UNIT- IV Petrochemicals

Petroleum is derived from the Latin words “petra” and “oleum,” which means “rock” and
“oil,” respectively. Petroleum is also known as crude oil or fossil fuel. It is a thick, flammable,
yellow-to-black mixture of gaseous, liquid, and solid hydrocarbons formed from the
decomposition of organic matter over millions of years under high pressure and temperature
beneath the Earth's surface. The organic mixture changes chemically and broke down into
hydrocarbons. Petroleum is classified as a non-renewable energy source primarily because of its
geological formation process and the timescale it takes for its replenishment
Composition of crude petroleum
Petroleum can be in gas, liquid, and solid forms of hydrocarbons. The forms of petroleum
are functions of pressure, temperature, and other surrounding conditions such as rock and soil.
Under low surface pressure and temperature conditions, lighter hydrocarbons such as methane,
ethane, propane, and butane occur as gases, while heavier hydrocarbons such as octane, benzene,
xylenes, and paraffin wax are in the form of liquids or solids.
Chemical composition of crude oil:

Element Composition (Weight%)

Carbon 83 to 85%
Hydrogen 10 to 14%
Nitrogen 0.1 to 2%
Oxygen 0.05 to 1.5%
Sulfur 0.05 to 6.0%
Metals < 0.1%
Petroleum is a mixture of a very large number of different hydrocarbons. The four most
commonly found categories of molecules are paraffins, naphthene, aromatics and more
complicated chemical compounds such as asphaltenes.

Paraffins are saturated hydrocarbons with straight or branched chains containing only carbon and
hydrogen. They have the general formula CnH2n+2. Examples of alkanes in crude oil are hexane,
decane, and 2,2,4-trimethylpentane (iso-octane).

1
Naphthene (cycloalkanes) are saturated hydrocarbons that have one or more carbon rings to which
hydrogen atoms are attached. The general formula of naphthene is C nH2n. Examples of
cycloalkanes are cyclopentane and cyclohexane.
Aromatics are unsaturated hydrocarbons that have one or more planar benzene rings to which
hydrogen atoms. They have the general formula CnH2n−6. Examples of aromatics are benzene,
toluene, xylenes, ethylbenzene, 1,2-dimethylbenzene, naphthalene, and biphenyl.

Asphaltenes contain heteroatomic compounds and metals in trace amounts as detailed below:
Heteroatomic compounds:
All atoms other than carbon and hydrogen are called heteroatoms and such compounds are
known as heteroatomic compounds. The minor constituents of crude oil are sulfur, nitrogen,
oxygen and metals.
Sulfur compounds in crude oil are typically found as mercaptans such as ethylmercaptan
and cyclic sulfides such as tetrahydrothiophen and benzothiophen.
Nitrogen based compounds in petroleum are classified into two types. The first type is basic
nitrogen molecules that have an extra lone pair of electrons. Basic nitrogen compounds are
pyridine, quinolone, and phenanthridine. The second type of nitrogen compounds is non-basic. In
this type, the lone pair of electrons with the nitrogen is delocalized in the ring structure. Indole and
carbazole are two non-basic nitrogen compounds.
Some crude oils contain trace containing organic compounds such as benzoic acid and
phenol.
Metals:
Metals such as Fe, Ni, Cu, V, Ca, Mg, Hg, As, and Na are generally found in petroleum.
Metals can be in the form of organic or inorganic salts. For example, V can be found in an organic
porphyrin structure and CaCl2, MgCl2, and NaCl suspended or dissolved as entrained water
inorganic salts. Metals in petroleum must be removed or neutralized before processing, as they
cause corrosion and fouling to refinery equipment and poison of catalysts.

2
Refining and different types of petroleum products and their applications
PETROLEUM REFINING PROCESS:
The petroleum refining industry converts crude oil into more than 2500 refined products,
including liquefied petroleum gas, gasoline, kerosene, aviation fuel, diesel fuel, fuel oils,
lubricating oils, and feedstocks for the petrochemical industry. The petroleum refining industry
employs a wide variety of processes, which can be categorized into five processes as follows:
1. Separation processes:
The first phase in petroleum refining operations is the separation of crude oil into its major
constituents using 3 petroleum separation processes: atmospheric distillation, vacuum distillation,
and light ends recovery (gas processing). Crude oil consists of a mixture of hydrocarbon
compounds including paraffinic, naphthenic, and aromatic hydrocarbons with small amounts of
impurities including sulfur, nitrogen, oxygen, and metals. Refinery separation processes separate
these crude oil constituents into common boiling-point fractions.
2. Petroleum conversion processes
The second phase of petroleum refining typically involves conversion processes aimed at
breaking down heavier hydrocarbon molecules into lighter and higher value products. Cracking,
coking, and visbreaking processes are used to break large petroleum molecules into smaller ones.
Polymerization and alkylation processes are used to combine small petroleum molecules into
larger ones. Isomerization and reforming processes are applied to rearrange the structure of
petroleum molecules to produce higher-value molecules of a similar molecular size. The
commonly resulting products are liquefied petroleum gas (LPG), naphtha, and kerosene gasoline
and diesel.
3. Petroleum treating processes
Petroleum treating processes stabilize and upgrade petroleum products by separating them
from less desirable products such as sulfur, nitrogen, and oxygen are removed by processes such
as hydrodesulfurization, hydrotreating, chemical sweetening, and acid gas removal respectively.
Treating processes, employed primarily for the separation of petroleum products, include such
processes as deasphalting and desalting.
4. Feedstock and Product Handling
The refinery feedstock and product handling operations consist of unloading, storage,
blending, and loading activities.

3
5. Auxiliary Facilities:
There are other processes and equipment not directly involved in the refining of crude oil
is used in functions vital to the operation of the refinery. Examples are boilers, waste water
treatment facilities, hydrogen plants, cooling towers, and sulfur recovery units. Products from
auxiliary facilities (clean water, steam, and process heat) are required by most process units
throughout the refinery.

PETROLEUM PRODUCTS & THEIR APPLICATIONS

Petrochemicals as the name suggests are chemical products obtained from petroleum. Its
boiling range is between 30 ⁰C and 200 ⁰C. Petrochemicals are produced by the fractional
distillation of crude oil. Petrochemicals are used in fertilizers, wax, polish, detergents, food
additives, synthetic shoes, dyes, plastic bottles and so on.

The following is the list of the common petroleum products and their applications:

Liquified Petroleum Gas (LPG)

Liquefied Petroleum Gas is a flammable liquid that is a combination of various
hydrocarbons. Propane (C3H8) and butane (C4H10) are the main constituents comprising around
90% of the composition of LPG. These gases are liquefied and supplied in cylinders or piped to
homes for cooking purposes. It is also used for powering electrical appliances and vehicles.
Gasoline
Gasoline, also referred to as Petrol, is the most widely used petroleum product around the
globe. Gasoline is a transparent liquid obtained from the fractional distillation of crude oil. It
consists of hydrocarbons (C5- C10) and is mainly used in internal combustion engines. Gasoline is
used to power vehicles and other electrical appliances.
Naphtha
Naphtha is a light liquid hydrocarbon mixture derived from petroleum refining, typically
obtained during the initial distillation process. It is a versatile feedstock to produce ethylene and
propylene, which are fundamental building blocks for manufacturing plastics, synthetic fibers, and
other materials. Naphtha serves as a solvent and is used for making paints, coatings, adhesives,
beauty products and other such purposes.

4
Paraffin oil
Paraffin oil, also known as kerosene, is a combustible liquid containing hydrocarbons (C 10 -
C16). Paraffin oil is used to power jet engines, for cooking, heating, lighting fuels and toys. The
boiling range for paraffin oil is between 150 ⁰C to 275 ⁰C. Kerosene lamps are extremely popular.
Other applications of Kerosene are as a pesticide, as a solvent, lubricant, and so on.
Kerosene
Kerosene is indeed a vital component of Aviation Turbine Fuel (ATF), commonly known
as jet fuel. The fuel is a combination of various hydrocarbons with boiling range in between 150
⁰C and 275 ⁰C. Kerosene serves as the primary component of jet fuel due to its desirable properties,
including high energy density, low freezing point, and excellent combustion characteristics.
Kerosene is widely used for cooking and heating purposes. It also finds its uses as a solvent for
paints and other chemicals in India.
Diesel oil
Diesel is obtained by the fractional distillation of crude oil with a boiling range of 250 ⁰C
- 350 ⁰C at atmospheric pressure. The quality of diesel fuel is measured in terms of Cetane number.
Diesel is comparatively easier to refine from petroleum than gasoline. Diesel is mainly used as a
vehicle fuel and engines using diesel are considered to be more energy efficient and have better
fuel economy than gasoline. Diesel is also used in gas turbines and external combustion engines.
Fuel oil
Fuel oil is commonly used for lamps, heaters, stoves, engines and lanterns in India. This is
also one of the most common types of petroleum products because it is the energy source for
industries that use boilers and furnaces. Fuel oil also drives juicing machines as well as machinery
used for farming, quarrying, mining and certain types of ships.
Bitumen
Bitumen is commonly known as asphalt. Asphalt is a black and thicker mass of petroleum
that is obtained as a refined product. Asphalt is obtained by fractional distillation of crude oil at
525⁰C. Bitumen is commonly used in the construction of roads and runways at airports. Bitumen
is also used for waterproofing especially to seal roofs. Bitumen paper is also used for coating
pipelines and electrical cables.

5
Fractional Distillation (Principle and process)
Petroleum or crude oil is also known informally as ‘black gold’ and sometimes as ‘liquid
gold’. Fractional distillation is a separation process used in the refining of crude oil to separate its
components into fractions based on their boiling points. The principle behind fractional distillation
is the difference in boiling points of the components of the mixture.
Crude oil is heated to around 600 ⁰C and converted into the vapour form before entering
the bottom of the fractional distillation column. As the vapour rises, it becomes cooler. The
distillation column is filled with trays or plates which collect the liquids as the vapour condenses.
The trays collect the various liquid fractions, which then follow pipework outside the column. The
collected liquid fractions may pass to condensers, which cool them further, and then go to storage
tanks, or to other areas for further chemical processing.

Fractional distillation of the crude oil

After fractional distillation of crude oil, the products are further subjected to other refining
processes such as cracking, reforming, hydrodesulfurization and so on.
6
Cracking (Thermal and catalytic cracking)
Cracking:
Cracking is a process in which long chain hydrocarbon molecules are broken down into
smaller, more useful hydrocarbon molecules. Cracking is used to enhance the octane number of
the product. Cracking can be carried out with or without a catalyst.
C10H22 → C5H12 + C10H12
The main objective of cracking is to convert heavier hydrocarbons into lighter fractions such as
gasoline, diesel, and jet fuel. There are in general three types of cracking.

1. Thermal Cracking:
Thermal cracking relies on the principle of thermal decomposition. Thermal Cracking is
the process of heating long chain hydrocarbons at high temperatures (500-700°C) and under high
applied pressure to break them down into smaller molecules. The cracking reactions occur in the
absence of oxygen to prevent combustion and ensure the desired chemical transformations.
Types of Thermal Cracking:
1. Visbreaking:
Visbreaking is a mild form of thermal cracking used to reduce the viscosity of heavy crude
oils. It involves heating the feedstock at temperatures typically ranging from 420-480°C
for a short time to induce partial cracking. The primary objective of visbreaking is to reduce
the viscosity of the feedstock for easier handling and further processing.
2. Delayed Coking:
Delayed coking is a more severe form of thermal cracking that converts heavy residual oils
into lighter fractions and solid coke. The process involves heating the feedstock to
temperatures around 500-550°C in a furnace, followed by quenching to induce cracking
and coke formation. Delayed coking is employed to upgrade low-value residual oils
into higher-value products such as gasoline, diesel, and petroleum coke.
3. Catalytic Cracking:
Catalytic cracking utilizes a catalyst to facilitate the cracking process at lower
temperatures and moderate pressure, enhancing selectivity and efficiency. The catalyst
provides active sites where the hydrocarbon molecules can adsorb and lead to the formation
of smaller hydrocarbon molecules.

7
 The product distribution in catalytic cracking is influenced by factors such as
temperature, pressure, catalyst activity, and residence time. Shorter residence times and higher
temperatures tend to favor the production of lighter hydrocarbons like gasoline, while longer
residence times and lower temperatures favor the production of heavier products like diesel
and gas oil.
1. Fluid Catalytic Cracking (FCC):
o FCC is the most widely used catalytic cracking process in modern petroleum
refineries.
o It involves the cracking of heavy hydrocarbon feedstocks in a fluidized bed reactor
using a powdered catalyst.
o FCC offers high conversion rates and flexibility in product distribution.
2. Fixed Bed Catalytic Cracking:
o In fixed bed catalytic cracking, the feedstock is passed over a fixed bed of catalyst in
a reactor.
o It is typically used for heavier feedstocks and may require higher temperatures and
longer reaction times compared to FCC.

Reforming Petroleum and non-petroleum fuels - LPG, CNG, LNG, biogas, fuels
derived from biomass.
Reforming is a process used in petroleum refining and other industries to convert
hydrocarbon feedstocks into products with desired properties or compositions. It typically involves
the rearrangement of molecular structures through the breaking and forming of chemical bonds.
Reforming processes are commonly applied to petroleum-based fuels, such as gasoline and diesel,
to improve their octane number or cetane index, respectively. However, reforming can also be
applied to non-petroleum fuels and feedstocks to produce hydrogen, syngas (a mixture of hydrogen
and carbon monoxide), or other valuable chemicals.
1. LPG (Liquefied Petroleum Gas):
o LPG typically consists of propane and butane, which are obtained from natural gas
processing and petroleum refining.

8
 o Reforming processes, such as steam reforming or catalytic reforming, can be applied
to LPG to produce hydrogen, which is used in various industrial processes, fuel cells,
and hydrogenation reactions.
2. CNG (Compressed Natural Gas):
o CNG is mainly composed of methane and is derived from natural gas wells or biogas
production.
o While CNG itself may not undergo traditional reforming processes, methane
reforming can be applied to natural gas feedstocks to produce hydrogen or syngas (a
mixture of hydrogen and carbon monoxide), which can be further processed into fuels
or chemicals.
3. LNG (Liquefied Natural Gas):
o LNG is primarily methane that has been liquefied for transportation and storage
purposes.
o Reforming processes are not typically applied directly to LNG. However, LNG can be
regasified and then subjected to reforming processes for hydrogen or syngas
production.
4. Biogas:
o Biogas is produced from the anaerobic digestion of organic matter, such as agricultural
waste, food waste, or wastewater.
o Biogas reforming can involve steam reforming or dry reforming to produce hydrogen
or syngas, which can be used as a renewable energy source or as a feedstock for various
chemical processes.
5. Fuels Derived from Biomass:
o Biomass-derived fuels, such as bioethanol, biodiesel, or synthetic hydrocarbons, can
undergo reforming processes for various purposes.
o For example, bioethanol can be steam-reformed to produce hydrogen, while biomass-
derived oils can be subject to hydrodeoxygenation to improve their quality and
properties.
In summary, these processes play a crucial role in diversifying the energy landscape and
transitioning towards more sustainable and renewable fuel sources.