Recent Advances in Cumene/Phenol/Acetone Technology

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Recent Advances in Cumene/Phenol/Acetone Technology: Energy Efficient Versalis/Lummus Cumene - Phenol Technology for Minimizing Operating Costs Ronald Venner Ajay Gami versalis technology conference : value to compete 15 November 2013

Bangkok, Thailand

A World of Solutions Lummus Chemical Processes

Methanol to Methanol Dimerization Ethylbenzene Styrene Polystyrene Olefins

Ethane Ethylene Olefins Polypropylene BPA LPG Conversion Steam Naphtha Cracking

Propylene AGO/VGO Cumene Phenol Polycarbonate C4s

C6-C8s CO O2 Dimethyl Diphenyl Methanol Carbonate Carbonate

Hydro- Benzene Aromatics dealkylation Saturation

Butene-1 Propane Propane Propylene Comonomer Dehydrogenation Production Hexene-1

Butanes Maleic Butadiene Anhydride Extraction Paraxylene

Butadiene Reformate or Separation & Butane Mixed Xylenes Isomerization Dehydrogenation Butylene

1 Agenda

• Overview • Cumene • Phenol-Acetone • Acetone Recycle • Summary

2 Technology Alliance

• Versalis SpA

• CB&I Versalis Cumene-Phenol Experience

• Producing cumene and phenol since 1964 • Started liquid-phase cumene operation in 1996 • Plant operations at two sites – Mantova, Italy – 300,000 MTA – Porto Torres, Italy – 200,000 MTA (recently shutdown) • One phenol licensee plant in operation – Domo, Germany – 160,000 MTA

Over 45 years of cumene and phenol plant operations experience

More than 98% on-stream factor

4 Role of Partners

Technology Licensing CB&I Versalis Marketing and licensing  Process design  Training   Start-up assistance   Catalyst supply  Follow-up technical service   Technology Maintenance Process enhancements   Catalyst R&D  Technology Development  

5 Cumene/Phenol Technology Experience

Capacity (mta) FCFC, Taiwan (Expansion) 400,000 GE Plastics, USA 300,000 Herdillia Chemicals, India 100,000 ThreeFCFC, new Taiwan Versalis /Lummus technology200,000 projects: ErtisaPetronas, Spain , Malaysia – 203 kMTA 86,000phenol FCFC,Allied China Chemical, - 450 USA kMTA cumene/300 175,000kMTA phenol EssarKumho, India Chemicals, - 270 Korea kMTA cumene/200 kMTA26,000 phenol Dow Chemical, USA 182,000 Union Carbide, Puerto Rico 91,000 Georgia-Gulf, USA 82,000 Texaco Chemical, USA 43,000 BTL of Illinois, USA 39,000

6 Agenda

• Overview • Cumene • Phenol-Acetone • Acetone Recycle • Summary

7 Versalis /Lummus Cumene Process

• State-of-the-art, liquid-phase, zeolite technology • Highly experienced Versalis/Lummus partnership – Versalis: leading petrochemical company with production plants based on PBE-type proprietary zeolite catalyst – CB&I: long history of development and commercialization with zeolitic aromatic alkylation processes, both cumene and ethylbenzene • Superior PBE-1 zeolite catalyst based technology • High quality products suitable for all requirements • Low investment and plant operating cost

8 Chemistry – Alkylation & Transalkylation

Alkylation CH(CH3)2

C 3H 6 +

(Propylene) (Benzene) (Cumene)

[CH(CH3)2]2 CH(CH3)2

C 3H 6 + ,etc... (Propylene) (Cumene) (Diisopropylbenzene)

Other side products: n-propylbenzene, non-aromatics, heavies,

Transalkylation

[CH(CH3)2]2 CH(CH3)2 + 2 , etc... (Diisopropylbenzene) (Benzene) (Cumene)

Other side products: EB, butylbenzene, heavies

9 Cumene Process Flow Scheme

Benzene Benzene Cumene PIPB Alkylator Transalkylator Column Steam CW Column Steam Column Steam

Heat

Heat Heat Heat

Steam

Water PIPB Recycle Recycle Benzene

Propylene Cumene Residue

10 PBE-1 Catalyst Advantages

• Versalis PBE-1 Proprietary Beta Zeolite – Alkylation and transalkylation • Superior yield • Superior catalyst formulation – Unique morphology – Optimum zeolite acidity and porosity – Demonstrated superior stability/durability – Ease of regeneration • Non-detectable catalyst deactivation rate – Extended catalyst life – Unique catalyst performance tracking system – Proprietary catalyst rejuvenation procedure • High mono selectivity and negligible formation of coke

Cumene Technology Highlights

• 99.7 wt% product yield • 100% propylene conversion throughout entire run • Ultra high cumene product purity of 99.95 wt% – N-propylbenzene (<300 wppm) – low Bromine Index (< 1) without clay treatment • Water injection allows for higher reactor operating temperatures without increasing impurity make • Efficient LP steam production which is utilized in the phenol unit • All carbon steel construction • Simple operation and low maintenance

12 Agenda

• Overview • Cumene • Phenol-Acetone • Acetone Recycle • Summary

13 Versalis /Lummus Phenol Process

• State-of-the-art technology – Safe and reliable wet oxidation technology based on gas lift reactors – Optimized cleavage technology based on loop reactors – Glycol based extractive distillation technology

Spent Air

Cumene CHP

Air

14 Process Chemistry

OH O

CH3 - C- CH 3 Phenol Acid

Cumene Hydroperoxide O O 2 O H CH 3 -C - CH3

CH3 - C -CH 3 CH 3 -C Acetone

Cumene Acetophenone OH O 2 CH - C CH CH3 - C- CH 3 3 2 Acid

Dimethyl benzyl alcohol Alpha-Methylstyrene

15 Process Chemistry

OH O

CH3 - C- CH 3 Phenol Acid

Cumene Hydroperoxide O O 2 O H CH 3 -C - CH3

CH3 - C -CH 3 CH 3 -C Acetone

Cumene Acetophenone OH O 2 CH - C CH CH3 - C- CH 3 3 2 Acid

Dimethyl benzyl alcohol Alpha-Methylstyrene

16 Process Steps

• Oxidation • Acetone fractionation • Cumene stripping • Phenol extraction • Cleavage • AMS hydrogenation • Neutralization • Dephenolation

Cumene Cumene Oxidation Cleavage Neutralization Dephenolation Air Stripping

AMS Acetone Acetone Hydrogenation Fractionation

Phenol Phenol Extraction

Fuel

17 Technology Advantages

• High yield – Cumene consumption of < 1.31 kg/kg of phenol • Highest quality products – Only phenol/acetone process commercially proven to produce pharmaceutical grade acetone • Low environmental impact of air and water emissions • Low energy consumption – Glycol based extractive distillation

18 Agenda

• Overview • Cumene • Phenol-Acetone • Acetone Recycle • Summary

19 Acetone Recycle Technologies

• Over 90% of world’s phenol production currently via cumene hydroperoxide route that produces acetone as a by-product

OH H O CH - C -CH 3 3 CH -C - CH 3 3 Phenol O 2 Acid

Cumene O Cumene Hydroperoxide CH - C- CH3 3

Acetone

• Phenol and acetone produced in fixed ratio: 0.62 ton of acetone per ton of phenol • Market demands for phenol and acetone not in same ratio

20 Acetone Flexibility Solutions

• Two new Versalis/Lummus technology solutions: 1. Alternate product – Acetone to isopropyl alcohol (IPA)

Commercial Grade IPA Acetone Raw IPA Raw IPA IPA Purification Production H Section 2

2. Propylene feedstock reduction – Acetone recycle to cumene (under development)

21 Agenda

• Overview • Cumene • Phenol-Acetone • Acetone Recycle • Summary

22 Versalis /Lummus Partnership

• New technology solutions to minimize acetone byproduct • State of the art commercially proven technologies • Only licensor/operator with over 45 years of operating experience • Unique position to offer full range of phenolic technologies for green polycarbonate production

BPA

Propylene Benzene Cumene Phenol Polycarbonate

CO O2 Dimethyl Diphenyl Methanol Carbonate Carbonate