Liquid Fuels and Electricity from IT-Fuel Cells

Carl A. Willman

16th Annual SOFC WorkshopPittsburgh, PAJuly 16th, 2015

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.

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

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 and indirectly oxidize CH4 to CH3OH and HCHO.

Partners

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

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

SEM micrograph of potential EC-GTL cell under development at

FCE

Cell Materials - Support

Initial investigation focused onmodified NiO as cathode sidesupport, including productionline MCFC cathode, but wasfound to have insufficientmechanical strengthAnode side ceramic supportwas chosen, with desirableconductivity and mechanicalproperties

SEM micrograph of ceramic anode support with functional layer and

electrolyte

Cell Manufacturing

To reduce future cell cost and streamlinecommercialization, advanced manufacturingtechniques, that can be readily scaled to highvolume are being investigated as primarysource of laboratory sample testingReactive Spray Deposition Technology(RSDT) is employed to produce cellfunctional layers, in both porous and denseforms, with minimal to no post depositionprocessing/sintering required

Economically viable RSDT for fabrication of the EC-GTL cell components and

thin film layers

GTL Catalyst Development

Development of GTL catalyst that favorsthe production of methanol/al with highselectivity as opposed to reformation tohydrogenCatalyst selection using candidatematerials tested in batch-reactor modeOver twenty catalyst compositions havebeen evaluated, with multiple promisingcandidates identifiedPromising catalysts, based on selectivityand activity in ideal cell operation range, tobe incorporated into button cells, thenlarge area anodes

Batch mode reactor for catalyst evaluation.

GTL Catalyst Development

Catalyst screening has identified candidates with promising selectivity over desired range of temperatures

Less than 1% CO observed, no CO2

>90% Selectivity up to 600 °CContinued development will focus onincreased activity and conversion, whilepreserving selectivity

EC-GTL System ModelingSystem Process Flow Sheet Identifying the balance-of-plant processingrequirements developedPerformed system simulations based on thermodynamics first principlemethodsFocus on low-volume (~100 MCFD) associated gas systemsCost estimate based on prior fuel cell system development

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

IT-GTL System

IT-GTL Anode

IT-GTL Cathode

Fresh AirBlower

Nat Gas

Exhaust

CatalyticOxidizer

Desulfurizer

AnodeRecycleBlower

Suplemenary Water

Air

Cathode Air Preheater

IT-GTL Module

Oxidant-side Process LoopFuel-side Process Loop

Anode HRU

Liquid Product

Separation

Liquid Product

EC-GTL System Cost

PILOT EC-GTL SYSTEM ANNUAL OPERATING COST

ANNUAL OPERATING COST ITEMSFUEL CELL STACK REPLACEMNT(3 RPLCMNTS) $ 11,459

FUEL (FLARED GAS) 0FUEL DESULFURIZER (10% UNIT COST) $ 29,883

SYSTEM OPERATION(O&M)2 TECHS ,$50/HR, 2200HR/YR) $ 220,000

TOTAL $ 261,342

ANNUAL REVENUES

POWER SALE (486.4 KW) (6 CENTS/KWHR) $ 229,050

METHANOL SALES (1.14GPM)($1.33/GAL) $ 716,909 TOTAL $ 945,959

ANNUAL COSTANNUALIZED CAPITAL COST @ 8% $ 173,000 ANNUAL OPERATING COST $ 261,342 ANNUALIZED INSTALLATION COST $ 153,000

TOTAL $ 587,342

PAYBACK PERIOD, YRSANNUAL COST/REVENUES 0.62

RATE OF RETURN,% ANNUAL REVENUES - 21%ANNUAL COST/INITIAL COST

Case Study for 40 BPD Plant

Cell performance assumptionsbased on end of project milestonesEquipment and Stack costestimated based on SOFCsystems of comparable scaleGas composition based on Bakkenassociated gas

Results

Material selection – parallel path developmentof multiple cell designs show promise to meetproject performance milestonesFabrication – RSDT parameters have beenrefined to new material sets to deposit layerswith desired characteristicsCatalyst development – Multiple catalysts haveshown very high selectivity to desired productsSystem analysis has shown the EC-GTL hasthe potential of co-generating 10 kw netelectricity while producing one Barrel ofmethanol per day (BPD), with promisingeconomics

RSDT Fabricated Anode Functional Layer for EC-

GTL cell

Future Plans

Continued development of GTL catalystIncorporation of GTL catalyst to anode layer forelectrochemical evaluationContinued fabrication development of RSDT formaterialsRefined Techno-economic analysis with actualcell performance

Acknowledgements

DOE/ARPA-E: Ping Liu, John Lemmon, John Tuttle, Mark PouyPNNL: Olga A. MarinaEERC: Ted AulichUCONN: Radenka Maric, Mark Aindow, Na LiMIT: Bilge YildizFCE: Hossein Ghezel-Ayagh, Alireza Torabi, Mick Barton, RobertSanderson