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2003 texas
Membranes for Hydrocarbon Recoveryin Petrochemical, Refinery and
Natural Gas Processing Applications
R.W. Baker, A.R. Da Costa, D.E. Gottschlich, M.L. Jacobs, K.A. Lokhandwala, A.P. Mairal, I. Pinnau and J.G. Wijmans
Membrane Technology and Research, Inc.Menlo Park, CA 94025www.mtrinc.com
Texas Technology ShowcaseHouston, Texas
March 17 – 19, 2003
Membrane Technology and Research, Inc.
• Company founded in 1982, dedicated to development and commercialization of membrane-based separation technologies.
• Novel technologies based on innovative R&D, funded largely through U.S. government contracts (Department of Energy, Environmental Protection Agency, National Science Foundation, Office of Naval Research, Department of Agriculture).
• Most commercial applications to date involve separations in the gas phase.
• Several liquid phase separation applications are under development
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COMPANY STRUCTURE
• Marketing and Sales– Houston and Brussels Sales Offices
• Engineering• Membrane and Module Manufacturing• Research and Development• Finance and Administration
Approximately 40 employees total.Large installations are constructed by third party fabricators based on MTR engineering packages.
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MTR Multilayer Composite Membrane
SelectiveLayer
MicroporousLayer
Supportweb
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MEMBRANE PERMEATION BEHAVIOR
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Permeation through nonporous polymer film is governedby diffusion and sorption.
Diffusion favors smaller molecules.Sorption favors larger molecules.
Permeation behavior of glassy polymers (diffusion dominates):
He > H2 > CO2 > O2 > CO > N2 > CH4 > C2H6 > C3H8
Permeation behavior of glassy polymers (sorption dominates):
C3H8 > C2H6 > CO2 > CH4 > H2 > O2 > He > CO > N2
MTR’s Spiral-Wound Module
SpacerMembraneSpacer
Permeate flowafter passing through
membrane
Feed flowCollection pipe
Feed flow
Module housing
Permeate flowResidue flow
Residue flowFeed flow
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MTR GAS SEPARATION HISTORYMTR has achieved a number of world wide “firsts” in commercializingnovel and innovative gas separation applications:
1988: First CFC and HCFC Recovery System,20 membrane systems installed
1992: First VCM Recovery System in PVC Plant,14 membrane systems installed
1996: First Monomer Recovery System in PP/PE Plant,25 membrane systems installed, Kirkpatrick Award
1999: First Ethylene Recovery System in OxidationReactor Process, 3 systems installed
2001: First Fuel Gas Conditioning System Installed3 systems installed
2002: First Natural Gas Nitrogen Removal System Installed
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VOC Recovery Capacity of VaporSep SystemsInstalled in Chemical Processing Industry
Total Amount Recovered Since 1992: 355,000 ton
0
20,000
40,000
60,000
80,000
100,000
20022001200019991998199719961995199419931992
Year
AnnualVOC
RecoveryCapacity(ton/year)
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Energy Savings Capacity of VaporSep SystemsInstalled in Chemical Processing Industry
Total Energy Saved Since 1992: 19 trillion Btu
AnnualEnergySavingsCapacity(trillion
Btu/year)
0
1
2
3
4
5
6
Year
20022001200019991998199719961995199419931992
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VaporSep Application Example:Recovery of VCM from PVC Manufacturing
• Problem: Loss of VCM through PVC reactor purge gas
– Lost material = 0.5 to 5 million lb per year– Emissions restrictions
• Treatment alternatives:– Incineration + HCl scrubber– MTR VaporSep system
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Vinyl Chloride Recovery in PVC Plant
Compressor
Condenser
Membrane
Reactor
Residue
Condensed VCM
PVC
To incinerator
FreshVCM
Permeate
99% VCM
20 - 70% VCM
1 - 5% VCM
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Capital: 10% of Incineration
Payback: less than 1 year
Polyolefin Production Process
Nitrogen
To flare (N2, C4, C3, C2)Monomer
supply and purification
Monomer supply and purification
Other raw materials
supply and purification
Other raw materials
supply and purification
Polymerization reactor
Polymerization reactor
Extrusion/pelleting
Extrusion/pelleting
Resin degassing
Resin degassing
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Membrane Recovery of Hydrocarbons in Polyolefin Manufacture: Purge Bin
Monomer supply and purification
Monomer supply and purification
Other raw materials
supply and purification
Other raw materials
supply and purification
Polymerization reactor
Polymerization reactor
Resin degassing
Resin degassing
Extrusion/pelleting
Extrusion/pelleting
Recycled N2
Recovered C4, C3, C2Membrane
systemMembrane
system
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Propylene Recovery System
Compressor
Purge bin
Polymer product
Hydrocarbons in nitrogen
Refrigerant
Recovered propylene
Recycle topurge bin(99.9% nitrogen)
Knock-out Nitrogen
purge gas
Resin
Permeate
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Monomer supply and purification
Monomer supply and purification
Other raw materials
supply and purification
Other raw materials
supply and purification
Polymerization reactor
Polymerization reactor
Resin degassing
Resin degassing
Extrusion/pelleting
Extrusion/pelleting
C4, C2
Membranesystem
Membranesystem Inerts to flare
Membrane Recovery of Hydrocarbons in Polyolefin Manufacture: Reactor Purge
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Reactor Purge Recovery
Ethylene-depleted streamPolymerization
Reactor
Recycle Gas:30% Ethylene in H2 (6%), C4 (8%), N2 (56%)(800 lb/hr)
Membrane
Ethylene-enriched stream
Monomer feed
Polymer discharge
Inert purge
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Component Recovery (lb/hr) Credit ($/lb) Annual Value ($1000)
Ethylene 290 0.20 493Butene 284 0.20 483
Total: $ 976
VaporSep system cost: $ 300,000Power requirement: none
Reactor Purge Recovery
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Ethylene Recovery in EDC Production
Condenser
Membrane
Scrubber
ReactorRecovered Ethylene and EDC
Recycle Gas
To incinerator
FEEDC2H4, HCl, O2,
Impurities
EDC product
HCl + CO2
Inert Purge 25% C2H4,
3% EDC, 72% Inerts
VaporSep Unit
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Inerts to be purged:
Ethane (present in Ethylene feed)Argon (present in Oxygen feed)
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Ethylene Recovery in EDC Production: Recovery Economics
Component CurrentLosses (lb/hr)
Losses withVaporSep
(lb/hr)
Annual Value ofrecovered Material
($/yr)Ethylene 141 13 218,000EDC 74 1 93,000
Total: $ 311,000
VaporSep system cost: $ 400,000Power requirement: 50 HP
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LIQUID PHASE SEPARATIONS
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• Pervaporation– Aroma and FRlavor recovery– Solvent Recovery / Waste Reduction– Ethanol Production through Fermentation
• Aqueous Nanofiltration– Oil / Water Separation (Bilge and Ballast Water)
• Organic Nanofiltration– Separation and Purification of vegetable Oils and
Proteins from Extraction Solvents– Heterogeneous Catalysis
Polyethylene Purge Bin Application
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Chemopetrol Propylene Recovery System
FabricationInstalled
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Kemya Propylene Recovery System
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