Professional Documents
Culture Documents
1 R. Perry 02/22/2013
GE a heritage of innovation
Founded in 1892
2 R. Perry 6/19/2013
GE today
Energy Healthcare GE Capital
Aviation
Transportation
Market-focused R&D
First U.S. industrial lab Began 1900 in Schenectady, NY Founding principle improve businesses through technology One of the worlds most diverse industrial labs
4 R. Perry 6/19/2013
A tradition of innovation
1909 1913 1927 1932 1938 1942 1953 1955 1962 1973 1984 1994 1999 2004 2009 2010 2012 Ductile tungsten Medical X-ray First television broadcast reception Langmuir Nobel Prize in chemistry Invisible/glareless glass First US jet engine LEXANTM polycarbonate Man-made diamonds Semi-conductor laser Giaever Nobel Prize in physics Magnetic resonance imaging GE90 composite fan blade Digital X-ray Lightspeed VCT Wide Bore 1.5T MR System Energy SmartR LED Durathon Battery
5 R. Perry 6/19/2013
7 R. Perry 02/22/2013
CO 2 Capture Technologies
Post-combustion CO 2 capture
Pre-combustion CO 2 capture
Separation processes
Amine solvent
(baseline) Low P CO2 High steam loss
TM
(baseline)
8 R. Perry 02/22/2013
Develop a novel, CO2 capture solvent with: 90% Carbon capture efficiency 25% Increase in capacity vs MEA
Robert Perry Research Experience in Carbon capture At NCCC, Birmingham, AL June 19, 2013
9 R. Perry 6/19/2013
Acknowledgement . The information, data, or work presented herein was funded in part by the Advanced Research Projects Agency Energy (ARPA-E), U.S. Department of Energy, under Award Number DE-AR0000084 and DOE- NETL under Award Numbers DE-NT0005310 and DE-NT0007502. Disclaimer. The information, data, or work presented herein was funded in part by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.
10 R. Perry 6/19/2013
Team Members
GRC Bob Perry Mike OBrien Sarah Genovese Ben Wood Gosia Rubinsztajn Tiffany Westendorf Rachel Farnum John McDermott Irina Spiry Harish Acharya Surinder Singh Mark Doherty Paul Wilson Paul Buckley GEE Ravi-Kumar Vipperla Lisa Wichmann Ray Steele Michael Yee Martin Tabbita U Pitt Bob Enick Deepak Tapriyal Lei Hong Alex Stola
11 R. Perry 6/19/2013
Generation of Electricity
http://www.eia.gov/electricity/
~40% of US electricity comes from coal This source of power will not be eliminated in near future
12 R. Perry 6/19/2013
Absorb CO2 at 50oC/ 1 atm Rich solvent heated to 120 oC to release CO2 Lean solvent recycled to absorber CO2 compressed for storage Typical capture process
R. Vipperla
15 R. Perry 6/19/2013
30% power lost in conventional MEA process (~80% increase in COE). Significant portion of that due to heating/condensing water Other issues with MEA: - Corrosivity - Thermo-oxidative instability - Volatility
16 R. Perry 6/19/2013
Thermal stability
High CO2 loading High desorption pressure
Aminosiloxanes
Low cost
17 R. Perry 6/19/2013
Aminosiloxanes
High molecular weight amino polysiloxanes used in conditioners for hair & in textile treatment Amine content of these commercial polysiloxanes low little CO2 capacity
Need low molecular weight monomeric or oligomeric versions Commercially available examples:
Bis(aminopropyl)tetramethyldisiloxane
Bis(aminoethylaminomethyl)tetramethyldisiloxane
GAP-0
GAP-AEAM
18 R. Perry 6/19/2013
Variety of aminosiloxanes
GAP-0 MDM
GAP-1
GAP-AEAM M3T
DAB-0
GAP-AEAP
DAB-Me
GAP-nPr
GAP-Dytek
DAB-Me2
19 R. Perry 6/19/2013
Examples:
M. OBrien
Example:
NaOMe / EtOAc/MeOH
PdCl2L2 / PPh3
R. Perry
Example:
M. OBrien R. Perry
mp = 132-134C
Ether/THF Ether
60 98
40 2
M. OBrien R. Perry
Cyclic disiloxane formed instead of linear material Some reductive decyanation seen in LAH
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MM
D4
MDxM
(linears)
Dy
(cyclics)
M. OBrien
Example:
GAP-0
MDM (GAP-1)
Siloxanes mixed and reaction allowed to go to equilibrium Catalyst is then removed or destroyed and volatiles (cyclics) stripped Can use functional D groups as well to control amine content Material is actually a mixture of species with average composition equal to target
24 R. Perry 6/19/2013
Silicone Nomenclature
-CO2
Me Si Me 4 O
Me Si Me
Me Si Me
M. OBrien
However these materials showed inferior CO2 uptake (<10% wt gain). - Very viscous carbamates => again poor mass transfer tested in bulk
Given that carbamates are mostly solids or very viscous liquidswanted to test in non-aqueous co-solvents
27 R. Perry 6/19/2013
Co-solvent Selection
Needs to solubilize both aminosiloxane and carbamate at high concentrations
High boiling to minimize evaporative loss on desorption
Thermally stable/low toxicity/etc Low specific heat Best results obtained with ethylene glycol oligomers
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Si O Si Me
Me
17.3% (98%)
14.6% (92%) 13.5% (94%) 9.5% (72%)
10.2% (115%)
8.6% (108%) 8.2% (116%) 5.4% (84%)
Me
Me NH2
H2N
Si O Si Me Me
Me H2N
Me NH2
Si O Si Me
Me
Me
Me NH2
H2N
Si O Si Me Me
All 1:1 TEG solutions gave liquid carbamate blends Improved mass transfer in liquid => closer to theoretical uptake
13C{1H}
164.34
RNH 3 O
NHR
159.96
RNH 3 O
OH
168
167
166
165
164
161
160
159
158
157
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H N
21.8% (69%)
NH2
Me
Me N H
Si O Si Me Me
16.7% (64%)
16.5% (79%)
11.8% (90%)
9.9% (95%)
H2N
Me N H
Me N H
Si O Si Me Me
NH2
Tetra-amines: theoretically 2 CO2 s per molecule High CO2 weight gain number neat but not as close to theoretical - Half the amines are secondary - Solids not as powdery mass transfer issue TEG solutions all liquid, uptake closer to theoretical
31 R. Perry 6/19/2013
Corrosion Studies
Neat GAP-0
GAP-0 0.00
0.00
C1018 @ 50 C
50/50 GAP-0/TEG
GAP/TEG 0
Weight Loss (%)
0 -0.05
500
1000
1500
oC
2000
2500
C1018 @ 100 C C1018 @ 150 C
3000
500
1000
1500
2000
2500
3000
-0.05
C1018 @ 50 C C1018 @ 100 C C1018 @ 150 C 340L @ 50 c 40l @ 100 c 340 l @ 150 c
-0.15
-0.15
30% MEA/TEG
30% MEA/TEG 0.00 0
Weight Loss (%)
500
1000
1500
2000
3000
-0.10
Carbon steel stable in neat GAP-0 to 1000 h Weight loss/corrosion seen with carbon steel @ 150 oC in GAP-0 /TEG and large effect with 30% MEA/TEG @ 100 oC
33 R. Perry 6/19/2013
K. Zarnoch
Physical Properties
lnP (psia)
0.0026
0.0028
0.0030
0.0032
Viscosity
5000 4500 4000 3500
R. Enich, D. Tapriyal
1/Temperature (1/K)
0.0034
Vapor pressure
0% carbamate 30% carbamate 60% carbamate 100% carbamate
Viscosity (cP)
S. Genovese
Density
B. Wood B. Wood
35 Successfully demonstrated with GAP-0 and GAP-1/TEG blend R. Perry 6/19/2013 Over time GAP-0 carbamate crystallized while GAP-1 version did not
Energy Penalty
ASPEN Plus model built for CO2 separation using GAP-1; Updated with experimental results Energy Penalty: GAP-1 EP for the overall system ~24% vs. ~31% for MEA
36 R. Perry 6/19/2013
Aminosiloxanes efficiently & reversibly react with CO2 Primary amine functionality works best Enhanced thermal stability and vapor pressure over MEA
Polyethylene glycol derivatives like TEG can be used to maintain solution liquidity during CO2 absorption Mass and heat transfer may be mitigated using TEG
Best candidate currently appears to be GAP-1/TEG Received additional DOE grant to scale this process up to 80-100X previous lab scale
37 R. Perry 6/19/2013
Bench-Scale Unit
38 R. Perry 6/19/2013
30% power lost in conventional MEA process (~80% increase in COE) Significant portion of that due to heating/condensing water Low water based processes reduce energy/cost (~50% COE increase) Eliminate all non-reactive co-solvents (potential of ~40% COE increase)
39 R. Perry 6/19/2013
Phase-Changing Absorbent
Some were high quality, free-flowing powders Those that were powder exhibited high CO2 uptake.
- Some >50% higher weight gain than 30% MEA Could we devise a process to allow use of these materials?
40 R. Perry 6/19/2013
1
1 Make the solid (Solvent development)
2 Collect the solid (Solid isolation)
Low Pressure
High Pressure
4
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Low hygroscopicity as salt Low volatility (vapor pressure) High reaction rates
High desorption pressure
6/19/2013
17.3 (98)
13.1 (96) 17.8 (99) 18.8 (103)
Powder
Powder Powder Powder
18.4 (104)
14.1 (103) 16.6 (92) 17.4 (96)
Chunky Solid
Sticky Wax Glass Sticky Gum
17.3 (92)
Powder
20.7 (109)
Powder
M. OBrien
NH2 NH2
Pure compounds GAP-0 & cyclic diamine looked best Oligomer-based salts softened with H2O & became sticky
43 R. Perry 6/19/2013
Thermal Stability
Determine inherent stability by heating to 150oC for 3 months
120 100 % Starting material remaining
80
60
40
20
Time (days)
Many materials show good inherent stability Cyclic diamine and GAP-AEAM are exceptions Studying decomposition products to provide insight into potential stabilization approaches (additives are commonly used in these 44 R. Perry systems) 6/19/2013
Thermal Stability
Vapor Pressure
MEA control shows excellent agreement with literature 1- 2 orders of magnitude reduced vapor pressure vs MEA
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Heats of Reaction
MEA
R. Farnum
47 R. Perry 6/19/2013
Heats of Reaction
Compd
GAP-0 1 2 3 4 5 6 7 8
R
H Methyl Ethyl Propyl Isopropyl Butyl Isobutyl t-Butyl Cyclohexyl
% Wt Gain
17.3 18.3 16.5 14.3 6.1 13.1 10.8 0.6 8.5
% of Theory
100 115 114 108 46 107 89 5 85
Heat of Absorption (kJ/kg CO 2) 2554 2168 2151 2125 2026 2175 2013 ND 2035
48 R. Perry 6/19/2013
Microscopy of Particles
35%
Cumulative Number
% passing
STATISTICS Mean: 4.3 Std. Dev.: 3.8 Minimum: 0.2 Maximum: 38.0 Object Count: 1646 (based on number)
100.0%
80%
90.0%
80.0%
70.0% 60.0% 50.0%
15%
10%
40%
30% 20%
40.0%
30.0% 20.0% 10.0% 0.0% 1 10 100 1000 10000
5% 0%
10% 0%
11
13
15
17
19
21
23
25
27
29
31
33
35
37
39
particle size, um
T. Westendorf
51 R. Perry 6/19/2013
Slurry Transport
2wt%
5wt%
10wt%
15wt%
20wt%
30wt%
40wt%
50wt%
52 R. Perry 6/19/2013
Desorption
Desorption Isotherms
R. Farnum S. Genovese
Unit Operations
Two spray reactors, 1 w/ MS capability
Slurry transfer unit with ISCO pumps
Desorber Unit
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Improvements in Desorption
Not satisfied with desorption process Sacrificing inherent ability of GAP-0 Revisit solids transport
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56 R. Perry 6/19/2013
Further Improvements
Take process one step further Use extruder to desorb CO2 from carbamate combine 2 unit operations save space and money
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58 R. Perry 6/19/2013
GAP-0
carbamate
Increasing pressure
psig
63 27 80
60 0
>68 62
84
Effective tool for in-situ monitoring of carbamate formation Real time measurement
Extruder parameters varied both back-pressure and feed rate and rpm.
60 R. Perry 6/19/2013
Early model
Refined Model
IR composition data permitted early model development Refined model with additional data shows closer agreement Expand experimental parameters
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Continuous System
System ~90% complete
62 R. Perry 6/19/2013
R. Vipperla
63 R. Perry 6/19/2013
Technology Commercialization
Highly desirable to have strong business pull Network to know your colleagues/competitors Be realistic dont over sell the process/technology Focus on product areas that are strengths Bite off manageable pieces of opportunity Look for smaller scale operations that can retire risks
64 R. Perry 6/19/2013
Summary
Novel use of aminosilicone sorbents for CO2 capture 5th year of effort
Partner with external industries to validate process(es) and bring value to both
65 R. Perry 6/19/2013
Thank You
66 R. Perry 6/19/2013