Table Of ContentCopyright
by
Steven Michael Fulk
2016
The Dissertation Committee for Steven Michael Fulk Certifies that this is the
approved version of the following dissertation:
Measuring and Modeling Aerosols in Carbon Dioxide Capture by
Aqueous Amines
Committee:
Gary T. Rochelle, Supervisor
Roger T. Bonnecaze
Eric Chen
Lea Hildebrandt Ruiz
Elena McDonald-Buller
Measuring and Modeling Aerosols in Carbon Dioxide Capture by
Aqueous Amines
by
Steven Michael Fulk, B.S.
Dissertation
Presented to the Faculty of the Graduate School of
The University of Texas at Austin
in Partial Fulfillment
of the Requirements
for the Degree of
Doctor of Philosophy
The University of Texas at Austin
August 2016
Dedication
To Joy Desta Fulk
Acknowledgements
First, I would like to thank Dr. Gary Rochelle for his continued flexibility and
understanding as an advisor. My transition into graduate school was anything but a
smooth landing, but he continued to gently guide, and at times negotiate, my path to
professional development and becoming a critical thinker while always providing room
for life outside of the lab. His seemingly infinite well of ideas is inspirational and taught
me a lot about higher level problem solving and how to not get so caught up in the weeds
of excessive detail. I am tremendously grateful for his influence in my life.
Dr. Eric Chen was a valuable mentor in my development when I began working
out at the Pickle Research Center with seemingly no hands-on skills. I learned a lot about
being organized, how to manage projects, and getting my hands dirty. He also managed
an endless army of undergraduates who contributed greatly to the pilot plant work in this
study; special thanks go to Yong Kim for his work on the rack-mount FTIR.
I would like to acknowledge the numerous members of the Rochelle group who
came before me, worked beside me, and those with some time still to go. We got to
travel to many international conferences, problem solve, and talk about sports way too
much; I’m grateful for it all. To the people following in my project’s footsteps, I’d like
to extend my gratitude for providing me feedback from modeling work and for your help
finding mistakes in my data: Conlin Kang and Yue Zhang. I’d also like to give special
thanks to my on-campus officemates for their friendship, great conversation (both
research and non-research related), and numerous coffee runs: David Van Wagener,
Jorge Plaza, Peter Frailie, Darshan Sachde, and Brent Sherman. And to my Pickle
compatriots, thank you for endlessly entertaining me and your help with running
v
experiments or simply carrying things around for me: Matt Beaudry and Di Song. Most
importantly, I want to thank Stephanie Freeman and Fred Closmann for pulling me aside,
unsolicited, to give me encouragement when I need it the most.
For their financial support, I would like to thank the members of the Luminant
Carbon Management Program, the Texas Carbon Management Program, the John L.
Gidley Endowed Graduate Fellowship in Engineering, and the Department of Energy
under Award Number DE-FE0005654.
I would also like to thank several industry partners and vendors who helped
during pilot plant campaigns and development of the PDI. AECOM provided manual
sampling data and project support during SRP pilot campaigns. Southern Company
allowed us to sample at NCCC and provided support for those measurements. And
Artium, specifically Chad Sipperley and Will Bachalo, did demonstrations and ultimately
designed the custom PDI used in this work.
I owe gratitude for the numerous staff, both on-campus and at the Separations
Research Program, that have helped me in multiple facets. Special thanks to Maeve
Cooney for her endless work on quarterly reports and for keeping the lab organized and
moving. Frank Seibert, Steve Briggs, Robert Montgomery, and Micah Perry of SRP
played major roles in running the PRC pilot plant and taking data.
To my family, thank you for your years of love and support. Thank you to my
parents for encouraging me to work hard and keep a positive attitude. And to my
siblings, John and Erin, thank you all of the fun we’ve had together, our great stories, and
for the phone calls. I’m incredibly lucky to have you all in my life.
I’d personally like to thank my Gateway family for all the amazing opportunities
and support they’ve shown me. I’m incredibly blessed to have people who give me no
excuses to be a better person, give me a place to serve, and are always glad to see me.
vi
Special thanks to Tracy Guthrie for giving me a door, Karin Harper who helped me
stumble through, and Steven Mary getting me back on my feet. And for their time and
great life lessons, Rick Wells and Nathan Collins. I’d also like to thank the Greens, not
only for opening their home for small group, but for their interest in my life and
consistent encouragement for me and those who mean the most to me.
Victoria, thank you for your constant grace, kindness, optimism, and
encouragement. Though we are still new to each other, you feel like an old friend. I
hope to continue this incredible season of growth and adventure with you well into the
future. I’m tremendously grateful for you.
Finally, thank you to God for His continuous grace, courage, and wisdom as well
as His endless work in my life. Thank you for giving me life, sustaining me in health,
and providing me with a good future.
vii
Measuring and Modeling Aerosols in Carbon Dioxide Capture by
Aqueous Amines
Steven Michael Fulk, Ph.D.
The University of Texas at Austin, 2016
Supervisor: Gary T. Rochelle
Pilot scale CO capture plants have shown that amine condensation onto seed
2
nuclei results in very high amine emissions which are very difficult to control using
traditional aerosol removal techniques. Aerosol emissions can be suppressed by
adjusting operating conditions such that drops evaporate, or, alternatively, grow to a size
that can be efficiently captured by low cost methods. The effects of operating conditions
on aerosol growth were investigated by experimental measurement and numerical
modeling with sensitivity analyses.
Total particle densities and particle size distributions (PSDs) were measured using
a custom-built phase Doppler interferometer (PDI) on bench and pilot scale CO
2
absorbers. Seed nuclei were generated using vaporized H SO , gaseous SO , and flue gas
2 4 2
from a coal-fired power plant. PSDs were used to calculate the aerosol amine
concentration when compared to total phase (gas and aerosol) measurements collected by
FTIR.
The effects of operating conditions on aerosol growth were simulated in a
combined heat and mass transfer model coded in MATLAB®. Aerosol transport
equations included corrections for surface curvature and transport length scale regimes.
Absorber and water wash models were simulated using Aspen Plus®.
viii
Inlet CO is crucial in creating supersaturation in the absorber; the loading
2
difference between the aerosol and bulk solvent creates an amine driving force for
condensation. Aerosols grow faster in non-intercooled columns due to differences in
solvent composition (CO loading) and temperature.
2
H O condensation is the primary growth mechanism in the water wash. Reducing
2
the water wash amine concentration and providing additional residence time leads to
more aerosol growth. Doubling the water wash height results in a 13.7 % increase in the
final aerosol diameter for a generic 8 m PZ absorber.
Similar to some other volatile amines, PZ forms 1–5 μm aerosols because its
amine volatility is a strong function of CO loading. The amine concentration in
2
measured aerosol distributions, calculated by PDI/FTIR comparison, was one-to-two
orders of magnitude lower than the bulk solvent.
SO forms aerosol with PZ. 65 % of injected SO leaves in the aerosol phase.
2 2
Therefore, SO polishing scrubbers are essential and systems should not be designed for
2
simultaneous absorption of CO and SO .
2 2
ix
Table of Contents
Dedication ............................................................................................................. iv
Acknowledgements .................................................................................................v
Table of Contents ....................................................................................................x
List of Tables ...................................................................................................... xxi
List of Figures ................................................................................................... xxvi
Chapter 1: Introduction ..........................................................................................1
1.1.1 CO2 Capture by Amine Absorption/Stripping ..............................1
1.1.2 Volatile Losses ..............................................................................3
1.2 Aerosols at Pilot Plants ..........................................................................5
1.2.1 Mitsubishi Heavy Industries .........................................................5
1.2.2 SINTEF and TNO .........................................................................6
1.2.3 National Carbon Capture Center ...................................................8
1.3 Aerosols at the Bench Scale ...................................................................8
1.3.1 Laborelec, KIT, and TNO .............................................................8
1.3.1.1 Brachert et al. (2014) ......................................................9
1.3.1.2 Mertens et al. (2014) ......................................................9
1.3.2 Khakharia (2015) ........................................................................10
1.3.2.1 Particle Concentration ..................................................10
1.3.2.2 Supersaturation .............................................................10
1.3.2.3 Amine Reactivity..........................................................10
1.3.2.4 Overall Theory .............................................................11
1.3.3 Key Findings ...............................................................................11
1.4 Abatement Strategy ..............................................................................12
1.5 Research Scope ....................................................................................13
1.5.1 Aerosol Analytical Development ................................................13
1.5.2 Experimental Measurements .......................................................14
1.5.3 Numerical Modeling ...................................................................15
x
Description:Jorge Plaza, Peter Frailie, Darshan Sachde, and Brent Sherman. And to my Pickle compatriots, thank you for endlessly entertaining me and your help
