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Alpha Olefins

Production Expertise

Fabien Lundy

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Agenda

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

Axens Egypt Downstream Summit, February 2016 2


Agenda

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

Axens Egypt Downstream Summit, February 2016 3


Axens Major Actor
Differentiating and integrated offer to its customers

Technology supply Catalyst supply


Pioneering technologies Continuous R&D
Conditions for optimum Cost effective product
performances developments
Flexible design LD series and more

Innovative high Follow-up all along


efficiency internals the life of the unit
Troubleshooting
EquiFlow trays
Contamination experience
Catapac dense loading
Advanced process control

Continuous improvement process

Axens Egypt Downstream Summit, February 2016 4


On Demand Alpha Olefins Production

Co-monomer requirements: 1-butene and 1-hexene for


polyethylene applications
Annual growth
World demand index 1980-2030 Sustained growth for
900
Polymer demand ~4% LLDPE and HDPE
800
700 demand
600 ~3%
GDP* 1-butene and 1-hexene
500
400
Gas prod. ~2% 2010-2015 AAGR ~ 5 %
300
200
100 Oil prod. ~1%
0
1980 1990 2000 2010 2020 2030
1-butene and
GDP*: Gross Domestic Product Source : Total 1-hexene sourcing?

Axens Egypt Downstream Summit, February 2016 5


Co-monomers Sourcing

1-butene and 1-hexene in C4 and C6 fractions

1-butene
1-hexene

1-butene and 1-hexene sourcing?


Beyond simple distillation to extract the desired isomer
New technology answers: on-purpose ethylene oligomerization
AlphaButol & AlphaHexol dedicated processes
for polymer grade 1-butene and 1-hexene

Axens Egypt Downstream Summit, February 2016 6


Axens Technologies for Ethylene Plants
Ethylene
MAPD selective Purification Propylene
hydrogenation Multibed
Steam Cracker Furnaces & Distillation Section Butadiene

C3/C4 total Trimerization


Trimerization
AlphaHexol
1-hexene
1-hexene
hydrogenation AlphaHexol
Dimerization
Dimerization
AlphaButol
AlphaButol 1-butene
1-butene
C4 acetylenes
Butadiene Isobutane
selective
Extraction
hydrogenation BD
BD lean selective
lean selective Isobutene
hydro
hydro Super
Super 2-butenes
Butadiene
Butadiene C 1-butene
1-butene fractionation
fractionation rich cut Dimerization
C44 Octenes
BD rich
BD rich maximization
maximization Dimersol-X
etherification
etherification
selective
selective Catacol
Catacol BD lean selective
hydrogenation
hydrogenation Isobutene N-butane
hydro Hydration
Purif
2-butene
Isopure Dehydrogenation MEK
maximization
MTBE, ETBE
Oligomerization Olefins
Selectopol Solvents
hydrogenation
Skeletal Polynaphtha
C4/C5 olefins isomerization PolyFuel TAME, TAEE
hydrogenation Iso-5 Benzene
saturation Cyclohexane
C5 etherification Cyclohexane
Catacol
Advanced Pygas Benzene
Removal of C5 Upgrading
arsenic & APU Toluene
mercury
RAM II Pygas 1st Stage Pygas 2nd Stage Aromatics recovery
Mixed xylenes
Hydrogenation Hydrogenation Sulfolane
(GHU-1) C6+ (GHU-2) C6-C8 Morphylane

Condensates to car
C9+ Benzene production fuels pool
(HydroDeAlkylation)

Axens Egypt Downstream Summit, February 2016 7


Homogeneous Catalysis
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 8


Axens Experience in Homogeneous Catalysis
Research initiated mid 60s: > 50 years involvement
Several processes applying this breakthrough technology
Maintained know-how along the years
Yves Chauvin: Nobel prize in chemistry 2005

More than 100 references

Axens Egypt Downstream Summit, February 2016 9


Agenda

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

Axens Egypt Downstream Summit, February 2016 10


1-butene from Raw C4 Cut (1/3)
Raw C4 cut Handling the butadiene rich cut
from debutanizer
overhead BD rich cut selective
hydrogenation BD transformed
Or into n-butenes
BD extraction or extracted
C4 Fraction BD
Recovered

BD spec
Methanol
ensured
Hydrogen Isobutane
rich cut

MTBE High BD traces


Conversion hydrogenation with
1-butene
Specific know-how. 1-butene
maximization
Catalytic distillation
involved Isobutene 2-butenes+n-butane
removed MTBE

Axens Egypt Downstream Summit, February 2016 11


1-butene from Raw C4 Cut (2/3)
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

Axens Egypt Downstream Summit, February 2016 12


Agenda

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

Axens Egypt Downstream Summit, February 2016 13


Axens Answer to Alpha Olefins Sourcing
100.0
1-butene purity, vol%
99.5

99.0
Typical required specification: 99.0 %
98.5

98.0
Date
On-site production
On-demand capacity
High and constant co-monomer quality

Axens Egypt Downstream Summit, February 2016 14


Selectivity On-purpose Mechanism
Selective formation of the alpha-olefin
Not a chain growth mechanism Catalysts +
co-catalysts
Highly selective towards desired oligomer

Mechanism in brief M 2 C2H4

Activation of catalyst complex


Concerted coupling of ethylene
H
Stabilized metallacycle intermediate
Intramolecular hydrogen transfer M M
Metallacycle opening: alpha olefin
formation

Selectivity induced by the stability of the metallacyclic


intermediate = Axens know-how in catalyst design

Axens Egypt Downstream Summit, February 2016 15


AlphaButol Key Features
Selective ethylene LnM + L nM
dimerization mechanism
1-butene
M = Metal
2 C2H4
Polymer grade 1-butene for Ln = Ligand

LLDPE & HPDE


Recycle 1-butene
Process simplicity and Reactor column
ease of operation Ethylene
High flexibility feed 1-butene
column
Low operating temperature
and pressure
Operating in liquid phase
with no solvent required
No heat input Catalyst
preparation
Catalyst
removal C6+ cut
to the reaction section and storage

Carbon steel equipment Spent catalyst

Axens Egypt Downstream Summit, February 2016 16


Agenda

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

Axens Egypt Downstream Summit, February 2016 17


AlphaHexol Key Features
Selective ethylene LnM + LnM
trimerization mechanism
1-hexene
M = Metal
3 C2H4
Similar to AlphaButol, backed by Ln = Ligand

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

Axens Egypt Downstream Summit, February 2016 18


Conclusion
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

Axens Egypt Downstream Summit, February 2016 19


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