The DMC/DPC route to Polycarbonate Feeds :

Integrated DMC-DPC Plant for Green

Polycarbonate Production
Ajay Gami

versalis technology conference: value to compete

November 14, 15 2013

Bangkok, Thailand

A World of Solutions
 Lummus Chemical Processes

Methanol Methanol to
Dimerization Ethylbenzene Styrene Polystyrene
Olefins

Ethane
Ethylene Olefins
LPG Polypropylene BPA
Conversion
Steam
Naphtha Cracking

AGO/VGO Propylene
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
• DMC
• DPC
• Technology Integration
• Summary

2
 Technology Alliance

• Versalis SpA

• CB&I

A World of Solutions 3
 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  

A World of Solutions 4
 Agenda

• Overview
• DMC
• DPC
• Technology Integration
• Summary

5
 Versalis/Lummus DMC-DPC Partnership

2007
Versalis/Lummus
Partnership
Proven history...
2002
Spain revamp to
96,600 tons/year

Licensed 100kTA DPCGE builds 2 Plant

1992-1998
plants: for
Japan & Spain
Polycarbonate
1989Production
GE License in 2010
Licensed to GE for production
of polycarbonates
1988 Ravena Revamp
Production increased to
8,000 tons/year by adding second train

1983 Ravena Plant

5,000 tons/year Prototype DMC Plant

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 What Makes DMC “Green”?

Dimethyl Carbonate (DMC) –

a “green” industrial chemical

• Benign solvent with low HSE impact

– used in Li ion battery production
• Versatile reagent
• Excellent fuel additive properties
• Phosgene substitute in the production of aromatic
polycarbonates (PC)

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 DMC – Commercial Production Routes

Phosgenation process
• Reaction of methanol with phosgene
• One European plant shut down after accident
• Chinese companies still operating

Carboxylation processes using an organic oxide

• Reaction of organic oxides with carbon dioxide yielding cyclic carbonates
followed by trans-esterification with methanol
• Japanese process uses ethylene oxide
• Chinese companies use propylene oxide

Oxidative carbonylation processes using an oxidizing compound

• Reaction of methanol with carbon monoxide and an oxidizing compound
• Japanese process uses nitrous oxide (NO)
• Versalis/Lummus process uses oxygen (O2)

A World of Solutions 8
 Comparison of DMC Processes

Main By-Product
Route Company
By-Product Recycle
Chinese Hydrochloric
Phosgenation Difficult
Companies Acid
Ethylene
Japanese Difficult
Glycol
Carboxylation
Chinese Propylene
Difficult
Companies Glycol
HNO3
Japanese Difficult
Oxidative (Diluted Solution)
Carbonylation Versalis
CO2 Easy
Europa

A World of Solutions 9
 DMC via Oxidative Carbonylation

Using O2 (Versalis/Lummus Process)

2CH3OH + CO + 0.5 O2 (CH3O)2C=O + H2O

Advantages
• 1-step reaction process
• No dangerous intermediates and by-products
• No catalyst make-up in normal operation
• Proven at large, world-scale capacity plants
• Typical plant capacity: 25-75 kta - larger plant capacity also
possible

A World of Solutions 10
 Versalis/Lummus DMC Process

2CH3OH + CO + 0.5 O2 (CH3O)2C=O + H2O

CO/CO2 Products DMC

CO2
Separation Purification H2O

CO CO Reaction HCl Methanol

Compression Line Recovery Recovery

Oxygen
O2
Compression

CH3OH

HCl

Gas Streams
Liquid Streams
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 DMC Process Features

• Single stage CSTR reactor operating at moderate pressure

and temperature
• Employs partially soluble copper based catalyst
• In situ continuous catalyst regeneration – no catalyst make-
up in normal operation
• Extensive energy integration

A World of Solutions 12
 DMC Process Performance

Methanol selectivity to DMC >95%

Methanol selectivity to by-products < 5%

Oxygen conversion per pass >99%

Oxygen selectivity to DMC >60%
Oxygen selectivity to CO2 < 40%

A World of Solutions 13
 Versalis/Lummus DMC Technology Advantages

• ‘On purpose’ technology

– No byproducts formation

• Commercially well proven technology

– Four commercial plants designed and operated
– Currently three units operating (one in Japan and two in Spain)

• Inherently safe technology

– Use of phosgene avoided
– No intermediate chemicals unlike competing technologies
– Reactor kept well outside of the flammability envelope

• Superior product quality

– 99.9% purity with less than 5 wppm chlorine

• High purity DMC design option (HDMC)

– Increase purity to 99.99+% with proprietary design

A World of Solutions 14
 Agenda

• Overview
• DMC
• DPC
• Technology Integration
• Summary

15
 Overview

Diphenyl Carbonate (DPC) – key intermediate for

polycarbonate production

• Phosgene substitute in the production of aromatic

polycarbonates (PC)
• White solid powder at room temperature

A World of Solutions 16
 Versalis/Lummus DPC Process

Two step reaction

• Step 1 – PMC formation: Phenol + DMC  PMC + Methanol
• Step 2 – DPC formation: 2 PMC  DPC + DMC
DMC/Methanol
CO2 (to DMC unit)
Step 1
DMC PMC Lights Anisole Anisole
Phenol Reaction Recovery Recovery

DPC Catalyst DPC

DPC
Reaction Recovery Purification

Step 2
Catalyst Heavies
Preparation

Heat integration with DMC unit

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 Non-phosgene Route to Polycarbonate

2 CH3OH BPA
CO
DMC DPC Melt
DMC DPC
0.5 O2 Polymerization PC
Unit Unit
Unit
2 PhOH
CO2 H2O

Versalis/Lummus Technology

• Non-phosgene route – avoids toxicity

• No use of chlorinated solvent – avoids environmental
issues
• Improved quality of polycarbonate product suitable
for optical grades
• No glycol byproducts
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 Versalis/Lummus DPC Technology Advantages

• Superior yield
– 99.3% yield – best in the market

• Commercially well-proven technology

– Four commercial plants designed and operated
– Currently two units operating (in Spain)
– New 100 kta DPC plant starting up in November 2013

• Superior product quality

– 99.6% purity with less than 0.1 ppm titanium and iron
– Better polycarbonate purity

A World of Solutions 19
 Agenda

• Overview
• DMC
• DPC
• Technology Integration
• Summary

20
 Integrated DMC-DPC Plant

• DMC and DPC technologies can be integrated to achieve the

best raw material and energy efficiencies
– Methanol from DPC unit is recycled back to DMC unit along with
some DMC
• Avoids additional processing in DPC unit
• Internal recycle of DMC and methanol

– DPC unit uses high pressure steam and allows low pressure steam
production
• Low pressure steam is then used in DMC unit - overall reduction
in energy requirements

A World of Solutions 21
 Integrated DMC-DPC Plant

CHLORINATED SPENT
CO PURGE CO2 VENT PHENOL CO2 CATALYST

DIMETHYLCARBONATE
METHANOL
DPC TO PC
HCl
DIMETHYLCARBONATE HEAT RECOVERY DIPHENYLCARBONATE

CO UNIT UNIT
ANISOLE
METHANOL / DMC RECYCLE
O2

PROCESS WATER FRESH CATALYST PHENOL / DPC

FROM PC

A World of Solutions 22
 Agenda

• Overview
• DMC
• DPC
• Technology Integration
• Summary

23
 Versalis/Lummus Partnership

• Unique position to offer full range of phenolic

technologies for green polycarbonate production
• State of the art commercially proven technologies
• Only licensor/operator with over 45 years of
operating experience
BPA

Propylene
Benzene Cumene Phenol Polycarbonate

CO
O2 Dimethyl Diphenyl
Methanol Carbonate Carbonate

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 Versalis/Lummus DMC-DPC Technologies

• Commercially well proven DMC-DPC technologies

• DMC technology
– On-purpose DMC production technology
– High product purity of 99.9%
– HDMC (high purity DMC) of 99.99%+ design available
• DPC technology
– High conversion of phenol per pass
– Highest selectivity (99.3% yield) of phenol
– Nearly stoichiometric consumption of DMC and phenol
– Product purity of > 99.6%
• Integration options
DMC ↔ DPC ↔ PC

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