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?

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. Using the AAFRF to facilitate accelerated development of alternative fuel compositions and preparative routes

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 H 2 and hydrocarbons iFIX ® SCADA control of the system Safety PLC

SPU Process Diagram (Configuration Used for Commissioning)

SPU Parameters System Pressure Design Limits ● Reaction System psig ● Naphtha Splitter10-25 psig ● Naphtha Fractionator20-85 psig ● Vacuum Column2-20 psia ● H 2 Booster Pump psig System Temperature Design Limits ● Reaction System550 – 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 °F ● H 2 /Light Gas Recycle °F

Examples of Capabilities Producing a specialized research surrogate fuel – isomerized C 14 H 30 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 Conversion of Fischer-Tropsch wax to Synthetic Paraffinic Kerosene An example utilizing the full range of the SPU’s capabilities

AAFRF SPK Produced from FT Wax AAFRF SPK properties are nearly identical to other SPKs Feed FT wax – IGI-1339A C 22 -C 60 (Shell Bintulu distilled fraction) Hydrocrack long-chain n-alkanes to highly isomerized alkanes Recover C 9 -C 15 SPK product Recycle incompletely converted hydrocarbons and mix with fresh feed Recycle to extinction

Examples of Capabilities Conversion of Fischer-Tropsch wax to Synthetic Paraffinic Kerosene An example utilizing the full range of the SPU’s capabilities Demonstrate fuel-making using limited quantity materials Converting Algal triglycerides to HEFA and diesel fuel Producing a specialized research surrogate fuel – isomerized C 14 H 30 Solving the basic preparative problems at the lab scale Preparing the specifically required catalysts for SPU-scale use Scaling problem-specific unit operations

Test isomerized C 14 H 30 as a surrogate for potential narrow boiling bio-fuel types Amyris makes farnesane (C 15 H 32 ):

Can we make highly isomerized C 14 H 30 that meets -47° C freeze? The n-C 12 impurity The cracked products are down there We will pull some in the fractionator the rest in the vacuum column AND need to limit C 14 losses n-C 14 Mono-branched C 14 Multi-branched C 14 Use a bifunctional metal/acid catalyst to isomerize the normal alkane while minimizing cracking losses: Pt/Ultrastable Y-zeolite Separate the C 11- cracked fraction with distillation 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 C 14 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

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 Scale dewaxing hardware and procedures using 8 liters of iso-C 14 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 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 C 14 H 30 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 H 2 – Pd/Carbon FAST H 2 O + FASTH 2 – Pd/CarbonSLOW?H 2 – Pd/Carbon H 2 O + Hydrodeoxynation through reduction produces even numbered alkanes + (CO + H 2 O) or CO 2 H 2 – Pd/Carbon Decarbonylation or Decarboxylation produce odd numbered alkanes H 2 – Pd/CarbonSLOW Converting algal triglycerides to either diesel or jet fuels explores a rich chemistry SLOW

Use laboratory practices which are scalable to SPU operations n-C 15 n-C 16 n-C 17 n-C 18 Deoxygenated alkane mixture hydro-converted to isomers and cracked products with Pt/US-Y 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 F and FA 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 # 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 ). 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 Commissioning goals and objectives met