A World of Solutions

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

Methanol

Butadiene

Butylene

Lummus Chemical Processes

Cumene

Polystyrene Styrene Ethylbenzene

Butadiene

Extraction

Maleic

Anhydride

Naphtha

AGO/VGO

Steam

Cracking

Ethane

LPG

Propane Dehydrogenation

Butanes

Propane

Propylene

Ethylene

Hydro-

dealkylation

C6-C8s

Benzene Aromatics

Saturation

C4s

Propylene

Polypropylene

Phenol

Dimethyl

Carbonate

Diphenyl

Carbonate

Olefins

Conversion

Dimerization

Butane Dehydrogenation

CO O2

Methanol to

Olefins Methanol

1

Separation &

Isomerization

Paraxylene

Reformate or

Mixed Xylenes

Hexene-1 Comonomer

Production

Butene-1

Polycarbonate

BPA

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

5

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

Capacity (mta)

FCFC, Taiwan (Expansion) 400,000

GE Plastics, USA 300,000

Herdillia Chemicals, India 100,000

FCFC, Taiwan 200,000

Ertisa, Spain 86,000

Allied Chemical, USA 175,000

Kumho Chemicals, Korea 26,000

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

Cumene/Phenol Technology Experience

Three new Versalis/Lummus technology projects:

Petronas, Malaysia – 203 kMTA phenol

FCFC, China - 450 kMTA cumene/300 kMTA phenol

Essar, India - 270 kMTA cumene/200 kMTA phenol

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

9

Alkylation

+ C 3 H

6

Transalkylation

C 3 H

6 + CH(CH3)2

,etc...

(Cumene)

(Diisopropylbenzene)

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

+ 2 , etc...

Other side products: EB, butylbenzene, heavies

(Propylene) (Benzene)

(Cumene) (Propylene)

(Diisopropylbenzene) (Cumene) (Benzene)

CH(CH3)2

[CH(CH3)2]2

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

Propylene Cumene Residue

Alkylator Steam Steam

Heat Heat

Transalkylator Benzene Column

Cumene

Column

PIPB

Column

PIPB

Heat

CW Steam

Steam

Recycle

Recycle

Benzene

Heat

Water

Benzene

Cumene Process Flow Scheme

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

11

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

14

Cumene

Spent Air

CHP

CW

Air

OH

Phenol

Acetone

CH 3 - C - CH

3

O

Alpha-Methylstyrene

CH 3 - C - CH

3

H

CH 3 - C - CH

3

O

Acid

Cumene Hydroperoxide

CH 3 - C - CH

3

O OH

CH 3 - C

Acetophenone

CH 3 - C CH

2

OH

Dimethyl benzyl alcohol

Cumene

Acid

O 2

O 2

O 2

H 2

Process Chemistry

15

OH

Phenol

Acetone

CH 3 - C - CH

3

O

Alpha-Methylstyrene

CH 3 - C - CH

3

H

CH 3 - C - CH

3

O

Acid

Cumene Hydroperoxide

CH 3 - C - CH

3

O OH

CH 3 - C

Acetophenone

CH 3 - C CH

2

OH

Dimethyl benzyl alcohol

Cumene

Acid

O 2

O 2

O 2

H 2

Process Chemistry

16

• Oxidation

• Cumene stripping

• Cleavage

• Neutralization

• Acetone fractionation

• Phenol extraction

• AMS hydrogenation

• Dephenolation

Process Steps

17

Cumene

Air

Fuel

Phenol

Acetone

Oxidation Cumene

Stripping Cleavage Dephenolation

AMS

Hydrogenation

Neutralization

Acetone

Fractionation

Phenol

Extraction

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

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

• 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

OH

Phenol

Acetone

CH 3 - C - CH 3

O

CH 3 - C - CH

3

H

Acid

Cumene Hydroperoxide

- CH 3

O

OH

CH 3 - C

Cumene

O 2

Acetone Recycle Technologies

20

Acetone Flexibility Solutions

Acetone Raw IPA Commercial Grade IPA

H2

21

Raw IPA

Production

IPA Purification

Section

• Two new Versalis/Lummus technology solutions:

1. Alternate product

– Acetone to isopropyl alcohol (IPA)

2. Propylene feedstock reduction

– Acetone recycle to cumene (under development)

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

23

Methanol

Cumene Phenol

Dimethyl

Carbonate

Diphenyl

Carbonate

CO O2

Polycarbonate

BPA

Propylene Benzene