PETROCHEMICALS

You are aware, petroleum is a complex mixture of hydrocarbons formed by the

decomposition of fossil remains. It exists as a liquid (crude oil), gas (natural gas) or as
solids (oil shales) and is found deep underground or below seabed.
You have also studied that petroleum is refined to several useful fractions, which are
used as fuel (LPG, petrol, diesel, etc.) or lubricants. About 10% of the petroleum is
used to prepare a range of chemicals called petrochemicals, we may define,
petrochemicals as a group of chemicals produced directly or indirectly from the
hydrocarbons of petroleum or
natural gas. Some gaseous hydrocarbons are also obtained as a by product during
petroleum refining. These hydrocarbons may contain one to five carbon atoms, for
example, methane, ethane, propane, butane, iso-butane, pentane, etc. Methane (CH4)
is also a major hydrocarbon component of natural gas, which occurs in association
with petroleum. At one time these gaseous hydrocarbons were of almost no use and
the only way to dispose them was to burn them. With passage of time these gaseous
hydrocarbons have found important use as starting material to produce a large variety
of petrochemicals.
Today, the demand of petrochemicals and the materials derived from petrochemicals
is so great that we need to deliberately convert higher hydrocarbons to smaller
gaseous hydrocarbons by the process of cracking.
The list of petrochemicals is endless. Some important petrochemicals are methyl
alcohol, ethyl alcohol, acetaldehyde, acetic acid, acetic anhydride, acetone, benzene,
toluene, xylenes, phenol, vinyl chloride, etc. some of these can be used directly or as
raw materials for the manufacture of other useful products. These are used to
manufacture a vast variety of useful materials like solvents, adhesives, antifreezes,
synthetic rubbers, synthetic fibers, nylon, polyester, plastics, synthetic detergents,
rocket fuels, etc. Since every area of human activity makes use of petrochemicals or
the materials made from petrochemicals, our life without petrochemicals would be
very different and less CONFORTABLE
3
CLASSIFICATION OF PETRICHEMICALSetrochemicals
The nature of petrochemical industry is very complex. The journey from petroleum to
useful end products is long and there are many steps in the process. Let us try to
understand
feed-stock, primary and intermediate petrochemicals and the end products in the
context
of petrochemicals.
FEED-STOCK:
The starting material used for the production of petrochemicals is called feed stock.
There
are two common feed stocks for the manufacture of petrochemicals; these are :
1. Natural gas
2. Naphtha and reformed naphtha
You would recall that natural gas occurs in nature in association with petroleum. The
major hydrocarbon component of natural gas is methane. Naphtha is a fraction
obtained
during refining of petroleum.Some countries or industries prefer to use natural gas
while some other use naphtha as a
starting material (feed stock) for the production of petrochemicals. The choice for the
use of natural gas or naphtha as feed stock by a particular country or industry depends
upon the availability of a particular feed stock or the availability of technology for the
manufacture of petrochemicals.

PRIMARY PETROCHEMICALS
Primary petrochemicals are the molecules obtained from the feed stock and are used
to
manufacture petrochemical intermediates. Since the feedstock consists of natural gas,
naphtha and reformed naphtha, these give different primary petrochemicals. The
primary
petrochemical obtained from these are compiled in Table 32.1

.
SECONDARY PETROCHEMICALS

The petrochemicals obtained from primary petrochemicals by chemical reaction are

called(secondary) intermediate petrochemicals. Petrochemicals are also refered to as
first generation petrochemicals and second generation petrochemicals, First
generation petrochemicals are converted to second generation petrochemicals. These
intermediate petrochemicals may be put to some use or these may be further
processed to get derivatives of petrochemicals by a chemical reaction or a series of
reactions to get products for other end uses.

32.2.3 Down Stream Petrochemicals

The petrochemicals obtained from a given feedstock by a series of reactions are called
down stream petrochemicals. Down stream means that a particular petrochemical
comes at a later stage in the sequence of chemicals produced. For example in the
following reaction.
CH4  CH3Cl  CH3OH
Methyl alcohol is referred to as a down stream petrochemical. It is not possible to list
here all the petrochemicals and the chemical processes used for their manufacture.
Uses of the petrochemicals are very diverse and it is impossible to give a complete list.
Therefore, we are giving methods of manufacture of some of the petrochemicals and
their derivatives along with their uses. We will discuss in detail the petrochemicals
obtained from methane and ethene as two typical examples. While for some other
starting materials we will give, only the names of the petrochemicals which can be
obtained from them You can learn more details in higher classes or in more advanced
books. Here you will have some idea about the vastness and importance of the
Petrochemicals
32.2.4 Petrochemicals from Methane
Methane is the major hydrocarbon component of natural gas. CNG is the compressed
natural gas and LNG is the liquified natural gas. Moreover, methane is also obtained
in
large quantities as a by product of petroleum refining.
The major petrochemicals produced from methane are:
1. Chlorinated products
2. Unsaturated hydrocarbons
3. Carbon black
4. Hydrogen
5. Methyl alcohol
1. Chlorinated products of methane
Methane is chlorinated to get methyl chloride (CH3CI), methylene chloride (CH2CI2),
chloroform (CHCI3) and carbon tetrachloride (CCI4). Most of the chlorinated products
of methane are used as a solvent.

2. Unsaturated hydrocarbons
Methane is cracked (by pyrolysis) with the help of suitable catalysts to get ethylene,
propylene and acetylene. These are used to get other products, which will be
discussed

later.
3. Carbon black
Methane is converted into carbon black (a form of carbon) by pyrolysis (cracking)
and
Sulfur removal from crude oil and hydrocarbons
The poor quality of crude oil currently can obviously result in the high sulfur contents
of oil products, which can lead to corrosion, catalyst poisoning, environmental
pollution and other negative consequences. The treatment of high-sulfur crude oil is
becoming the focus of research in China’s oil refining industry. The conventional
equipment cannot deal with the high-sulfur crude oil during petroleum refining
processes.
The increasing sulfur content of crude oil also results in an increase in sulfur content
in automotive gasoline, diesel fuel, and jet fuel. To meet the needs for producing
clean fuels, decreasing the sulfur content of crude oil becomes an urgent task.
Studying new desulfurization technology and raising the efficiency of desulfurization
processes are the keys to bringing more profits to the oil refining companies.

Caustic washing method for oil desulfurization

Caustic washing method is mainly aimed at removing the sulfides from the crude oil
by using the caustic solution. At present, this method is widely used in the oil industry.
The advantage of this method is that the process is simple and the cost is lower. But
this method contains many defects such as the poor quality of oil products and lower
efficiency of desulfurization. However, this method can’t remove all sulfur
compounds from the crude oil, especially the organic sulfides. At the same time, it
brings too much sulfide-containing wastewater, which greatly pollutes the
environment. So, it is urgent to improve this method or find a better way to reduce the
sulfur contents in petroleum products.

Dry gas desulfurization method

According to the report, the first equipment in China for treating heavy crude oil
through dry gas desulfurization method has been used in the No.3 joint oil gathering
station at Tahe Oilfield of the Northwest Oilfield Branch Company. The cost of this
equipment is about 500 million RMB, and it is the first time in China to use this dry
gas treatment method at the crude oil desulfurization system in reality.

Hydrodesulfurization (HDS)

Hydrodesulfurization is one of the catalytic desulfurization processes, which aims at

turning organic sulfur compounds into H2S using H2 as the reactant in the presence of
metal catalysts operating at high temperature and pressure. The resultant hydrogen
sulfide is then removed from the system. This method is widely used in oil industry in
China since 1955. However, the HDS process features a complicated procedure, high
production cost and high materials consumption. With an increasing ratio of heavy
crude oil supply to the oil refinery, the sulfur content in crude slate is growing, which
leads to a shortened catalyst life at the refinery. Furthermore, the HDS process needs
more H2, so the production cost will increase a lot.

Biodesulfurization (BDS)

BDS is a new bio-catalytic desulfurization method, which has been applied since the
1980s. According to the principle of enzyme catalysis for implementing the specific
reaction for C—S bonds cleavage performed by micro biological flora, sulfides in
crude oil can be turned into elemental sulfur that can be removed. In the process of
desulfurization, the sulfur containing pollutants are transformed into sulfides and H2S
by biological reduction, and the elemental sulfur can be removed via the process of
biological oxidation.

Merox Sweetening Process

Merox sweetening processes are reserved for heavier hydrocarbons such as kerosene,
aviation fuels, and diesel. These fuels contain longer-chain mercaptans which are not
soluble in caustic. They require the conversion of mercaptans to disulfides in a single
fixed-bed reactor in the presences of oxygen, caustic, and Merox catalyst.
All of the fundamental chemical reactions in the sweetening Process remain the same
as in the prior extraction process. Similar to the previously described extraction
process; the feedstock for a sweetening process must be free of H2S.
A caustic pre-wash is used for sulfur removal. After prewash, both air and caustic are
injected into the feedstock directly ahead of the fixed bed reactor. As the mixture
enters the reactor it is exposed to activated charcoal containing the Merox catalyst.
The charcoal serves to extend catalyst life by absorbing phenols, naphthenic acids and
other contaminants which may harm the catalyst.
The Feedstock mixture with entrained caustic and air trickles through the fixed bed
where exposure to the catalyst directly converts the mercaptans to disulfides. It should
be noted that these disulfides are soluble in the hydrocarbon fuel but not soluble in
caustic. They remain with the fuel throughout the sweetening process and will be
removed in downstream processing if deemed necessary.

EXERCISE(answer these questions in your books).Submission of

books will be on Wednesday

1. Define feedstock, primary petrochemical and secondary petrochemical

2. Describe the production of ethlyn oxide
3. Explain the extraction of hydrogen, sulfer and carbon black
4. List uses of hydrogen. Sulpher and carbon black
5. Explain the uses of methanol
6. Define paraffin
7. Explain isolation of butane
8. Explain isolation of benzene
9. Define and discuss the importance of
I. synthetic petroleum based polymers
II. Thermosetting plastics
III. Synthetic rubbers
IV. Syntheic fibres