Group 5 Cracking
Group 5 Cracking
Group 5 Cracking
SUBMITTED TO
OF
FACULTY OF ENGINEERING
BY
GROUP E
i
Table of Contents
WHAT IS PETROLEUM?....................................................................................1
Refining of Petroleum.......................................................................................1
CRACKING PROCESS........................................................................................7
Thermal Cracking..............................................................................................7
Catalytic Cracking...........................................................................................18
Pyrolysis..........................................................................................................23
REFERENCES....................................................................................................25
ii
WHAT IS PETROLEUM?
Petroleum, also called crude oil, is a naturally occurring liquid found beneath the
earth’s surface that can be refined into fuel. A fossil fuel, petroleum is created by
the decomposition of organic matter over long period of time, and can be extracted
to be used to power vehicles, heating units, and machine, and can be converted into
plastics. Petroleum is gotten from the Latin word “Petra” meaning “rock,” and
“oleum” meaning “oil.” It consists of hydrocarbons of various molecular weights
and other organic compounds. Majority of the world relies on petroleum for many
goods and services. This has made the petroleum industry a major influence on
world politics and the global economy. Petroleum is recovered from underneath the
earth surface by drilling and then refined and separated into different types of fuels
of differing molecular weights and varying compositions. Key components of
petroleum include hydrocarbons such as methane, ethane, propane, and complex
molecules like benzene. After extraction, crude oil undergoes refining processes to
separate and purify its components, yielding products like gasoline, diesel, jet fuel,
and petrochemicals.
Refining of Petroleum
Petroleum refining is a complex industrial process that transforms crude oil into a
variety of valuable products, meeting market demands and regulatory standards.
Petroleum refining begins with the distillation, or fractionation, of crude oils into
separate hydrocarbon groups. The resultant products are directly related to the
characteristics of the crude processed. Most distillation products are further
converted into more usable products by changing the size and structure of the
hydrocarbon molecules through cracking, reforming, and other conversion
processes.
iii
Distillation in Petroleum Refining
Distillation, being the fundamental step in petroleum refining, serves as the initial
separation process to obtain various hydrocarbon fractions from crude oil. The
process begins with the crude oil feedstock, a mixture of hydrocarbons obtained
from beneath the earth’s surface. The crude oil is pretreated to a high temperature
to facilitate ease in distillation. After pretreatment, the crude in introduced into a
distillation tower, also known as crude unit, where the crude undergoes
fractionation into different components based on their boiling points. As the crude
moves up the tower, it encounters decreasing pressure, causing it to vaporize. The
hydrocarbons vaporize at different heights within the tower. The vaporized
hydrocarbons rise through the tower and are condensed back into liquid form as
they meet cooler temperatures at higher levels of tower.
iv
Fig 1 Process flow diagram for Atmospheric distillation of crude oil
v
Why Cracking is Required
Due to the limitations on distillation of petroleum, cracking is required for the
following reasons.
vi
The rate of cracking and the end products are strongly dependent on
the temperature and presence of catalysts. Cracking is the breakdown of a
large hydrocarbons into smaller, more useful alkanes and alkenes. Simply put,
hydrocarbon cracking is the process of breaking a long chain of hydrocarbons into
short ones. This process requires high temperatures More loosely, outside the field
of petroleum chemistry, the term "cracking" is used to describe any type of
splitting of molecules under the influence of heat, catalysts and solvents, such as in
processes of destructive distillation or pyrolysis. Fluid catalytic cracking produces
a high yield of petrol and LPG, while hydrocracking is a major source of jet
fuel, diesel fuel, naphtha, and again yields LPG.
Initiation: Here a single molecule breaks down into 2 free radicals. Only a
smaller portion of freed radicals undergoes initiation, but it is sufficient to
produce free radicals that are necessary to carry forward the reaction.
CH3CH3 → 2CH3
Abstraction of Hydrogen: here the second molecules become a free radical
as it removes a hydrogen atom from another molecule
CH3● + CH3CH3 → CH4 + CH3CH2●
Radical Decomposition: Here free radicals break into other free radical and
an alkane. This reaction gives rise to alkene products.
CH3CH2● → CH2=CH2 + N
vii
Radical Addition: this reaction results in the formation of aromatic products.
Here radical reacts with an alkene to produce a free radical.
CH3CH2● + CH2=CH2 → CH3CH2CH2CH2●
Termination: Here 2 radicals react with each other to form products that are
not free radicals. This reaction results in two forms namely recombination
and disproportionation.
CH3● + CH3CH2● → CH3CH2CH3
CH3CH2● + CH3CH2● → CH2=CH2 + CH3CH3
The first thermal cracking method known as the Shukhov cracking process was
the Standard Oil Company (Indiana), which later became the Amoco Corporation.
Burton used the process to break up large nonvolatile hydrocarbons into gasoline.
Various improvements to thermal cracking were introduced into the 1920s. Also in
the 1920s, French chemist Eugène Houdry improved the cracking process
1936 by the Socony-Vacuum Oil Company (later Mobil Oil Corporation) and in
1937 by the Sun Oil Company (later Sunoco, Inc.). Catalytic cracking was itself
powdered catalyst. During the 1950s, as demand for automobile and jet fuel
viii
employs hydrogen gas to improve the hydrogen-carbon ratio in the cracked
gasoline, kerosene (used in jet fuel), and diesel fuel. Modern low-temperature
hydrocracking was put into commercial production in 1963 by the Standard Oil
CRACKING PROCESS
The cracking process is very important for the commercial production of light fuels
such as gasoline, fuel oil, and gas oils. Because the simple distillation of crude oil
produces amounts and types of products that are not consistent with those required
accomplishing this change is through cracking. There are two main cracking
1. Thermal cracking
2. Catalytic cracking
Thermal Cracking
Thermal cracking is a crucial process in the petroleum industry. It allows for the
efficient production of useful products such as gasoline, diesel fuel, and jet fuel
ix
the range of 450 °C to 750 °C) and pressures (up to about 70 atmospheres) to break
the large hydrocarbons into smaller ones. Thermal cracking gives mixtures of
Visbreaking
significantly lowers the viscosity of heavy crude-oil residue without affecting the
x
boiling point range. The conversion of the residues is achieved by heating the
external drum, under controlled temperature and pressure. The heater effluent is
then quenched with a quenching medium (usually gas oil) to stop the reaction and
control overcracking.
Atmospheric vacuum residues and Solvent Deasphalter bottoms are typical feeds
of the Visbreaking unit which transforms the feed to gas, gasoline, gas oil, and
conversion techniques.
Product stability of the visbreaker residue is the main concern in selecting the
initially lead to a reduction in the visbroken fuel oil viscosity. However, fuel oil
stability will decrease as the level of severity increases beyond a certain point.
xi
Coil Visbreaking Process
facilitates the thermal cracking and altered viscosity necessary for further
processing. The feedstock is introduced into the heated coil in the furnace and
slightly cracked. Reaction temperatures range from 450 to 495 °C while working
xii
After exiting from the furnace, the visbroken products are quickly quenched to stop
the cracking reactions. To avoid coking in the fractionation tower, the quenching
phase is crucial. The most frequent quenching streams are gas oil and Visbreaker
section, where it is flashed. The fractionator separates the yield into gas, gasoline,
gas oil, and Visbreaker tar (residue). The fractionated gas oil is steam stripped to
remove volatile components before being mixed with the Visbreaker bottoms or
hydrocracking.
The main advantage of the coil-type design is the two-zone fired heater. This
type of heater provides a high degree of flexibility in heat input, resulting in better
control of the material being heated. With the coil-type design, decoking of the
The soaker-type Visbreaking process is very similar to the coil-type process except
the conversion is proceeded mainly in a vessel called Soaker after the heater. It
achieves some conversion within the heater. However, the majority of the
conversion occurs in a reaction vessel or soaker which holds the two-phase effluent
xiii
at an elevated temperature for a predetermined length of time. Soaker visbreaking
The soaker drum design allows the heater to operate at a lower outlet temperature
by providing the residence time required to achieve the desired cracking reactions.
This lower heater outlet temperature results in lower fuel cost which is the
advantage over the coil-type visbreaking process. The basic configuration of the
Soaker Process includes the heater, soaker, and fractionators, and a vacuum tower
Soaker cracking often involves less capital investment, uses less energy, and has
longer on-stream durations. Product qualities and yields from the coil and soaker
xiv
drum design are essentially the same at a given severity and are independent of the
visbreaker configuration.
Steam Cracking
or ethane is diluted with steam and briefly heated in a furnace in the absence of
oxygen. Typically, the reaction temperature is very high, at around 850 °C. The
reaction occurs rapidly with the residence time of the order of milliseconds and
flow rates approaching the speed of sound. After the cracking temperature has been
reached, the gas is quickly quenched to stop the reaction in a transfer line heat
time. Light hydrocarbon feeds such as ethane, LPGs, or light naphtha give mainly
feeds give some of the same products, but also those rich in aromatic
of propene, butene and liquid products. The process also results in the slow
deposition of coke, a form of carbon, on the reactor walls. This degrades the
Nonetheless, a steam cracking furnace can usually only run for a few months at a
time between de-coking’s. Decoking requires the furnace to be isolated from the
process and then a flow of steam or a steam/air mixture is passed through the
furnace coils. This converts the hard solid carbon layer to carbon monoxide and
carbon dioxide. Once this reaction is complete, the furnace can be returned to
service.
Coking
into lighter products or distillates. It is often considered to be the last stage in the
xvi
refining process since the heaviest fractions (tar) are converted into very useful
Different types of coking processes exist but the two most common processes are:
1. Delayed coking
Delayed Coking
The process includes a fractionator, furnace, two coke drums, and stripper. the
feedstock is charged directly to the fractionator, where it is heated, and the lighter
pumped to the coking furnace and then heated to the temperature range of 485–
500°C. The heated feedstock enters one of the pairs of coking drums, where the
sufficient to perform the cracking reaction when the coking drum is filled. In the
addition, to prevent the formation of coke in the furnace, short residence time and
high mass velocity in the furnace are required. Overhead stream in the coking
xvii
drum, gases, naphtha, middle distillates and coker heavy gas oil are sent to the
fractionator for separation, then separated and sent to downstream units for post-
treatment and coke deposits on the inner surface. For continuous operation, two
coke drums are used; while one is onstream, the other is decoking. The temperature
in the coke drum ranges from 415 to 465°C and the pressure varies between 2 and
6 bar. Coker heavy gas oil is recycled as a coker feed and combined with fresh
preheated feed and fed to the furnace, or used in other refining processes such as
hydrocracker or gas oil hydrotreater or as a catalytic fluid cracking feed. The Coke
drum is usually onstream about 24 hours before filling with porous coke.
xviii
Fig 6 Schematic of Delayed Coking Process
Fluid Coking
Fluid coking is a thermal cracking process consisting of a fluidized bed reactor and
a fluidized bed burner. Vacuum residue is preheated and fed to a scrubber that
550°C, and the feed is converted to vapour and lighter gases, which enter the
scrubber after passing through the cyclones at the top of the reactor. From the
scrubber, the reactor products are sent to the fractionator. Steam enters from the
bottom of the reactor to remove heavy hydrocarbons from the coke surface. The
xix
evolution of vapour from the cracking of the feed, and the addition of steam, gives
intense mixing of the coke particles within the reactor. The coke formed in the
burns with partial combustion of 15–30% of the coke by injecting air into the
burner. Coke combustion produces flue gases with low heating value which are
rich in carbon monoxide. Parts of the heated coke particles are returned to the
reactor to provide energy for the endothermic cracking reactions and to maintain
the reactor temperature. After cooling, the remaining coke is removed from the
plants or cement industries. This coke is very isotropic, rich in ash and sulphur and
The lower limit on operating temperature for fluid coking is set by the behaviour of
the fluidized coke particles. If the conversion to coke and light ends is too slow,
then the coke particles become sticky and agglomerate within the reactor. This
phenomenon occurs in localised zones of the reactor, likely near the nozzles that
inject the (colder) liquid bitumen feed, giving rise to chunks of coke that fall to the
bottom of the bed. For this reason, optimising the method for introducing feed into
the reactor is crucial. This process generally yields less coke and more gas oil and
olefins compared to the delayed coking process. One disadvantage of the fluid
coking process is the high rate of coke accumulation inside the unit. The reactor
xx
operates in a fouling mode, so coke deposits continuously on the interior surfaces
during operation. The reactor must be shut down for a month or more every 2 or 3
years to remove the accumulated coke, which can grow to be as thick as 1 meter on
the interior walls of the coker. The second disadvantage is the emission of
significant amounts of hydrogen sulphide and sulphur dioxide from the reactor
burner.
Catalytic Cracking
Catalytic cracking is similar to thermal cracking except that catalysts facilitate the
material that assists a chemical reaction but does not take part in it) in the cracking
xxi
reaction increases the yield of improved-quality products under much less severe
operating conditions than in thermal cracking. Typical temperatures are from 850°-
950° F at much lower pressures of 10-20 psi. The catalysts used in refinery
cracking units are typically solid materials such as zeolite, aluminum hydrosilicate,
treated bentonite clay, fuller’s earth, bauxite, and silica-alumina. They are used in
This process is used in petroleum refineries to convert the low-value heavier long-
chain hydrocarbon refinery fractions such as heavy vacuum gas oils into greater
economic value lighter products, mainly gasoline, distillate, and LPG. The rapid
cracking reactions of the FCC unit depend upon the circulating or fluidization of a
powder zeolite catalyst with the liquid feed into a riser of the FCC reactor for a few
seconds. This unit is normally, installed to produce more gasoline with high octane
There are various amounts of contaminants present in the FCC feed such as sulfur,
nitrogen, conradson carbon residue (CCR), and metals, particularly in high boiling
xxii
Hydrodesulfurization, Hydrodenitrogenation, Hydrodemetallization, Aromatic
The FCC feed is heated up to a temperature of about 315~425 oC and mixed with
hot regenerated catalyst (640~760 oC) at the bottom of the riser, which is a long
vertical pipe. The liquid feed is vaporized due to the hot catalyst and goes up in the
xxiii
The temperature at the riser outlet is a key factor in determining conversion and
product quality. At the top of the riser, the temperature reaches nearly 550 oC. The
riser is the main reactor in which the endothermic reactions take place. High
From the top of the riser, the gaseous products flow into the fractionator column,
while the separated catalyst and some heavy liquid hydrocarbons flow back into
the disengaging zone of the FCC reactor. Steam is also injected into the stripper
section to remove the oil from the spent catalyst. The oil is stripped from the
catalyst and moves along with rising vapors to the fractionator. The spent catalyst
The coke on the spent catalyst, produced in the FCC cracking reactions, is burned
off in the regenerator by introducing air. The produced hot flue gases exit at the top
of the regenerator that contains carbon dioxide, carbon monoxide, water, and
excess air at the regenerator temperature. The flue gases can also be sent to the
The FCC unit operation remains at a steady state as long as a heat balance exists
between the heat produced in the regenerator and the heat consumed in the reactor.
xxiv
In both the reactor and the regenerator, hydro cyclones are installed to remove any
A hydrocracking unit, takes gas oil which is heavier and has a higher boiling range
than distillate fuel oil, and cracks the heavy molecules into distillate and gasoline
heavy gas oils from the atmospheric or vacuum distillation tower, the fluid
catalytic cracker, and the coking units into high-quality, clean-burning jet fuel,
There are two main chemical reactions occurring in the hydrocracker: catalytic
xxv
saturation of these newly formed hydrocarbons with hydrogen. The catalytic
cracking of the heavier hydrocarbons uses heat and causes the feed to be cooled as
releases heat and causes the feed and products to heat up as they proceed through
the reactor. Hydrogen is also used to control the temperature of the reactor—it is
fed into the reactor at different points. This keeps the reactor temperature from
cooling to the point that cracking will not occur and from rising too high as to
Pyrolysis
air with the application of heat. Pyrolysis of higher alkanes to produce a mixture of
lower alkanes and alkenes are referred to as cracking. Usually, it is carried out by
heating the higher alkanes to high temperatures (670K – 970K) under pressure
ranging from 6-7 atm, either in the presence or absence of a catalyst. The chemical
When alkane vapors are passed in the absence of air through red-hot metal, it
breaks down into smaller or simpler hydrocarbons. This specific process occurs at
high pressure and high temperatures without a catalyst. But can be carried out at
xxvi
lowed pressures and temperatures in the presence of a catalyst such as palladium or
platinum.
Pyrolysis can be used to extract materials from items like tires or remove organic
contaminants from oily sludges and soils, and make biofuel from crops and waste.
It can assist in the breakdown of vehicle tires into some useful components on the
other hand also reducing the environmental impact of disposal of tires. Simply put,
cracking operations are essentially pyrolysis but not all pyrolysis operations are
cracking operations.
xxvii
REFERENCES
7. Hashemi R, Nassar NN, Almao PP. Nanoparticle technology for heavy oil
xxviii
10.Sawarkar AN, Pandit AB, Samant SD. Petroleum residue upgrading via
10.1016/j.fuel.2012.02.022
6701(96)88538-9
xxix
17.Gray MR. Upgrading Oilsands Bitumen and Heavy Oil. 1st ed. Edmonton:
19.Huc AY. Heavy Crude Oils: From Geology to Upgrading: An Overview. 1st
9782710808909
20.Speight JG. Heavy oil Recovery and Upgrading. 1st ed. Cambridge: Gulf
21.Speight JG. Heavy Oil and Extra-Heavy Oil Upgrading Technologies. 1st ed.
22.Clark JG. The Modification of Waxy Oil for Preparing a Potential Feedstock
xxx
High Value [thesis]. Pennsylvania: The Pennsylvania State University; 2008
xxxi