University of Pannonia

Bio-, Environmental and Chemical Engineering Research and

Development Centre
MOL Department of Hydrocarbon and Coal Processing

Petrochemistry
(VEMKOLM255P)

Norbert Miskolczi, PhD

Associate professor
Head of MOL Department of Hydrocarbon and Coal Processing

University of Pannonia
Veszprém, Hungary
2021/2022
Fall semester
 Lecture 2
Olefin production
Steam cracking

2
Olefins

Others
Most important 9%
petrochemical flows Ethylene-oxide
15%
4-5% increasing rate
worldwide
Ethylene production Polyethylene EDC
10%
98% steam cracking 60%
Styrene
2% others 6%

Uses of ethylene
Propylene production
55% steam cracking
38% refinery operation Acrilic acid Others
7% others 4% 13%
Propylene-oxide
End users: polymers and 8%
Acrylonitrile
chemicals 7%

Cumene
Polypropylene 5%
63%
Uses of propylene

3
Olefins

Process Raw material Reactor Catalyst Temperature, °C

400-600
Refinery Depending on Noble meatls on
Crude oil (depending on
processes the process zeolite supporter
the process)
Gas 800-1000
Steam cracking and/orliquid Tubular - (depending on
hydrocarbons the process)
Fischer Trops
Syngas Fluid Metal-oxide 200-400
synthesis
Zeoite, metal-
Methanol to oxide, silica
LNG Moving bed 350-450
olefin alumina
phosphate
Methane Metal-oxide on g-
Methane Quartz bed 500-1000
oxidation Al2O3 supporter
Green Biomass, Batch or
Microorgnism 700-850
processes bioethanol continuous

4
Steam cracking

5
Scheme of the steam cracking

Raw mateirals

Steam cracking

Ethylene Separation Propylene

Hydrogen Flue gas

C4 hydrocarbons Heavier products
Pyro-naphtha

6
Raw materials

Hydrocarbon Steam

• Gaseous feedstocks • Etane (0,2-0,4 t steam/t)

• Ethylene • Propane (0,3-0,5 t steam/t)
• Propylene • Naphtha (0,4-0,8 t steam/t)
• N-butane or i-butane • Gas oil (0,8-1,0 t steam/t))
• LPG
• Liquid feedstocks
• Naphtha
• Condensates from naphtha
• AGO (atmospheric gas oil)
• HCR (hydrocracker residue)
• HVGO (hydrogenated vacuum gas oil)

Two cracker sites in TVK (both are Linde process, 370ktpa (by
debottlenecking) (1975) and 290ktpa (2004)
MOL represents 30% of the regional 3,1Mt capacity by its 900ktpa ethylene
capacity

7
Gaseous products

Hydrogen: is used in the site after purification (hydrogenation unit), The excess
hydrogen is sold or used as a fuel in the technology
Methane: see earlier, for sale
Ethylene: see earlier, for petchem use
Propylene: see earlier, for petchem use
Acetylenes: the C2-C3 acetylene gases obtained form the process can be
converted to alkane or olefinic products by hydrogenation
C4 fraction: can further be refined into butene, isobutene butadiene products
for polymerization (e.g. polybutadiene, styrene-butadiene rubber (SBR) and
nitrile rubber production), the excess C4-diene and olefin are returned to the
pyrolysis process after hydrogenation

8
Liquid products

Aromatics: can be used as solvents or as a blending component of the pyrolysis

gasoline by their beneficial properties
C5 olefins: used for isoprene, piperylene and cyclopentadiene production or as
a blending component of pyrolysis gasoline after hydrogenation
Fuel oil: used within the technology as a fuel, or the production of coke or
black coal
Naphthalene: for sale
Tar: used as a fuel, raw material for coke production or diluted with
hydrocarbons for resin production
Pyrolysis gasoline: raw material for aromatic products or fuel blending
component after hydrogenation

9
Olefin production by steam cracking

10
Reaction

Initation 𝐶𝐻3 𝐶𝐻3 → 𝐶𝐻3 ∙ + 𝐶𝐻3 ∙

Propagation 𝐶𝐻3 𝐶𝐻3 + 𝐶𝐻3 ∙ → 𝐶𝐻4 + 𝐶𝐻3 𝐶𝐻2 ∙

𝐶𝐻3 𝐶𝐻2 ∙ → 𝐶𝐻2 = 𝐶𝐻2 + 𝐻 ∙
𝐻 ∙ + 𝐶𝐻3 𝐶𝐻3 → 𝐻2 +𝐶𝐻3 𝐶𝐻2 ∙

Termination 2 𝐶𝐻3 𝐶𝐻2 ∙ → 𝐶𝐻3 𝐶𝐻2 𝐶𝐻2 𝐶𝐻3

𝐶𝐻3 𝐶𝐻2 ∙ + 𝐻 ∙ → 𝐶𝐻3 𝐶𝐻3

Disproportionation
𝐶𝐻2 = 𝐶𝐻2 + 𝐶𝐻3 𝐶𝐻2 ∙ → 𝐶𝐻3 𝐶𝐻2 𝐶𝐻2 𝐶𝐻2 ∙
2 𝐶𝐻3 𝐶𝐻2 𝐶𝐻2 𝐶𝐻2 ∙ → 𝐶𝐻3 𝐶𝐻2 𝐶𝐻 = 𝐶𝐻2 + 𝐶𝐻3 𝐶𝐻2 𝐶𝐻2 𝐶𝐻3
𝐶𝐻2 = 𝐶𝐻2 + 𝐶𝐻3 ∙ → 𝐶𝐻3 𝐶𝐻2 𝐶𝐻2 ∙
2 𝐶𝐻3 𝐶𝐻2 𝐶𝐻2 ∙ → 𝐶𝐻3 𝐶𝐻 = 𝐶𝐻2 + 𝐶𝐻3 𝐶𝐻2 𝐶𝐻3

11
Reaction

Initiation 𝐶𝐻3 𝐶𝐻2 𝐶𝐻3 → 𝐶𝐻3 𝐶𝐻2 𝐶𝐻2 ∙ + 𝐻 ∙

𝐶𝐻3 (𝐶𝐻2 )6 𝐶𝐻3 → 2 𝐶𝐻3 𝐶𝐻2 𝐶𝐻2 𝐶𝐻2 ∙

Propagation 𝐶𝐻3 𝐶𝐻2 𝐶𝐻3 + 𝐻 ∙ → 𝐶𝐻3 𝐶𝐻 ∙ 𝐶𝐻3 + 𝐻2

𝐶𝐻3 𝐶𝐻 ∙ 𝐶𝐻3 → 𝐶𝐻3 𝐶𝐻 = 𝐶𝐻2 + 𝐻 ∙
𝐶𝐻3 𝐶𝐻2 𝐶𝐻2 ∙ → 𝐶𝐻2 = 𝐶𝐻2 + 𝐶𝐻3 ∙

Propagation by β-scission

𝐶𝐻3 𝐶𝐻2 𝐶𝐻2 𝐶𝐻2 ∙ → 𝐶𝐻3 𝐶𝐻2 ∙ + 𝐶𝐻2 = 𝐶𝐻2 ∙

12
Olefin production by steam cracking

H2; ethene, ethane, propene; propane, etc.; CO2,

Hydrocarbons + H2O CO, water; aromatics, diolefins, heavier
hydrocarbons

𝐶𝑛 𝐻2𝑛+2 = 𝐶𝐻4 + 𝐶2 𝐻4 + 𝐶3 𝐻6 + 𝐶4 𝐻8 + 𝐶5 𝐻10 𝐶2 𝐻6 + 𝐶3 𝐻8 + 𝐶4 𝐻10 + 𝐶5 𝐻12 + ⋯ + 𝐻2

Free radical mechanism

Endothermic reactions
Short residence time (0,1-0,5sec) to avoid secondary reactions and promote the
olefin production by b-scission
0,3-0,8kg/kg dilution steam
Prevents coke formation
Better heat transport
Better mixing
Reduce the hydrocarbon partial pressure
Prevent secondary reactions

13
Olefin production by steam cracking

2-3 bar pressure (to avoid secondary reactions and low pressure promotes the
olefin production by b-scission)
800-850°C operating temperature
Fast temperature rise for ethylene and propylene production
High temperature for ethylene and propylene production
Heavier feed needs lower temperature to avoid coke formation
Thin tubes in furnace for advanced mass/volume ratio
Steam cracker is one of the most complex system in petrochemical sector
Feed preheating and dilution steam by utilization of waste heat
Complex cooling system for cracked gases
Low product and investment costs
High energy efficiency
Low environmental emission

14
 Olefin production by steam cracking

Multiplied furnaces
Radiation (thermal cracking at 800-850°C) & convection sections (heat recovery
from hot flue gas)
Auxiliraies
 Feed preheater
 Feed water preheater
 Process steam superheating
 HP steam superheating
Quench exchanger
Sudden coling for freezing the cracking reactions to 400-600°C (to avoid
secondary reactions)
Heat recovery by HP system production

Source:http://www.google.hu/url?sa=t&rct=j&q=&esrc=s&source=web&cd=4&sqi=2&ved=0CC4QFjAD&url=http%3A%2F%2Fwww.tvk.hu%2F 15
repository%2F713326.pdf&ei=RmK-VI23KKTiywOWy4JY&usg=AFQjCNHuNqEDzjDPr6a_7tXd0c-Us2URYw (TVK Plc )
Steam cracker feedstocks

Dilution steam
100
Pyrolysis oil
Product yields, in wt%

Pyrolysis gasoline
75
C3
C3H8
50 C3H6+C3H4
C2H6
C2H4
25
C2H2
CH4
0 H2+CO
Ethane Propane Naphtha AGO

The effect of reaction temperature on component yields

16
Steam cracker feedstocks

Asia & Pacific

Africa

Middle East Ethane

Propane
S-America Butane
Naphtha
N-America Gas oil
Other
CEE

W-Europe

0% 25% 50% 75% 100%

Steam cracker feedstocks by regions

17
 Olefin production by steam cracking

Steam cracker plants (2005)

18
Source: Hydrocarbon Processing’s Petrochemical Processes 2005 Gulf Publishing Company
 ABB Lummus process
Steam

Quench
Acid

Naptha fractionation
washing

Quench tower
Feed

Water washing
Heating oil
separation

Condenser
Furnace
Separato
Water r
Heating separation Dryer
oil

Methane Ethylene
Heating Propylene
gas
Acetylene
Hydrogen separation C4
Demethanizer converter Depropanizer
separation
Deethanizer Debutanizer
Hydrogen Heating
gas
Ethane Fractionation
C3 LPG Naphtha

Source: Robert A. Meyers: Handbook of Petrochemicals Production Processes, McGraw-Hill Handbooks 19

Barbara Elvers: Encyclopedia Of Industrial Chemistry
 Linde process
Cold train Hydrogen
Methane

Deethanizer
Ethylene

Demethanzer
Feed
Compressed

ethylene coloumn
Steam gas cooling

Low-pressure
Absorber

Hydrogen
Steam
cracker
Cracked gas
compressor
Quench water tower

Ethane recycling
fractionation
Primary

Quench Sour gas Propylene

Depropanizer
removal

Hydrogenation
Diluting steam C4 mix
generation

Fuel oil
Debutanizer

Propane recycle
Pyrolysis gasoline
20
Source: Petrochemical Processes Handbook, 2005, Gulf Publishing Company (http://www.scribd.com/doc/57518274/Petrochemical-Processes-Handbook)
 Technip process

Compressor Hydrogenation
Raw material Removal of acidic gas of acetylene
Drying Acetylene

C2 fractions

Pyrolysis Deethaniser Hydrogen-rich Demethanizer

furnaces stripper heating gas stripper

Propylene
C3/C4/C5+ Recycle of
Cooling C4- fractions Ethylene/ ethane
processing
Pyrolysis gas oil ethane
separation Ethylene

Gasoline, tar

Source: http://www.technip.com/sites/default/files/technip/publications/attachments/Ethylene_September_2013_Web_0.pdf (2016. április 8.) 21

Petrochemical Processes Handbook, 2005, Gulf Publishing Company (http://www.scribd.com/doc/57518274/Petrochemical-Processes-Handbook)
 Stone & Webster process

Recycle of ethane/propane

Liquid feedstock
Removal of acidic
Cracking Deethaniser
gas and drying

C2 Hydrogen
Quench heat
exchanger Ethylene
Fractionation of
Depropanizer
ethylene

Gas oil
Primary
C3
fractionator
Hydrogenation of
acetylene
C3 Propylene
Cleaning of C3
Water heat
exchanger
C2

C4+
Compressor Demethanizer Debutanizer

Flue gas Pyrolysis gas oil C4

Source: Robert A. Meyers: Handbook of Petrochemicals Production Processes, McGraw-Hill Handbooks 22

Barbara Elvers: Encyclopedia Of Industrial Chemistry
 KBR Score process

High pressure overheated steam

High pressure Caustic
boiler feed washing
Acetylene
Hydrocarbon converter
Steam cracker

feed

Gas oil
High pressure Depropanizer
steam

C4 fraction Waste gas

Ethylene
Hydrogen
Heating
gas Depmethanizer
Propylene
Pyrolysis Depethanizer C2 stripper
gas oil

C3 stripper
Ethane recycle
Propane recycle

Source: Robert A. Meyers: Handbook of Petrochemicals Production Processes, McGraw-Hill Handbooks 23

Barbara Elvers: Encyclopedia Of Industrial Chemistry
Other processes for olefin production

24
Olefins from methanol

Raw materials 10mtpy worldwide MTO combined

(coal, natural gas, residues, etc.) capacity (ethyene & propylene)

CH4 + H2O → CO + 3H2

Syngas production
CO + H2O → CO2 + H2
CH4 + O2 → CO2 + H2O

Methanol production CO + H2 → CH3 OH

CO2 + O2 → CH3 OH

MTO process CH3-OH → CH3-O-CH3 + H2O →

→ C2H4 + H2O → C2-C6 olefins

Ethyelene & propylene MTO process has lower investment cost

than steam cracking
25
 Olefins from methanol

CH4 Ethylene

Dryer
Propylene

Demethanizer
Product

Caustic scrubber

C2 splitter
Caustic

C3 splitter
Propane

Deethanizer
Fluid-bed reactor

Separator
Regenerator

Depropanizer
Ethane
CO2

Water

C4+

MeOH
Air

UOP LLC/Hydro process

26
Source: Petrochemical Processes Handbook, 2005, Gulf Publishing Company (http://www.scribd.com/doc/57518274/Petrochemical-Processes-Handbook) 26
 Olefins by dehydrogenation

Air Feed preheater

HP
steam
Fuel gas

Heat recovery
Star reformer Process
condensate
Fuel gas
Gas separation
O2/air

Boiler feed
Oxy reactor water
Process Olefin product
Fractionation
steam

Hydrocarbon Hydrocarbon
feed recycle

27
Source: Petrochemical Processes Handbook, 2005, Gulf Publishing Company (http://www.scribd.com/doc/57518274/Petrochemical-Processes-Handbook)
 Olefins by dehydrogenation

Hydrogen

PSA
Optional

Reactor on stream Fuel gas

Deethanizer
Heater

C3-C5
Propylene
Reactor on purge

Reactor on reheat
Air Exhaust air

Steam C4+
generation
Propane

CATOFIN process

28
Source: Petrochemical Processes Handbook, 2005, Gulf Publishing Company (http://www.scribd.com/doc/57518274/Petrochemical-Processes-Handbook)