Week 2:

Hydrocarbon Intermediates
By
Ir. Dr. Zaki Yamani Bin Zakaria
School of Chemical & Energy Engineering,
Faculty of Engineering
University Teknologi Malaysia

1
Recall the top 2 raw materials?

2
 Introduction
• Natural gas and crude oils are the main sources for
hydrocarbon intermediates or secondary raw materials for the
production of petrochemicals.

• This Topic covers the properties of the different hydrocarbon

intermediates. Can you name 4 main HC intermediates?

1. Paraffins
2. Olefins,
3. Diolefins,
4. Aromatics.

3
 A) Paraffin Hydrocarbon
Paraffinic HC used for producing petrochemicals range from the simplest HC, CH4,
to heavier HC gases & liquid mixtures present in crude oil fractions & residues.

Is Paraffin HC active? Relatively inactive compared to olefins, diolefins, & aromatics

4
 Methane (CH4)
• Methane is the main component of natural gas.
• It is also a by-product in all gas streams from
processing crude oils.
• It is a colorless, odorless gas that is lighter than
air. Any other properties you can think?
• As a chemical compound, methane is not very reactive. It does not react with acids
or bases under normal conditions. It reacts, however, with reagents such as O2 and
Cl2 under specific conditions (Partial oxidation with O2 to CO at high temperature
over catalyst).
• Methane is mainly used as a clean fuel gas (~one
million BTU =burning 1,000 ft3 of dry natural gas
(methane).
• Methane may be liquefied under very high
pressures and low temperatures.

5
Ethane (CH3-CH3)

6
Propane (CH3CH2CH3)

7
Butanes (C4H10)

8
 B) Olefinic Hydrocarbons
• The most important olefins used for the production of petrochemicals are
ethylene, propylene, butylenes & isoprene.
• These olefins are usually co-produced with ethylene by steam cracking ethane,
LPG, liquid petroleum fractions, and residues.
• Olefins are characterized by their higher reactivities compared to paraffinic
hydrocarbons.
• They can easily react with inexpensive reagents such as water, oxygen,
hydrochloric acid, and chlorine to form valuable chemicals.
• Olefins can even add to themselves to produce important polymers such as
polyethylene and polypropylene.
• Ethylene is the most important olefin for producing petrochemicals and
therefore, many sources have been sought for its production

9
Ethylene (CH2=CH2)

10
 Propylene (CH3CH=CH2)
• From steam cracking of hydrocarbon

11
 Butylenes (C4H8)
• By product of refinery cracking process and steam cracking
unit for ethylene production

• Can you think of four butylene isomers, by yourself?

12
13
• The Two Process for separating n-butenes and
isobutylene

14
 C) Diolefins @ Dines
• Dines are aliphatic compounds having two double bonds.
• Name 3 types of Dienes?
Cumulated Dienes, Conjugated Dienes & Unconjugated Dienes

Example of Dienes?

15
 Butadiene (CH2=CH-CH=CH2)
• Butadiene is by far the most important monomer for synthetic
rubber production.
• Is obtained mainly as a coproduct with other light olefins from
steam cracking for ethylene production.
Can you name other dienes?

16
 D) Aromatic
• Benzene, toluene, xylenes (BTX), and ethylbenzene are the
aromatic hydrocarbons with a widespread use as petrochemicals.

• They are important precursors for many commercial chemicals

and polymers such as phenol, trinitrotoluene (TNT), nylons, and
plastics.

• Aromatic hydrocarbons are generally nonpolar. They are not

soluble in water, but they dissolve in organic solvents such as
hexane, diethyl ether, and carbon tetrachloride

17
 Extraction of Aromatics
• BTX and ethylbenzene are obtained mainly from the catalytic
reforming of heavy naphtha.
• The product reformate is rich in C6, C7, and C8 aromatics,
which could be extracted by a suitable solvent such as
sulfolane or ethylene glycol.
• Example of the process of producing aromatic
– The Tetra extraction by Union Carbide
– The Mobil xylene Isomerization Process

18
The Union Carbide aromatics extraction process using
tetraethylene glycol.

19
 C8 aromatic
Hard to be separated why??

20
Flow diagram of the Mobil xylene isomerization process

21
 Benzene
• Is the simplest aromatic and most widely used.
• Currently is mainly obtained from catalytic reforming

Delocalize
electron π

• Is the the precursor for many commercial chemicals

and polymers such as phenol, styrene for
polystyrenics, and caprolactom for nylon.
22
 Example: Substitution of Benzene
Acid nitric
• Substitution at normal
condition

Nitrobenzene

Cyclohexane

React with H2 under

pressure in presence of
catalyst

23
• Ethylbenzenes-is obtained by alkylation (the transfer of an alkyl group
from one molecule to another) of benzene with ethylene
C6H6 + C2H4 → C6H5CH2CH3

Methylbenzene (Toulene and Xylenes)

– occurs in small quantities of naphta and higher boiling fraction of
petroleum
– Primary source is produced from catalytic reforming unit
 Toulene, generally is converted to benzene.
 para-Xylene is mainly used to produce terephthalic acid for polyesters.
 o-Xylene is mainly used to produce phthalic anhydride for plasticizers

24
Liquid Petroleum Fraction (LPF) and
Residues
• LPF are
– light naphtha
– Heavy naphtha
– Kerosine
– Gas oil
– Residue (bottom
product)

25
26
 Naptha
• Full range naphtha is defined as the fraction of hydrocarbons
in petroleum boiling between 30°C and 200°C[1]

• It consists of a complex mixture of hydrocarbon molecules

generally (C5 to C12)

• It typically constitutes 15–30% of crude oil, by weight.

• Light naphtha is the fraction boiling between 30°C and 90°C

and consists (C5–C6)

• Heavy naphtha boils between 90°C and 200°C and consists

(C6–C12)
27
• Naphtha is used primarily as feedstock for producing high
octane gasoline (via the catalytic reforming process)
• It is also used in the petrochemical industry for producing
olefins in steam crackers and in the chemical industry for
solvent (cleaning) applications

28
 Gasoline/petrol
• Let’s discuss…

29
 Kerosene
• A distillate fraction heavier than naptha
• Cointaining paraffin, cycloparaffins, and
aromatics
• Used to produce jet fuel (adjust its burning
quality and freezing point)

30
 Gas Oil
• A major use of gas oil is a fuel for diesel
engines
• As feedstock to cracking and hydrocracking
unit
• Gas from (Cracking) are source for light olefin
and LPG

31
 Residue Fuel Oil
• Bottom product from petroluem fractional
• Content heavier molecules and metal

• For further cracking,

32