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Hybrid Distillation – Membrane Process to Increase Capacity and Reduce Costs
for Production of Propylene and Ethylene
AIChE Annual MeetingSalt Lake City, UT, November 8-13, 2015
Sudip Majumdar, Yosuke Koizumi, Ken Loprete, Evan Sohodski, Ken Pennisi, Stuart Nemser
Compact Membrane Systems, Wilmington, DEwww.compactmembrane.com
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Overview
• Opportunity for Olefin-Paraffin Separation• 30 Year Membrane History• CMS Stable Facilitated Transport Membrane• Preliminary Scale-Up• Engineering and Economic Evaluation• Path Forward
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Olefins are Big
Chemical Production*(1x106 lbs)
Nitrogen / Oxygen 69,600 / 58,300Ethanol 66,100Ethylene 52,900Propylene 31,100Ammonia 22,700Chlorine / Sodium Hydroxide 21,500 / 16,600Ethylene Dichloride 19,400Benzene 13,300Ethylene Oxide 5,900Acetone 3,200* 2010 Production of top 10 chemicals
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Ethylene and Propylene Product Chains
Membrane Can Touch Olefins Multiple Times
• Refinery (+ New on Purpose Propylene Sites)
• Polymer Purge Line
• Polymer Silo
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Experimental Upper Bound Based on Pure Propylene and Propane Permeation Data
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Ref: Burns and Koros, Journal of Membrane Science, 211, 299 (2003)
Historically Membranes for Olefin-Paraffin are Not Stable
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Ref: Merkel et al., Journal of Membrane Science 447, 177 (2013)
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Commercial Amorphous Fluoropolymers
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Teflon AF HyflonCytop
Facilitated Transport(Fixed Carriers)
OlefinParaffin
Facilitated Transport
Solution-Diffusion
Carrier
9Adapted from Cussler E.L.: Facilitated Transport. In: Membrane Separation Systems, vol. 2, US DOE Report, DOE/ER/30133-H1 (1990)
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Custom Amorphous Fluoropolymer (CAF)and
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• Silver is part of the polymer chain• Form stable, high flux, high selectivity
facilitated transport membranes• CAF and new synthesis procedure
potentially protects silver
Variation of Humidity
0
25
50
75
100
125
150
0
50
100
150
200
250
300
0 20 40 60 80 100
Sele
ctiv
ity
Prop
ylen
e Pe
rmea
nce
(GPU
)
Overall Humidity (%)
PermeanceSelectivity
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Effect of Feed Concentration
0
100
200
300
400
0 20 40 60 80 100
Prop
ylen
e Pe
rmea
nce
(GPU
)
Propylene Feed Concentration (Vol%)
Bot
tom
of C
3Sp
litte
r
Top
of C
3Sp
litte
rPo
lypr
opyl
ene
Rea
ctor
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Stable, Strong Performance Over Time
0
50
100
150
200
250
300
10 20 30 40 50 60 70 80
C3H
6Pe
rmea
nce
(GPU
) /
C3H
6-C3H
8Se
lect
ivity
Duration (Days)
Long Term Stability in Presence of SulfurC3H6 Permeance
C3H6-C3H8 Selectivity
Selectivity is a function of
feed stream composition and ranges
from~30 -80
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Ethylene-Ethane Mixture Separation
Olefin Permeance(GPU)
Paraffin Permeance(GPU) Selectivity
Ethylene / Ethane 275.5 3.6 76.2
Propylene /Propane 226.5 3.2 70.2
Feed: 20% Olefin - 80% Paraffin; Feed Pressure: 60 psig; Humidified Feed/Sweep; New Membrane
Preliminary Membrane Scale-up(47 mm Disc vs. 10 inch Square)
Propylene Permeance
(GPU)
SelectivityC3H6/C3H8
256 17.0 10”
10”
47 mm Disc Results
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Feed: 20% C3H6 - 80% C3H8Feed Pressure: 60 psig
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Permeance and Selectivity Map of CMS Membranes
CMSMembranes
Engineering and Economic Evaluation
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Key Assumptions: C3 Splitter Analysis
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Membrane Permeance (Propylene) 100 GPUMembrane Selectivity 20Feed Pressure 110 psiaPermeate Pressure 14.7 psiaMembrane Replacement Rate 33% per yearC3 Splitter Feedstock 50% PropyleneValue of Splitter Feed 21 cents/lbPrice of HD05 Propane 24.5 cents/lbPrice of Propylene 60 cents/lb
Distillation-Membrane Hybrid ProcessesConfiguration 2Configuration 1
• Membrane separates distillate• Retentate recycled to column• Reduces column top product purity required• Reduces reflux ratio required & saves
energy• Enables higher feed flow rate to column for
greater propane & propylene production
• Membrane separates bottom fraction• Permeate recycled to column • Very small increase in flood factor ~1%• Increases propane purity and
propylene yield
Tower
Propylene/PropaneFeed
PropyleneVapor
95% Propane
Distillation Column
Membranes
99.5% Propylene
Vacuum Pump& 2-stage intercooled
compressor
Compressor w aftercooler
Superheater
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0
2
4
6
8
10
12
14
16
18
20
0%
25%
50%
75%
100%
125%
150%
175%
200%
225%
250%
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Payb
ack
Perio
d (m
onth
s)
Inte
rnal
Rat
e of
Ret
urn
Case
Payback IRR
Selectivity
35 50
Base Steam & Electricity
Price-50% +50%
Propane/Propylene
Price-20% +20%
Replace Rate
25% 50%
Permeance
75 85
Propane & Energy Price
-20% +20%
Feed Value
-15% +15%
Membrane Completing Separation of HD10 Propane at Bottom of C3 Splitter with Propylene Capacity of 40,000 Tons per Year
Membrane System for Propylene Recovery from Polypropylene Reactor Purge
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Base Case Economics
Payback Months
C3 Splitter ~ 11
Polypropylene Reactor Purge ~ 8
Summary / Path Forward
CMS Demonstrated Stable Olefin-Paraffin Facilitated Transport Membrane
Attractive C3 Splitter Economics Payback < 15 months
Key Next Steps Optimize Process – 2016 Build Larger Membrane Modules – 1H / 2016 Demonstrate at Plants – 2H / 2016 - 2017
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The authors gratefully acknowledge the support of the US Department of Energy through Small Business Innovation Research (SBIR) Awards.
Acknowledgement
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