SEMESTER OCT. 2021-FEB.

2022: CHE 329

PETROCHEMICAL MANUFACTURING
&
APPLICATION
CHAPTER 2
FUELS AND DERIVATIVES STEAM CRACKING :
PRODUCTION OF LOWER ALKENES
(1/3Weeks)

MOHAMAD ZARQANI BIN YEOP

 LESSON OUTCOMES

Student 1
Explain the cracking reaction for lower
alkenes.

should be Describe the industrial process and

2
able to: equipment for lower alkenes.

Explain the product processing for

3 lower alkenes
 CONTENTS
2.0 Introduction

2.1 Cracking reaction

2.2 Industrial process and equipment.

2.3 Product processing

 CONTENTS
2.0 Introduction
2.1 Cracking reaction

2.2 Industrial process and equipment

2.3 Product processing

 INTRODUCTION

• The name steam cracking is slightly illogical: cracking of steam does not occur,
but steam primarily functions as a diluent and heat carrier, allowing higher
conversion.
• A more accurate description of the process might be “pyrolysis”, which stems
from Greek and means bond breaking by heat.
• The steam cracking process mainly produces ethene, which is a very important
base chemical.
• Valuable coproducts such as propene, butadienes, and pyrolysis gasoline
(pygas), are also produced.
• Feedstocks for steam cracking range from light saturated hydrocarbons, such
as ethane and propane, to naphtha and light and heavy gas oils.
INTRODUCTION
CRACKING PROCESS
 INTRODUCTION
The principal process used to convert the relatively unreactive alkanes into
much more reactive alkenes is thermal cracking, often referred to as “steam
cracking”.

In North America and the Middle East ethane/propane (from natural gas) is
the primary feedstock for the production of ethene.

In contrast, in Europe and Japan naphtha (from oil) is the major feedstock,
which explains why steam cracking is frequently referred to as
naphtha cracking.
INTRODUCTION
INTRODUCTION
INTRODUCTION
INTRODUCTION
 CONTENTS
2.0 Introduction

2.1 Cracking reaction

2.2 Industrial process and equipment

2.3 Product processing

 CRACKING REACTION

• Steam cracking yields a large variety of products,

ranging from hydrogen to fuel oil

• The product distribution depends on the feedstock

and on the processing conditions.
 CRACKING REACTION
• These conditions are determined by both :
1. Thermodynamic
2. Kinetic factors.

• This is achieved by using high pressures and

temperatures without a catalyst, or lower temperatures
and pressures in the presence of a catalyst
(eg. zeolites)
 CRACKING REACTION
THERMODYNAMIC
• In general, light alkenes, especially ethene, propene,
and butadiene, are the desired products of steam cr
acking.

• Treatment of light alkanes by steam cracking results

in dehydrogenation of the alkanes to form the corres
ponding alkenes and hydrogen.
 CRACKING REACTION
THERMODYNAMIC
• Figure below shows the equilibrium conversions for the dehydrogenation
reactions of the light alkanes represented by reactions 4.1, 4.2, and 4.3:
 CRACKING REACTION
KINETICS
• The rate of reaction of alkanes obeys first order
kinetics.
• The reactivity increases with chain length.
• The first order kinetics implies that the rate of reaction
increases with increasing partial pressure of the
reactants.
 CRACKING REACTION
KINETICS
• However, high hydrocarbon partial pressures also result in
unfavorable secondary reactions, such as condensation reactions
and the formation of coke.
• Hence, the partial pressure of the hydrocarbons must be kept
low. For the same reason, conversions should not be too high.
• It appears that a given conversion corresponds to an infinite
number of combinations of residence time and temperature
(through the rate coefficient).
 CRACKING REACTION
KINETICS
 CRACKING REACTION
MECHANISM
 CRACKING REACTION
MECHANISM
• Cracking occurs by free radical reactions.
• The reaction is initiated by cleavage of the C–C bond in an ethane molecule,
resulting in the formation of two methyl radicals.
 CRACKING REACTION
MECHANISM
• Propagation proceeds by reaction of a methyl radical with an ethane
molecule, resulting in the production of methane and an ethyl radical.
• The ethyl radical subsequently decomposes into ethene and a hydrogen
radical, which then attacks another ethane molecule, and so on.
 CRACKING REACTION
MECHANISM
• Termination occurs as a result of the reaction between two radicals to form
either a saturated molecule or both a saturated and an unsaturated molecule.
 CRACKING REACTION
MECHANISM
• Small quantities of heavier hydrocarbons can also be formed as a result of
the reaction of two radicals.
• Similar, although more complex, networks apply to thermal cracking of
higher alkanes.
Thank you
ANY QUSTION?????