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Transcript of Integrated DMC-DPC Plant for Green Polycarbonate · PDF fileIntegrated DMC-DPC Plant for Green...
A World of Solutions
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
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
A World of Solutions
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
2007
Versalis/Lummus
Partnership
1983 Ravena Plant
1988 Ravena Revamp
5,000 tons/year Prototype DMC Plant
Proven history...
1989 GE License
Production increased to
8,000 tons/year by adding second train
Licensed to GE for production
of polycarbonates
GE builds 2 plants:
Japan & Spain
1992-1998
2002
Spain revamp to
96,600 tons/year
Versalis/Lummus DMC-DPC Partnership
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Licensed 100kTA DPC Plant for
Polycarbonate Production in 2010
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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What Makes DMC “Green”?
A World of Solutions
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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)
DMC – Commercial Production Routes
A World of Solutions
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Route Company Main
By-Product By-Product
Recycle
Phosgenation Chinese Companies
Hydrochloric Acid
Difficult
Carboxylation
Japanese Ethylene Glycol
Difficult
Chinese Companies
Propylene Glycol
Difficult
Oxidative Carbonylation
Japanese HNO3
(Diluted Solution) Difficult
Versalis Europa
CO2 Easy
Comparison of DMC Processes
A World of Solutions
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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
DMC via Oxidative Carbonylation
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CO2
CO
O2
CH3OH
HCl
DMC
H2O
Gas Streams
Liquid Streams
CO/CO2
Separation
CO
Compression
Oxygen
Compression
Products
Purification
Reaction
Line HCl
Recovery Methanol
Recovery
Versalis/Lummus DMC Process
2CH3OH + CO + 0.5 O2 (CH3O)2C=O + H2O
A World of Solutions
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• 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
DMC Process Features
A World of Solutions
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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
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• ‘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
Versalis/Lummus DMC Technology Advantages
A World of Solutions
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Diphenyl Carbonate (DPC) – key intermediate for polycarbonate production
• Phosgene substitute in the production of aromatic polycarbonates (PC)
• White solid powder at room temperature
Overview
Catalyst
Preparation
DPC
Reaction
Catalyst
Recovery
DPC
Purification
CO2 DMC/Methanol
(to DMC unit)
DMC
Phenol
DPC
Anisole
Heat integration with DMC unit
Versalis/Lummus DPC Process
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PMC
Reaction
Anisole
Recovery
Lights
Recovery
Heavies
Two step reaction
• Step 1 – PMC formation: Phenol + DMC PMC + Methanol
• Step 2 – DPC formation: 2 PMC DPC + DMC
Step 1
Step 2
Non-phosgene Route to Polycarbonate
• 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
CO
0.5 O2 PC
2 PhOH
DMC DPC
CO2 H2O
2 CH3OH BPA
Versalis/Lummus Technology
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DMC
Unit
Melt
Polymerization
Unit
DPC
Unit
A World of Solutions
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• 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
Versalis/Lummus DPC Technology Advantages
A World of Solutions
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• 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
Integrated DMC-DPC Plant
A World of Solutions
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DIMETHYLCARBONATE
UNIT
DIPHENYLCARBONATE
UNIT
METHANOL
HCl
CO
O2
DIMETHYLCARBONATE
METHANOL / DMC RECYCLE
PROCESS WATER
CO PURGE CO2
CHLORINATED
VENT
DPC TO PC
ANISOLE
FRESH CATALYST
SPENT
CATALYSTCO2
PHENOL / DPC
FROM PC
HEAT RECOVERY
PHENOL
DIMETHYLCARBONATE
UNIT
DIPHENYLCARBONATE
UNIT
METHANOL
HCl
CO
O2
DIMETHYLCARBONATE
METHANOL / DMC RECYCLE
PROCESS WATER
CO PURGE CO2
CHLORINATED
VENT
DPC TO PC
ANISOLE
FRESH CATALYST
SPENT
CATALYSTCO2
PHENOL / DPC
FROM PC
HEAT RECOVERY
PHENOL
Integrated DMC-DPC Plant
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
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Methanol
Cumene Phenol
Dimethyl
Carbonate
Diphenyl
Carbonate
CO O2
Polycarbonate
BPA
Propylene Benzene
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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