Chapter one

Introduction and literature review

 Introduction

1.1 Historical Background:

According to some recent forecasts, the petrochemical market tends to

rise in the next years and, in middle term, will be responsible by a major
part of the crude oil consumption over passing the transportation fuels
this fact have been made the refiners to looking for closer integration
with petrochemical assets through the maximization of petrochemical
intermediates in their refining hardware as a strategy to ensure better
refining margins and higher value addition to the crude oil. Figure 1
present an overview of the trend of growing to the petrochemical market
in short term.

of the trend of growing to the petrochemical market in

short term (2017 – 2022)
1.2 Naphtha hydrocarbons structure:

Highly flammable liquid hydrocarbon mixtures used chiefly as solvents

and diluents and as raw materials to gasoline.
Naphtha contains varying amounts of paraffins, olefins, naphthene
constituents, and aromatics and olefins in different proportions, in
addition to potential isomers of paraffin that exist in naphtha boiling
range. As a result, naphtha is divided predominantly into two main
types: (1) aliphatic naphtha and (2) aromatic (naphtha). The two types
differ in two ways: first, in the kind of hydrocarbons making up the
solvent, and second, in the methods used for their manufacture.
Aliphatic solvents are composed of paraffinic hydrocarbons and
cycloparaffins (naphthenes), and may be obtained directly from crude
petroleum by distillation. The second type of naphtha contains
aromatics, usually alkyl-substituted benzene, and is very rarely, if at all,
obtained from petroleum as straight-run materials.
It consists of a complex mixture of hydrocarbon molecules generally
having between 5 and 12 carbon atoms. It typically constitutes 15–30%
of crude oil, by weight. Light naphtha is the fraction boiling between 30
°C and 90 °C and consists of molecules with 5–6 carbon atoms. Heavy
naphtha boils between 90 °C and 200 °C and consists of molecules with
6–12 carbons.
Naphtha is used primarily as feedstock for producing high octane
gasoline (via the catalytic reforming process or steam cracking).
1.3 Applications of benzene:

Benzene is not only the most important aromatic raw material in terms
of Quantity, but it is also the most versatile from the viewpoint of its
uses. The major industrial products from benzene are alkylated
derivatives such as Ethylbenzene and cumene, which are used as basic
materials for the production of Styrene and phenol, and long-chain
alkylbenzenes, which are used as feedstocks in The manufacture of
surfactants. Other significant processes for the conversion of benzene
include hydrogena-Tion to produce cyclohexane, oxidation to
manufacture maleic anhydride, nitra-Tion to obtain nitrobenzene as an
intermediate in the production of aniline, and Halogenation to obtain
chlorobenzene derivatives.

1.4 Physical and chemical properties of benzene:

1.4.1 physical properties

Benzene is colorless liquid with boiling point 80.1 ° C and melting point
5.5 ° C . Insoluble in water ,It has a density of 0.87g cm-3. It is lighter
than water. Miscible with alcohol , ether and chloroform . Itself is a
good solvent , vapours highly toxic , burns with luminous sooty flame .
1.4.2 chemical properties

 Nitration of Benzene Benzene reacts with nitric acid in the

presence of sulphuric acid for the formation of nitroBenzene. 

 Sulfonation of BenzeneIt is a process in which Benzene is heated

with fuming sulphuric acid, i.e. H2SO4 + SO3 for the formation of
Benzene sulphuric acid. It is a reversible reaction

 Halogenation of Benzenen the presence of Lewis acids (FeCl2,

FeBr2), Benzene reacts with the halogens for forming the aryl
halides
  Addition Reaction Adding chlorine to Benzene in the presence of
UV rays leads to the formation of Benzene hexachloride, also
known as gammaxene.
C6H6 + Cl2 → C6H5Cl + HCl

 Combustion of Benzene
During the combustion of Benzene, it burns with a sooty flame and
evolves
C6H6+O2→CO2+H2O

1.5 Health and environment impacts of Benzene:

Benzene exposure has serious health effects. Breathing high levels of

benzene can result in death, while low levels can cause drowsiness,
dizziness, rapid heart rate, headaches, tremors, confusion, and
unconsciousness. Eating or drinking foods containing high levels of
benzene can cause vomiting, irritation of the stomach, dizziness,
sleepiness, convulsions, rapid heart rate, and death.
The US Department of Health and Human Services (DHHS) classifies
benzene as a human carcinogen. Long-term exposure to high levels of
benzene in the air can cause leukemia, a potentially fatal cancer of the
blood-forming organs. In particular, Acute Myeloid Leukemia (AML)
may be caused by benzene.
The major effect of benzene from chronic (long-term) exposure is to the
blood. Benzene damages the bone marrow and can cause a decrease in
red blood cells, leading to anaemia. It can also cause excessive bleeding
and depress the immune system, increasing the chance of infection.
In the atmosphere, benzene can react with other chemicals to create
smog. This could break down naturally but it might also attach to rain
and snow and be carried to the ground to contaminate water and soil.
When aquatic life, like fish, shellfish and other creatures in our rivers,
lakes and oceans, is exposed to benzene, it makes them sick and shorten
their lives.
When plants are exposed to benzene in the soil their growth can be
slowed and they may even die
 Literature review

2.1 Background:
Benzene has been the subject of many studies by many famous scientists
ranging from Michael Faraday to Linus Pauling. In 1825 Faraday
reported its isolation from oil gas and gave it the name bicarburet of
hydrogen. In 1833, Eilhard Mitscherlich produced it via the distillation
of benzoic acid (from gum benzoin) and lime. Mitscherlich gave the
compound the name benzin. In 1845, Charles Mansfield, working under
August Wilhelm von Hofmann, isolated benzene from coal tar. Four
years later, Mansfield began the first industrial-scale production of
benzene, based on the coal-tar method
Up until World War II, most benzene was produced as a byproduct of
coke production in the steel industry. However, in the 1950s, increased
demand for benzene, especially from the growing plastics industry,
necessitated the production of benzene from petroleum. Today, most
benzene comes from the petrochemical industry, with only a small
fraction being produced from coal.

2.2 chemical processes contribute equally to industrial

benzene production:
Benzene can be made by various processes. However, most benzene
production is based on the recovery of aromatics derived from the The
catalytic reforming of naphtha in a petroleum refinery. On a global
basis, catalytic reforming accounts for some 55% of benzene production
including associated toluene conversion. The other method for
producing Benzene is Steam cracking it accounts for nearly 40% of
benzene production. The use of these sources, particularly crude oil, has
been decreasing due to the economic and environmental risks they pose.
Instead, the industry is turning to a naphtha feed.
Her in this project we are focused in production of benzene from
naphtha by steam cracking
2.2.1 Catalytic reforming:
Catalytic reforming is a chemical process used to convert petroleum
refinery naphtha as distilled from crude oil (typically having low octane
ratings) into high-octane liquid products called reformates, which are
premium blending stocks for high-octane gasoline. The process converts
low-octane linear hydrocarbons (paraffins) into branched alkanes
(isoparaffins) and cyclic naphthenes, which are then partially
dehydrogenated to produce high-octane aromatic hydrocarbons.
2.2.2 Steam cracking process:

Another method is steam cracking – where gaseous or liquid

hydrocarbons like Naphtha are diluted with steam and briefly heated in a
furnace without oxygen. Reaction temperatures can reach as high as 850
°C, with the resulting mixture depending heavily on the temperature
used.