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Alpha Olefins Production Expertise

Fabien Lundy 1

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

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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

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Axens Major Actor  Differentiating and integrated offer to its customers Technology supply

Catalyst supply

• Pioneering technologies • Conditions for optimum performances • Flexible design

• Continuous R&D • Cost effective product developments • LD series and more

Innovative high efficiency internals • EquiFlow trays • Catapac dense loading

Follow-up all along the life of the unit • Troubleshooting • Contamination experience • Advanced process control

Continuous improvement process Axens – Egypt Downstream Summit, February 2016

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On Demand Alpha Olefins Production  Co-monomer requirements: 1-butene and 1-hexene for polyethylene applications Annual growth 1980-2030

World demand index 900

~4%

Polymer demand

800 700 600

~3%

GDP*

500 400

Gas prod.

300

~2%

 Sustained growth for LLDPE and HDPE demand • 1-butene and 1-hexene 2010-2015 AAGR ~ 5 %

200 0

1980

~1%

Oil prod.

100

1990

2000

2010

GDP*: Gross Domestic Product

2020

2030

Source : Total

1-butene and 1-hexene sourcing?

Axens – Egypt Downstream Summit, February 2016

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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

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Axens Technologies for Ethylene Plants Ethylene

Removal of arsenic & mercury RAM II

Condensates

Steam Cracker Furnaces & Distillation Section

MAPD selective hydrogenation

Propylene

Purification Multibed

Butadiene

C3/C4 total hydrogenation C4 acetylenes selective hydrogenation

Butadiene Butadiene BD rich BD rich selective selective hydrogenation hydrogenation

Trimerization Trimerization AlphaHexol AlphaHexol

Dimerization Dimerization AlphaButol AlphaButol Butadiene Extraction

C C44 etherification etherification Catacol Catacol

1-hexene 1-hexene 1-butene 1-butene

BD selective BD lean lean selective hydro hydro 1-butene 1-butene maximization maximization

Super Super fractionation fractionation

BD lean selective hydro 2-butene maximization

Isobutene Purif Isopure

Isobutane Isobutene 2-butenes rich cut

Dimerization Dimersol-X

Hydration Dehydrogenation

Octenes N-butane MEK

MTBE, ETBE

Skeletal isomerization Iso-5

C4/C5 olefins hydrogenation

Oligomerization Selectopol Polynaphtha PolyFuel

Olefins hydrogenation

TAME, TAEE Benzene saturation Cyclohexane

C5 etherification Catacol

Pygas 1st Stage Hydrogenation (GHU-1)

C6+

Pygas 2nd Stage Hydrogenation (GHU-2)

C9+

C6-C8

Cyclohexane

Benzene

Advanced Pygas Upgrading APU

C5

Solvents

Toluene Aromatics recovery Sulfolane Morphylane Benzene production (HydroDeAlkylation)

Mixed xylenes to car fuels pool

Axens – Egypt Downstream Summit, February 2016

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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

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Axens Experience in Homogeneous Catalysis    

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

More than 100 references

Axens – Egypt Downstream Summit, February 2016

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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

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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 into n-butenes or extracted

Or

C4 Fraction Recovered

BD extraction

BD spec ensured

Methanol Hydrogen

MTBE High Conversion

Specific know-how. Catalytic distillation involved

BD

BD traces hydrogenation with 1-butene maximization

Isobutene removed

Isobutane rich cut

1-butene 2-butenes+n-butane

MTBE

Axens – Egypt Downstream Summit, February 2016

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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

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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

13

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

100.0

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

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Selectivity On-purpose Mechanism  Selective formation of the alpha-olefin Catalysts + co-catalysts

• 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

M

2 C2H4

H M

M

Selectivity induced by the stability of the metallacyclic intermediate = Axens’ know-how in catalyst design Axens – Egypt Downstream Summit, February 2016

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AlphaButol Key Features Selective ethylene dimerization mechanism  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

LnM + M = Metal Ln = Ligand

L nM

1-butene 2 C2H4

Reactor

Recycle column

Ethylene feed

Catalyst preparation and storage

1-butene

1-butene column

Catalyst removal

C6+ cut Spent catalyst

Axens – Egypt Downstream Summit, February 2016

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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

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AlphaHexol Key Features Selective ethylene trimerization mechanism  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

LnM + M = Metal Ln = Ligand

LnM

1-hexene 3 C2H4

Axens – Egypt Downstream Summit, February 2016

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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

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Axens Succeed Together Blog axens.net/blog

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