Liquid Fuels and Electricity from IT-Fuel Cells

Carl A. Willman

17th Annual SOFC WorkshopPittsburgh, PAJuly 21st, 2016

Partners

University of Connecticut – Cell manufacturingtechnology developmentPacific Northwest National Laboratory – GTL catalystand cell developmentEnergy and Environmental Research Center at theUniversity of North Dakota – GTL catalyst evaluation andpressurized testingMassachusetts Institute of Technology – Electrodeinterface characterization

Objective

Project Objective:To develop a cell technology capable of direct conversion of methane to liquid product, methanol or formaldehyde, by electrochemical partial oxidation at intermediate temperatures (<500°C), to provide means for an economic utilization of stranded gas.Targets:

High Methane Conversion YieldHigh Selectivity for Methanol Production Composite Low Temperature Electrolyte Redox Tolerant AnodeScalable Manufacturing Methods

Value Proposition

Western ND

Population ~100,000

Eastern NY, CT, MA & RIPopulation~25,000,000

Image – NASA Earth Observatory

Electrochemical Gas-to-Liquid (EC-GTL) offers a cost effective method forreducing emissions impact of strandedgas sourcesScalability, modular nature, andtransportability of electrochemicalsystem also provide the means toeconomically utilize associated gas atlow production wellheadsThe EC-GTL technology will meetARPA-E’s Mission Areas:

Enhance the economic and energysecurity of the United StatesEnsure that the United Statesmaintains a technological lead indeveloping and deploying advancedenergy technologies

Satellite image of visible light sources in US, demonstrating level of natural gas flaring

Value Proposition

US. Bureau of Labor Statistics, Producer Price Index by Commodity for Fuels and Related Products and Power: Industrial Electric Power [WPS054321], retrieved from FRED, Federal Reserve Bank of St. Louis; https://fred.stlouisfed.org/series/WPS054321US. Bureau of Labor Statistics, Producer Price Index by Commodity for Fuels and Related Products and Power: Industrial Natural Gas [WPU0553], retrieved from FRED, Federal Reserve Bank of St. Louis; https://fred.stlouisfed.org/series/WPU0553US. Bureau of Labor Statistics, Producer Price Index by Commodity for Chemicals and Allied Products: Synthetic Organic Alcohols, Mixed and Unmixed [WPU061403996], retrieved from FRED, Federal Reserve Bank of St. Louis; https://fred.stlouisfed.org/series/WPU061403996

Concept

O2-

AIR

CH4CH3OH, HCHO, H2O

LOAD

Electrocatalyst OxidationMOγ+δO2- MOγ+δ +2δe-

Fuel FormationMOγ+δ + δCH4 δCH3OH + MOγ

MOγ+δ + δCH4 δ/2 HCHO + Moγ + δ/2 H2O

Redox Anode

Ceramic or NiO(Li) Cathode

Electrolyte

2 e-

Electrochemical Gas-to-liquid cell utilizes a metal/metal oxide redox couple, which serves as the anode electrocatalyst, to partially oxidize CH4 to CH3OH and HCHO.

Development Approach

Development of a novel EC-GTLcell presents an opportunity fortop-down approachIncorporation of the catalyst withinthe EC-GTL anode requires abilityto withstand constant redox cyclingChosen cathode and electrolytemust provide sufficient electrodeactivity and O2- ionic conductivityto support the Redox reaction withthe EC-GTL anodeInstitutional experience with MCFCcommercialization can beleveraged to facilitate pathway tocommercialization

a) Green Support Tapeb) Pre Sintered Support

c) AFL Coated Anode Supportd) Anode Infiltrated with Catalyst

e) Electrolyte Deposited on Anode

Cell Support

Developed anode side supportwith adequate mechanical andelectrical properties, capableof withstanding redox cycling.Demonstrated operation withcarbonate electrolyte.

Catalyst Development

0

10

20

30

40

50

60

70

80

90

100

0 500 1000 1500 2000 2500 3000

Time(s)

CO

CH3OH

CO2

CH4

H2O

100 hr@ 600 °C

High Selectivity (>90%) catalyst has beensuccessfully infiltrated onto anode support.Infiltration process has shown stable particlesize after aging tests.Increased batch-mode conversion rate(~40%) observed with catalyst on anodesupport material vs. silica support. Fuel celloperation may increase further.Methanol product stability wasdemonstrated on fully activated catalyst.

Manufacturing via RSDT

Electrolyte DevelopmentRSDT has been adapted to co-deposit GDC and carbonate salts.Sufficient density achieved at ~ 20μm.Opportunity exists for optimizationto achieve full density with thinnerlayer.

Parallel path to utilize dense GDCis also under investigation.Both approaches have recentlyshown acceptable microstructureand leak analysis results, awaitingelectrochemical testing.

System Design

Developed system process flow sheet identifying balance-of-plantrequirements and performed system simulations based on first-principle methods.Cell performance based on project milestones, and cost on prior SOFCdevelopment, identified small systems as economically attractive.

Results of the System AnalysisBasis: One Barrel Per Day (BPD) of

Methanol ProductionRaw Gas Input 3.0 MCFDCell Area 12.5 M2

Gross DC Power 12.48 kWPlant Parasitic Loads 0.90 kWNet AC Power Output 10.9 kW

Development Roadmap

Finalize electrolyte fabrication process.Revisit cathode deposition with RSDT.Optimize anode catalyst deposition for higher activity.Map cell operating conditions for optimal performanceenvelope.Increase cell area.

Acknowledgements

DOE/ARPA-E: Grigorii Soloveichik, John Tuttle, Mark Pouy,Scott LitzlemanPNNL: Evgueni Polikarpov, Lirong Zhong, Alex Mitroshkov,HVP Nguyen, Larry Pederson, Olga MarinaEERC: Ted Aulich, Jivan Thakare, Malhar KhambeteUCONN: Radenka Maric, Mark Aindow, Na Li, AbhinavPoozikunnathMIT: Bilge YildizFCE: Hossein Ghezel-Ayagh, Alireza Torabi, Mick Barton,Steve Jolly