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1
Alpha Olefins
Production Expertise
Fabien Lundy
2
Introduction
Production of 1-butene Co-monomer
• Recovering Native 1-butene from Raw C4 Cut
• AlphaButol®: On-purpose Ethylene to 1-butene
Production of 1-hexene Co-monomer
• AlphaHexol™: On-purpose Ethylene to 1-hexene
Agenda
Axens – Egypt Downstream Summit, February 2016
3
Introduction
Production of 1-butene Co-monomer
• Recovering Native 1-butene from Raw C4 Cut
• AlphaButol®: On-purpose Ethylene to 1-butene
Production of 1-hexene Co-monomer
• AlphaHexol™: On-purpose Ethylene to 1-hexene
Agenda
Axens – Egypt Downstream Summit, February 2016
4
Differentiating and integrated offer to its customers
Axens Major Actor
Axens – Egypt Downstream Summit, February 2016
Technology supply • Pioneering technologies
• Conditions for optimum
performances
• Flexible design
Innovative high
efficiency internals • EquiFlow trays
• Catapac dense loading
Catalyst supply • Continuous R&D
• Cost effective product
developments
• LD series and more
Follow-up all along
the life of the unit • Troubleshooting
• Contamination experience
• Advanced process control
Continuous improvement process
5
0
100
200
300
400
500
600
700
800
900
1980 1990 2000 2010 2020 2030
On Demand Alpha Olefins Production
Co-monomer requirements: 1-butene and 1-hexene for
polyethylene applications
World demand index Annual growth
1980-2030
~ 4 %
~ 3 %
~ 2 %
~ 1 %
GDP*: Gross Domestic Product Source : Total
Polymer demand
GDP*
Oil prod.
Gas prod.
Sustained growth for
LLDPE and HDPE
demand
• 1-butene and 1-hexene
2010-2015 AAGR ~ 5 %
Axens – Egypt Downstream Summit, February 2016
1-butene and
1-hexene sourcing?
6
Co-monomers Sourcing
1-butene and 1-hexene in C4 and C6 fractions
1-butene and 1-hexene sourcing?
• Beyond simple distillation to extract the desired isomer
• New technology answers: on-purpose ethylene oligomerization
Axens – Egypt Downstream Summit, February 2016
1-hexene 1-butene
AlphaButol® & AlphaHexol™ dedicated processes
for polymer grade 1-butene and 1-hexene
7
Axens Technologies for Ethylene Plants
MAPD selective
hydrogenation
C4 acetylenes
selective
hydrogenation
Purification
Multibed
Dimerization
AlphaButol
Trimerization
AlphaHexol
Butadiene
BD rich
selective
hydrogenation
Butadiene
Extraction
C4
etherification
Catacol
Skeletal
isomerization
Iso-5
C4/C5 olefins
hydrogenation
C5 etherification
Catacol
Pygas 1st Stage
Hydrogenation
(GHU-1)
Pygas 2nd Stage
Hydrogenation
(GHU-2)
BD lean selective
hydro
2-butene
maximization
Isobutene
Purif
Isopure
Oligomerization
Selectopol
Polynaphtha
PolyFuel
Olefins
hydrogenation
Aromatics recovery
Sulfolane
Morphylane
Dimerization
Dimersol-X
Hydration
Dehydrogenation
Super
fractionation
BD lean selective
hydro
1-butene
maximization
Ste
am
Cra
ck
er
Fu
rna
ce
s &
Dis
tilla
tio
n S
ec
tio
n
Removal of
arsenic &
mercury
RAM II
1-hexene
Propylene
Butadiene
1-butene
Isobutane
Isobutene
Octenes
N-butane
MEK
MTBE, ETBE
Solvents
TAME, TAEE
Benzene
Toluene
Mixed xylenes
to car
fuels pool Condensates
Ethylene
Benzene production
(HydroDeAlkylation)
Benzene
saturation
Cyclohexane Cyclohexane
C3/C4 total
hydrogenation
C5
C6+ C6-C8
C9+
2-butenes
rich cut
Advanced Pygas
Upgrading
APU
Axens – Egypt Downstream Summit, February 2016
Dimerization
AlphaButol 1-butene
Butadiene
BD rich
selective
hydrogenation
C4 etherification
Catacol
Super
fractionation
BD lean selective
hydro
1-butene
maximization
Trimerization
AlphaHexol 1-hexene
8
Axens: long and extensive experience in the field of
heterogeneous catalysis
Heterogeneous catalysis: successful but with
identified fields for improvement
• Distribution
• Handling poisoning
• Controlling exotherms
• Evolution of the catalytic activity over time
Developing breakthroughs to improve the situation
Homogeneous Catalysis
Axens – Egypt Downstream Summit, February 2016
Homogeneous catalysis
9
Research initiated mid 60’s: > 50 years involvement
Several processes applying this breakthrough technology
Maintained know-how along the years
Yves Chauvin: Nobel prize in chemistry 2005
Axens Experience in Homogeneous Catalysis
Axens – Egypt Downstream Summit, February 2016
More than 100 references
10
Introduction
Production of 1-butene Co-monomer
• Recovering Native 1-butene from Raw C4 Cut
• AlphaButol®: On-purpose Ethylene to 1-butene
Production of 1-hexene Co-monomer
• AlphaHexol™: On-purpose Ethylene to 1-hexene
Agenda
Axens – Egypt Downstream Summit, February 2016
11
1-butene from Raw C4 Cut (1/3)
Axens – Egypt Downstream Summit, February 2016
BD transformed
into n-butenes
or extracted
Handling the butadiene rich cut
BD
Or
BD rich cut selective
hydrogenation
BD extraction
MTBE
Isobutene
removed
Methanol
Specific know-how.
Catalytic distillation
involved
MTBE High
Conversion
Hydrogen
BD spec
ensured
BD traces
hydrogenation with
1-butene
maximization
2-butenes+n-butane
1-butene
Isobutane
rich cut
C4 Fraction
Recovered
Raw C4 cut from debutanizer
overhead
12
Axens: single source supplier for all technologies
• High conversion MTBE
• Selective hydrogenation maximizing 1-butene production
• Superfractionation
• Purification (if required)
• Ancillary services
› Single source designer
› Single source operation support, advanced control
Latest started plant with Axens’ technology: 4Q42011
Specific technology items
• Catacol™& “Doublets” for catalytic distillation
• Highly selective catalyst towards 1-butene
• Heat pump option
1-butene from Raw C4 Cut (2/3)
Axens – Egypt Downstream Summit, February 2016
13
Introduction
Production of 1-butene Co-monomer
• Recovering Native 1-butene from Raw C4 Cut
• AlphaButol®: On-purpose Ethylene to 1-butene
Production of 1-hexene Co-monomer
• AlphaHexol™: On-purpose Ethylene to 1-hexene
Agenda
Axens – Egypt Downstream Summit, February 2016
14
Axens Answer to Alpha Olefins Sourcing
Axens – Egypt Downstream Summit, February 2016
98.0
98.5
99.0
99.5
100.0
1-b
ute
ne
pu
rity
, vo
l%
Date
Typical required specification: 99.0 %
• On-site production
• On-demand capacity
• High and constant co-monomer quality
15
Selectivity On-purpose Mechanism
Axens – Egypt Downstream Summit, February 2016
M M
H
M
Catalysts +
co-catalysts
2 C2H4
Selective formation of the alpha-olefin
• Not a chain growth mechanism
• Highly selective towards desired oligomer
Mechanism in brief
• Activation of catalyst complex
• Concerted coupling of ethylene
• Stabilized metallacycle intermediate
• Intramolecular hydrogen transfer
• Metallacycle opening: alpha olefin
formation
Selectivity induced by the stability of the metallacyclic
intermediate = Axens’ know-how in catalyst design
16
Polymer grade 1-butene for
LLDPE & HPDE
Process simplicity and
ease of operation
High flexibility
Low operating temperature
and pressure
Operating in liquid phase
with no solvent required
No heat input
to the reaction section
Carbon steel equipment
AlphaButol Key Features
Axens – Egypt Downstream Summit, February 2016
Selective ethylene
dimerization mechanism
Ethylene
feed
Reactor
Recycle
column 1-butene
C6+ cut Catalyst
removal
Catalyst
preparation
and storage
1-butene
column
Spent catalyst
LnM + L n M
1-butene 2 C2H4
M = Metal
Ln = Ligand
17
Introduction
Production of 1-butene Co-monomer
• Recovering Native 1-butene from Raw C4 Cut
• AlphaButol®: On-purpose Ethylene to 1-butene
Production of 1-hexene Co-monomer
• AlphaHexol™: On-purpose Ethylene to 1-hexene
Agenda
Axens – Egypt Downstream Summit, February 2016
18
Similar to AlphaButol, backed by
extensive industrial experience in
homogeneous catalysis
Polymer grade 1-hexene suitable
for LLDPE & HPDE
Efficient ethylene feed use
Process simplicity and
ease of operation
High flexibility
Mild operating temperature
and pressure
Carbon Steel Equipment
AlphaHexol Key Features
Axens – Egypt Downstream Summit, February 2016
Selective ethylene
trimerization mechanism LnM +
1-hexene 3 C2H4
M = Metal
Ln = Ligand
LnM
19
Succeeding in alpha-olefins production
1-butene production
• Extensive know-how of different available pathways
• Native 1-butene recovery from native raw C4 cut
› Scheme involving several steps
› Axens: single source supplier of all necessary technologies
• AlphaButol®: on-purpose ethylene dimerization
1-hexene production
• AlphaHexol™: on-purpose ethylene trimerization
Conclusion
Axens – Egypt Downstream Summit, February 2016
20
Axens Succeed Together Blog
axens.net/blog