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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15

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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