst fluidity is maintained by steam injection
at the bottom of the vessel. The cracked effluent leaves the top of the reactor vessel as a
vapor to enter the recovery section of the plant. Here the distillate products of cracking are
separated by fractionation and forwarded to storage or further treating.

The catalyst from the reactor is transferred to the regenerator on a continuous basis. In the
regenerator the catalyst is contacted with an air stream which maintains the catalyst in a
fluidized state. The hot carbon on the catalyst is burned off by contact with the air and
converted into CO and CO2. The reactions are highly exothermic rising the temperature of
the catalyst stream to well over 1,000-degree F and thus providing the heat source for the
oil cracking mechanism.
Products from this process are:

• Unsaturated and saturated LPG

• Light cracked naphtha
• Heavy cracked naphtha
• Cycle oil (mid distillate)
• Slurry

The Hydrocracking Process:

What is Hydrocracking?
Hydrocracking is the conversion process of higher boiling point petroleum fractions to light
hydrocarbons (mainly gasoline and jet fuels) in the presence of a catalyst. Hydrocracking is
catalytic cracking in the presence of hydrogen. The extra hydrogen saturates, or
hydrogenates, the chemical bonds of the cracked hydrocarbons and creates isomers with
the desired characteristics.
Hydrocracking is also a treating process, because the hydrogen combines with contaminants
such as sulphur and nitrogen, allowing them to be removed.

The two reactions that occur are

• Cracking (endothermic) and

• Hydrogenation (exothermic). Heat of cracking is supplied by the hydrogenation
reaction.

Why Hydrocracking?
The increasing demand for gasoline and jet fuel compared to diesel fuel and home heating
oils was a dominant factor in the development of hydrocracking process. Hydrogen as a by-
product of catalytic reforming process was available in large amounts and relatively cheap

Hydrocracking Processes:

This process is fairly new to the industry becoming prominent in its use during the late
1960s. As the title suggests the process cracks the oil feed in the presence of hydrogen. It is
a high-pressure process operating normally around 2,000 psig. This makes the unit rather
costly and, for many years, slowed its expansion in the industry compared with the FCCU
and thermal cracking. However, the process is very flexible and is capable of making
modern, high- quality distillate fuels and lubes.
The process consists of one or two reactors, a preheat system, recycle gas section, and a
recovery section. The oil feed (typically a vacuum gas oil) is preheated by heat exchange
with reactor effluent streams and by a fired heater. Make-up and recycled hydrogen
streams are introduced into the oil stream before entering the reactor(s).

The fresh feed is mixed with hydrogen gas and recycle gas (high in hydrogen content) and
passed through a heater to the first reactor. If the feed is high in sulfur and nitrogen a guard
reactor is employed to convert sulfur to hydrogen sulfide and nitrogen to ammonia to
protect precious catalyst in the following reactor.
Hydrocracking reactors are operated at high temperatures to produce materials with boiling
point below 400. The reactor gaseous effluent goes through heat exchangers and a high-
pressure separator where the hydrogen rich gases are separated and recycled to the first
stage.
The liquid product from the reactor is sent to a distillation column where C1-C4 and lighter
gases are taken off and the gasoline, jet fuel, naphtha and/or diesel fuel streams are
removed as liquid side streams. The distillation bottom product is sent to the second
hydrocracker which is maintained at a much lower pressure (around 150–100 psig). Because
of this reduction in pressure, a second gas stream is flashed off. This will have a much lower
hydrogen content but will contain C3s and C4s.
There are hundreds of simultaneous chemical reactions occurring in hydrocracking. It is
assumed that the mechanism of hydrocracking is that of catalytic cracking with hydrogen
superimposed. In catalytic cracking the C – C bond is broken, while in hydrogenation, H2 is
added to a carbon- carbon double bond. Cracking is an endothermic reaction.
Hydrogenation is an exothermic reaction.

Thermal Cracking Units:

Thermal cracking processes are the heavy work horses of the oil refining industry. The
processes are relatively cheap when compared with the fluid cracker and the 38 D.S.J. Jones
hydrocracker but go a long way to achieving the heavy oil cracking objective of converting
low-quality material into more valuable oil products. The process family of thermal crackers
has three members, which are:

• Thermal crackers
• Vis breakers
• Cokers

The term thermal cracking is given to those processes that convert heavy oil (usually fuel oil
or residues) into lighter product stock such as LPG, naphtha, and middle distillates by
applying only heat to the feed over a prescribed element of time.
The term thermal cracker when applied to a specific process usually refers to the processing
of atmospheric residues (long residues) to give the lighter products.
The term visbreaking refers to the processing of vacuum residues (short residues) to reduce
the viscosity of the oil only and thus to meet the requirements of a more valuable fuel oil
stock.
Coking refers to the most severe process in the thermal cracking family. Either long or short
residues can be fed to this process whose objective is to produce the lighter products and
petroleum coke.
The Coker process is extinctive – that is, it converts all the feed. In the other two processes,
there is usually some unconverted feed although the thermal cracker can be designed to be
“extinctive” by recycling the unconverted oil. The three thermal cracking processes have the
same basic process configuration. This consists of a cracking furnace, a “soaking” vessel or
coil, and a product recovery fractionator(s).
The feed is first preheated by heat exchange with hot product streams before entering the
cracking furnace or heater. The cracking furnace raises the temperature of the oil to its
predetermined cracking temperature. This is always in excess of 920-degree F and, by
careful design of the heater coils, the oil is retained in the furnace at a prescribed cracking
temperature for a predetermined period of time (the residence time). In some cases, an
additional coil section is added to the heater to allow the oil to “soak” at the fixed
temperature for a longer period of time. In other cases, the oil leaves the furnace to enter a
drum which retains the oil at its cracking temperature for a little time. In the Coker process,
the oil leaves the furnace to enter one of a series of Coker drums in which the oil is retained
for a longer period of time at its coking temperature for the production of coke.
It then enters a fractionator where the distillate products are separated and taken off in a
manner similar to the crude distillation unit.

Producing the Aromatic Feedstock:

The production of aromatic feedstocks originates with the catalytic reforming of a refinery
stream of a heavy naphtha range (say 120–420-degree F) and rich in naphthenes. A typical
stream that meets these criteria would be a naphtha stream from a hydrocracker. Thus, in
order to meet petrochemical needs, a hydrocracker may form part of a fuel refinery
configuration. This unit would be operated to maximize naphtha production. This would
mean running the unit at a low space velocity with a higher oil recycle rate (i.e., most
recovered product heavier than the naphtha would be recycled back to the reactors).
Another source of high naphthene feed to the cat reformer would be hydrotreated cat
cracker naphtha. Of course, the hydrotreating of unsaturated has a high demand on the
refinery’s hydrogen system, but this is balanced to some extent by the additional hydrogen
produced in reforming the naphthenes. Should the refinery configuration include a thermal
cracker and/or a steam cracker, the hydrotreating of the naphtha cut from these units also
yields high naphthene catalytic reformer feedstock.
Catalytic reforming of the high naphthene-content naphtha produces aromatics, but there
are also some unreacted paraffins and some naphthenes present. The downstream
petrochemical units that separate and purify the aromatic reformate are expensive both in
capital and operating costs. The specification for the BTX (benzene, toluene, xylene) feed is
very stringent and excludes nonaromatic components as much as possible. Another process
may therefore be included in the refinery configuration to “clean up” this aromatic feed
stream before leaving the refinery. This is an aromatic extraction plant. This is a licensed
process using a solvent to separate the paraffins and aromatics by counter current
extraction.
The rich aromatic stream is then forwarded to the BTX plant where benzene, toluene, ethyl
benzene, and o-xylene are separated by fractionation while the para-xylene is usually
separated by crystallization or by solid adsorption. The meta-xylene may also be recovered
by super distillation, but more often than not, it is converted into o-xylene or p-xylene in an
isomerization unit.

Producing the Olefin Feedstock:

The source of olefins in a refinery configuration is from either the FCCU, a thermal cracker,
or a steam cracker. The olefins produced as a gas are ethylene, propylene, and the C4s, such
as butylenes, butadiene, etc. Liquid olefinic products from these units are normally
hydrotreated to make reformer feedstock and thus the BTX feed. All products, of course, are
treated for sulfur control and cleaned up before leaving the refinery as petrochemical
feedstock. The specifications for these products are stringent and usually the “clean-up”
plants are dedicated to the treatment of these products. Olefins are used mostly in the
production of polymers such as the vinyl polymers (vinyl chloride, vinyl acetate, and the
like), polyethylene products, and polypropylene products. The heavier C4s are a major
constituent in the production of synthetic rubbers. Figure 17 shows a configuration for a
typical petrochemical refinery.

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