Using the capabilities of the Assured Aerospace
Fuels Research Facility to facilitate advances in
synthetic and alternative fuels development and
utilization
Heinz J. Robota
University of Dayton Research Institute
H. Nick Conkle
Battelle
Robert W. Morris, Jr.
Air Force Research Laboratory
2012 CRC Aviation Meetings
30 April – 3 May 2012
Embassy Suites Old Town Alexandria
Alexandria, VA
With the 50/50 blend technical
issues resolved, what comes next?
Using the AAFRF to facilitate accelerated
development of alternative fuel compositions
and preparative routes
The AAFRF provides a research and development
platform that can be used to answer practical
questions about fuels from alternative sources and
how these fuels might perform in a variety of
applications.
The Sample Production Unit can be available to
third parties through a variety of vehicles for
producing practical quantities of demonstration
fuel, testing and demonstrating synthetic routes at
larger than laboratory scale, or for coupling to
third party synthetic platforms as part of an
integrated demonstration.
Support for projects at the laboratory scale is also
available, in particular, for the purposes of
finalizing catalyst design and operating conditions
pertinent to SPU operations.
Sample Preparation Unit (SPU)
Features
• 2 Fixed-bed reactors with 3.5 L catalyst volume each
– can be operated in series, parallel, or independently
• Three distillation columns for intermediate and product
separation
• Ability to distill final product from 80 psig to ~2 psia
• Highly instrumented for critical process data capture
– Mass flow measurement on all streams supports excellent mass balance
– Temperature and pressure measurements at all critical locations
• Practical process flow: recycle of H2 and hydrocarbons
• iFIX® SCADA control of the system
• Safety PLC
SPU Process Diagram
(Configuration Used for Commissioning)
Hydrogen
Vent
Wax
Wax Feed
Tank
Naphtha
Splitter
Reactors
Vent
Vent
Recycle
Compressor
Cooler
Naphtha
Recovery
Vessel
Vent
Jet Fuel
Recovery
Vessel
Naphtha
High
Pressure
Separator
Pressurized
Naphtha
Fractionator
Jet Fuel
Vacuum
Column
Recycle
Heavy Liquid
SPU Parameters
SPU Parameters
System Pressure Design Limits
●
Reaction System
400-2000 psig
●
Naphtha Splitter
10-25 psig
●
Naphtha Fractionator
20-85 psig
●
Vacuum Column
2-20 psia
●
H2 Booster Pump
1200-2500 psig
System Temperature Design Limits
●
Reaction System
550 – 850 °F
●
Naphtha Splitter
Reboiler : 750 °F
Condenser: 100 °F (end)
●
Naphtha Fractionator
Reboiler : 750 °F
Condenser.: 100 °F (end)
●
Vacuum Column
Reboiler : 650 °F
Condenser.: 200 °F (end)
●
Wax Containing Equip
150-375 °F
●
H2/Light Gas Recycle
70-150 °F
Examples of Capabilities
Conversion of Fischer-Tropsch wax to Synthetic Paraffinic Kerosene
An example utilizing the full range of the SPU’s capabilities
Producing a specialized research surrogate fuel – isomerized C14H30
Solving the basic preparative problems at the lab scale
Preparing the specifically required catalysts for SPU-scale use
Scaling problem-specific unit operations
Demonstrate fuel-making using limited quantity materials
Converting Algal triglycerides to HEFA and diesel fuel
AAFRF SPK
Produced from FT Wax
Feed FT wax – IGI-1339A C22-C60 (Shell Bintulu distilled fraction)
Hydrocrack long-chain n-alkanes to highly isomerized alkanes
Recover C9-C15 SPK product
Recycle incompletely converted hydrocarbons and mix with fresh feed
Recycle to extinction
AAFRF SPK
properties are
nearly identical to
other SPKs
Examples of Capabilities
Conversion of Fischer-Tropsch wax to Synthetic Paraffinic Kerosene
An example utilizing the full range of the SPU’s capabilities
Producing a specialized research surrogate fuel – isomerized C14H30
Solving the basic preparative problems at the lab scale
Preparing the specifically required catalysts for SPU-scale use
Scaling problem-specific unit operations
Demonstrate fuel-making using limited quantity materials
Converting Algal triglycerides to HEFA and diesel fuel
Test isomerized C14H30 as a surrogate for
potential narrow boiling bio-fuel types
Amyris makes farnesane (C15H32):
Can we make highly isomerized
C14H30 that meets -47° C freeze?
n-C14 Use a bifunctional
metal/acid catalyst to
The cracked products are down there
isomerize the normal alkane
while minimizing cracking
We will pull some in the fractionator
losses:
the rest in the vacuum column
Mono-branched
Pt/Ultrastable Y-zeolite
AND need to limit C14 losses
C14
Separate the C11- cracked
Multi-branched
fraction with distillation
C14
The n-C impurity
12
Selectively reduce the normal
alkane residual to meet freeze
Support Scale-Up to SPU Operations: Use In-House
Extruded Catalyst to verify performance and prepare
test compositions for Dewaxing
Select and demonstrate catalyst at lab scale
Focus approach to making SPU operable
extruded catalyst and scaled operating conditions
Made 8+ liters of mixed C14 for solvent dewaxing
scale-up definition
Make the SPU catalyst charges and verify
performance – 3 L of hydrogenation
catalyst and 6 L of isomerization catalyst in
extruded form
Maintaining continuity of catalyst
formulation from lab to SPU scale critical
to success
Scale dewaxing hardware and
procedures using 8 liters of iso-C14
Three step dewaxing scale-up – must reach -65° C
At 4 L scale, recovered ~400 mL of
compliant product
At the 20 L scale – recovered 45% tetradecane as
compliant product
20 L experience has produced a design that will
Process 100 L of tetradecanes per day
Awaiting final hardware delivery
~6500 L of mixed tetradecanes ready to process
AAFRF has the facilities and knowhow required to
produce unique liquid fuel compositions
Examples of Capabilities
Conversion of Fischer-Tropsch wax to Synthetic Paraffinic Kerosene
An example utilizing the full range of the SPU’s capabilities
Producing a specialized research surrogate fuel – isomerized C14H30
Solving the basic preparative problems at the lab scale
Preparing the specifically required catalysts for SPU-scale use
Scaling problem-specific unit operations
Demonstrate fuel-making using limited quantity materials
Converting Algal triglycerides to HEFA and diesel fuel
Demonstrating the viability of new and novel
fuel sources: Algae Oils
H2 – Pd/Carbon
FAST
SLOW
H2 – Pd/Carbon
H2 – Pd/Carbon
H2O +
FAST
+ (CO + H2O)
or CO2
SLOW?
Decarbonylation or
Decarboxylation
produce odd
numbered alkanes
H2 – Pd/Carbon
H2 – Pd/Carbon
H2O +
Hydrodeoxynation through reduction
produces even numbered alkanes
Converting algal triglycerides to either diesel or jet fuels
explores a rich chemistry
Use laboratory practices which are
scalable to SPU operations
Deoxygenated alkane mixture
hydro-converted to isomers and
cracked products with Pt/US-Y
n-C17
n-C18
n-C15
n-C16
Selective removal of n-alkanes
improves cold weather flow –
Arctic Grade Diesel Fuel
Conclusions
•The AAFRF combination of scalable laboratory capabilities
linked to the practical scale SPU provides a flexible platform
for synthetic and alternative fuels research
•The physical space provides a site with a control system where
third parties can site upstream or downstream process units for
demonstrations or production of novel fuels
•The AFRL provides straightforward access through UDRI by
means of an existing CRADA
•Personnel are knowledgeable, capable, and experienced in
quickly converting concepts to testable fuels
Acknowledgements
This research was supported, in part, by the U. S. Air Force Cooperative Grant
Numbers F33615-03-2-2347 and FA8650-10-2-2934 with Mr. Robert W. Morris Jr.
serving as the Air Force Grant Monitor. The research was also sponsored by the
State of Ohio Subrecipient Award No. COEUS # 005909 to the University of
Dayton (Dr. Dilip Ballal as the Grant Monitor) under the “Center for Intelligent
Propulsion and Advanced Life Management,” program with the University of
Cincinnati (Prime Award NO. TECH 09-022). The authors gratefully acknowledge
this grant support.
Thank you to UDRI personnel: Steve Zabarnick, Matthew de Witt, Rich Striebich,
Linda Shafer, Ryan Adams, Zachary West, Dave Thomas, Gordon Dieterle, James
Shardo, Jerry Grieselhuber, Jeff Coleman, Jeff Unroe, Alan Wendel, Billy Kelley,
Dennis Davis, Ted Williams, David Gasper, Scott Breitfield, Rhonda Cook, Zachary
Sander, Mason Luo, Amanda Stewart, Jeremy Jones, Jhoanna Alger, Andrew
Palermo, Albert Vam, Roger Carr, Becky Glagola
Thank you to Battelle personnel: Satya Chauhan, Eric Griesenbrock, Kevin Rose, Nick
Conkle, Grady Marcum, Bill Jones, Mike O’Brian, George Wrenn
Thank you to Air Force Personnel: Lt. Mark Roosz, Lt. Adam Parks, Milissa Lawson
Thank you to UTC Personnel: Jennifer Stafford, Steve Procuniar
Test Results
For 3 Campaigns
Run 5 Campaign No.
Duration
1
2
3
10 days
10 days
6 days
Objectives
Reactor output C9-C16 level, %
Fractionator overhead C9-C16 retention
Fractionator bottoms C3-C8 level, %
Vacuum column overhead C9-C16 yield
Vacuum column overhead C17+ level, %
>
40
< 0.05
<
1
> 0.7
< 1.3
SPK production rate, gal/day
>
10
37
0.01
4
1.0
5
5
Initial Results
39
40
0.03
0.13
0
0
0.8
0.7
0.9
0.3
6
Commissioning goals and objectives met
10