Production of Olefins

Group 1
Aditya Gupta - 180107001
Aditya Vikram Singh Chauhan - 180107002
Index
1. What are Olefins?
2. History
3. Importance
4. Cracking
5. Industrial Process
6. Influence of Feedstock
7. Cracking furnace
8. Heat exchanger
9. Novel Developments
10.Metathesis of Olefins
11.Production of Olefins from syngas
12.Conclusion
What are Olefins?
● Olefins - compounds made up of hydrogen and carbon
○ contains a pair of carbon atoms linked by a double bond
○ also called alkenes
● Olefins have a formula of CnH2n .
● Examples -

Ethylene Propylene Butene-2

(C2H4) (C3H6) (C4H8)
History

● 1913: Standard Oil’s scientist patented thermal cracking process

● 1930s: Ethylene was first separated from coke oven gas and the first
commercial plant for the production of ethylene was built
● 1941: Standard Jersey developed the world’s first steam cracker
● 1950s: Ethylene emerged as a large-volume intermediate, replacing
acetylene as prime material for synthesis
● Today Ethylene is primarily produced by thermal cracking of hydrocarbons in
the presence of steam.
Plant capacities are up to 1-1.5 million t/yr ethylene. Other processes are
also available or under development
Importance/ Application

● Petrochemicals are produced in the largest quantity by volume.

● Lower olefins: ethylene and propylene
● Annual global production of ethylene in 2010 was about 120 million tons
○ continuous annual increase of some 4 - 5 %

● Building blocks for a large variety of chemicals and petrochemical products

○ Ethylene and propylene have no end use

● Polymers are the dominating end-use

 Building block for petrochemicals – consumption 2009

Ethylene Propylene

*https://www.researchgate.net
 Global consumption of ethylene and propylene

The Global Consumption of Ethylene and Propylene*

*https://www.grandviewresearch.com
Cracking Reactions
Introduction

● Laid the foundation for petrochemical industry.

● Thermal Cracking - The principle process for the conversion of alkanes to
alkenes.

● Steam Cracking - Hydrocarbon stream is thermally cracked in the presence

of steam
○ Yields a complex product mixture.
 Steam Cracking
● Steam cracking is a petrochemical process in which saturated hydrocarbons are
broken down into smaller unsaturated hydrocarbons.

For ethane the primary

reaction is
dehydrogenation:
C2H6 → H2C=CH2 + H2

Flow diagram of Cracking*

*https://www.britannica.com
 Thermodynamics

C2H6 ↔C2H4 + H2 ΔrH298 = 137.1 kJ/mol

C3H8 ↔ C3H6 + H2 ΔrH298 = 124.4 kJ/mol

C4H10 ↔ C4H8 + H2 ΔrH298 = 117.7 kJ/mol

● The reaction temperature should be high for Equilibrium conversion in the dehydrogenation of light
alkanes at 1 bar as a function of temperature*
sufficient conversion.
● The smaller the alkane the higher the temperature has to be for a given
conversion.

*Chemical Process Technology, by JACOB A. MOULIJN

 Mechanism

Mechanism of ethane dehydrogenation/cracking*

The reaction is initiated by cleavage of the C–C bond in an ethane molecule.

Propagation proceeds by reaction of a methyl radical with an ethane molecule.
Termination occurs as a result of the reaction between two radicals to form an unsaturated molecule.
*Chemical Process Technology, by JACOB A. MOULIJN
 Example of Heavier Alkanes

Example of reactions occurring during thermal cracking of heavier alkanes*

*Chemical Process Technology, by JACOB A. MOULIJN

 Kinetics

● The rate of reaction of

alkanes obeys first order
kinetics.
● The reactivity increases
with chain length.
● Ethane clearly shows the
lowest reactivity.

Reaction rate coefficients of various alkanes*

*Chemical Process Technology, by JACOB A. MOULIJN

Requirements of Steam Cracking

● considerable heat input at a high temperature level

● limitation of hydrocarbon partial pressure

● very short residence times (<1 s)

● rapid quench of the reaction product to preserve the composition.

Industrial Process

In industry, these requirements are met in the following way-

● A mixture of hydrocarbons and steam is passed through tubes inside

furnaces heated by combustion.
● The hydrocarbons undergo cracking and the products are rapidly quenched
and thus preserve the composition.
● The residence time in the tubes is very short (<1 s).
● The temperature is chosen to be as high as possible.
Influence of Feedstock on Steam Cracker Operation and
Products

● It is crucial to choose the reaction conditions

● The amount of ethene produced should be as high as possible.
● The product distribution in ethane cracking is determined solely by the
process parameters:
○ Temperature
○ Pressure
○ Residence time
○ Steam-to-ethane ratio
Influence of Feedstock on Steam Cracker Operation and
Products

Feedstock Total of ethylene Yield of ethylene, %

production, %

Ethane 35.6 45-50

Propane 11.2 30-32

n-Butane 3.0 30-31

Naphtha 47.0 23-33

Gas oil 3.2 19-22

Relative yield of ethylene and propylene from cracking
various hydrocarbons
Hydrocarbon Propylene/ ethylene wt.
ratio

Ethane 0.04

Propane 0.33

n-Butane 0.58

n-pentane 0.81

Naphtha 0.57

Gas oil 0.62

Crude oil 0.60

Uses of Cracking Furnace

● Production of ethylene and propylene by endothermic cracking reaction

● Preheating of feed and dilution steam by utilization of waste heat

● Cooling of the cracked gas to freeze chemical reactions

Cracking Furnace

● Radiant section: thermal cracking reactions (800 – 850 °C)

● Convection section: heat recovery from hot flue gas
○ Feed preheating
○ Boiler feed water preheating
○ Process steam superheating

● Linear quench exchanger

○ Freezing cracking reactions in order to avoid product losses by secondary reactions
(400 - 600 °C)
 Two Cell Cracking Furnace

● Fireboxes are connected to one

convection section.
● The convection section contains
various zones used for preheating
the steam and the feed.
● Reactions take place in the radiant
section

Typical two-cell cracking furnace configuration*

*Chemical Process Technology, by JACOB A. MOULIJN

Coke Formation

Coke formation during the cracking process causes undesired phenomena:

● Reduced heat transfer rates

● Increased pressure drop
● Lowered yields
● Reduced selectivity towards alkenes

Reducing Coke Formation

● Pretreatment of cracking tubes

● Passivation of the tubes
● Catalytic coating
Novel Developments
Selective Dehydrogenation of Light Alkanes

● Process of production of light olefins by selective dehydrogenation of the

corresponding alkanes.
● Alkane dehydrogenation is highly endothermic , high temperatures are
required .
● Cracking and coke formation become appreciable at high temperatures.
● Extensive deposition of coke on the catalyst takes place, so regeneration
schemes are necessary.
 UOP Oleflex Process

Adiabatic moving bed reactors*

The UOP Oleflex process uses radial flow, moving bed reactors in series with interstage heaters. The
process is operated in the same way as the UOP continuous-regenerative reforming process.

*Chemical Process Technology, by JACOB A. MOULIJN

 Catofin Process

Parallel adiabatic fixed bed reactors*

Reactors are alternately on stream for reaction and off stream for regeneration.
During regeneration by burning the coke off the catalyst, the bed is heated, while this heat is consumed
in the endothermic dehydrogenation reaction during the on-stream period.
*Chemical Process Technology, by JACOB A. MOULIJN
 STAR Process

Tubular fixed bed reactors in a furnace*

This process uses multiple tubular reactors in a firebox, similar to the steam reformer used for the
production of synthesis gas.

*Chemical Process Technology, by JACOB A. MOULIJN

 FBD

fluidized bed reactor and regenerator*

This process involves continuous catalyst circulation between a fluidized bed reactor and regenerator.

*Chemical Process Technology, by JACOB A. MOULIJN

 Metathesis of Olefins

● The conversion of olefins to produce olefins of different size.

● Double bonds are broken with the simultaneous formation of new ones.
● The reaction takes place via carbene complexes resulting in a slightly more
complex reaction network.

CH2 = CH2 + CH3CH = CHCH3 ↔ 2CH3CH = CH2 ΔrH298 ≈ 0

Metathesis of alkenes*
*Chemical Process Technology, by JACOB A. MOULIJN
 Equilibrium composition

● Metathesis is an equilibrium
reaction which is
thermoneutral.

Equilibrium composition of an ethene/propene/2-butene mixture*

*Chemical Process Technology, by JACOB A. MOULIJN

Production of Olefins from Syngas
 Fischer–Tropsch Process

The Fischer–Tropsch process is a collection of chemical reactions that converts

a mixture of carbon monoxide and hydrogen into liquid hydrocarbons.

General Reaction:

nCO + 2n H2 → CnH2n + nH2O ΔrH298 << 0

Ethene:

2CO + 4H2 → C2H4 + 2H2O ΔrH298 = −211 kJ/mol

*Chemical Process Technology, by JACOB A. MOULIJN

 Methanol-to-Olefins Process
● The methanol-to-olefins
process involves dehydration
of methanol to form dimethyl
ether (DME), which then further
reacts to form olefins.
● Coke formation plays an
important role in the MTO
process.
● The reaction is highly Reactions in the conversion of methanol to light alkenes and gasoline
components*
exothermic, which requires
good temperature control

*Chemical Process Technology, by JACOB A. MOULIJN

Dehydration of Bioethanol
○ CH3CH2OH ↔ CH2 = CH2 + H2O ΔrH298 = 45.3 kJ/mol
● Like in the MTO process, ethanol can be converted into its corresponding ether, which is
then converted into ethene:
○ 2CH3CH2OH ↔ CH3CH2OCH2CH3 + H2O ΔrH298 = −24.4 kJ/mol

○ CH3CH2OCH2CH3 → 2CH2 = CH2 + H2O ΔrH298 = 115 kJ/mol

● The most important by-products are acetaldehyde and hydrogen, which are formed by the
following reaction:
○ CH3CH2OH ↔ CH3CHO + H2 ΔrH298 = 68.5 kJ/mol
● Other by-products that are formed in small quantities, include acetic acid, methanol, higher
hydrocarbons, carbon monoxide, and carbon dioxide.
Direct Conversion of Methane

The direct conversion of methane into ethane and ethene can take place by
applying ‘oxidative coupling’

2CH4 + 1/2 O2 → C2H6 + H2O ΔrH298 = −177 kJ/mol

C2H6 + 1/2 O2 → C2H4 + H2O ΔrH298 = −105 kJ/mol

Large amounts of carbon monoxide and carbon dioxide are formed as by-
products: CH4,CH3CH3, etc. + O2 → CO,CO2 ΔrH298 << 0
 Olefin production by processes, 2008

Olefin production percentage by processes*

*https://www.researchgate.net
Conclusion
Present and future processes to ethylene and propylene production

Process Status

Steam cracking Dominating technology

Refinery processes Minor importance for ethylene, important

for propylene only

Methanol to Ethylene and Propylene Technology is ready but not yet

commercialized

Methanol selectively to Propylene Commercialisation phase

Olefins from Syngas via Fischer Tropsch Minor importance

Other Processes Minor Importance

Thank You