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Demonstration of Technology Options for Storage of Renewable Energy
S. Elangovan, J. Hartvigsen, and L. Frost Ceramatec, Inc.
Brainstorming Workshop Institute for Advanced Sustainability Studies e.V. (IASS)
Postdam, Germany November 19-20, 2013
Acknowledgement: DOE, ONR, State of WY
Outline
• Introduction • Technology Needs and Challenges • Technology Options Pursued at
Ceramatec – Electrochemical (Solid Oxide) Technology – Fuel Reformation
• Liquid Fuel Synthesis • Summary
Energy Need
Population/Standard of
Living
Emissions Global
Warming
Renewable Energy
Geo-Political
Energy Storage
Petroleum Need
Global Challenges
Energy Need
Population/Standard of
Living
Emissions Global
Warming
Renewable Energy
Geo-Political
Storage Petroleum Need
Where can we apply integrated solution
Increase in Standard of Living & Energy Demand
Shell International, Energy Needs, Choices and Possibilities, Scenarios to 2050, London, 2010
Energy
• Sources – Oil – Biomass – Gas – Coal – Nuclear – Renewable
• Forms – Electricity – Heat – Motive
Power
• Challenges – Supply/
Demand – Conversion – Tranportation – Storage – Efficiency – Emission
Ceramatec’s Focus Areas
Renewable Energy
• Abundant • Location
Constraint
Electrochemical
• High Efficiency • Technology
Maturity? • Scale up & Cost?
Synthesis Gas
• Source of Heat, Electricity, Chemicals
Liquid Hydrocarbon
• High Energy Density
Consumes CO2"Alternative to Sequestration"
Transportability"High Demand"
Focus/Interest/Experience • Electrochemical
ü Solid Oxide Fuel Cell/Solid Oxide Electrolyzer – Molten Salt Electrolyzer (potential scale up option)
• Syngas Generation ü Co-electrolysis of CO2 and H2O ü Reformation of methane containing gases
• Stranded natural gas • Biogas • Landfill gas
• Syngas to Liquid Fuels ü Fischer Tropsch
Electrochemical Conversion
• Solid Oxide Fuel Cells – Decades of R&D worldwide – Excellent Technical Progress – Numerous small and large demonstrations – Market introduction?? – How can we benefit from the progress made
• Build on progress • Expand Applications
• Leverage decades of SOFC R&D • Inputs
– e- (green electrons) – steam => hydrogen – co-electrolysis of H2O + CO2 => syngas – heat input optional, depends on operating point
• Most efficiency means of hydrogen production – e- to hydrogen
• η=100% at 1.285V • η= 95% at 1.35V • η=107% at 1.20V, (heat required)
• Hot O2 and steam byproducts – Valuable for biomass gasification
Electrolysis Is The Key To Synfuels
Synfuel Power Market Much Larger Than Grid Electrolysis at 1.285 V/cell $25/MW-hr Syngas cost $80/bbl
Annual US Electrical Energy
Demand GW-hr
Petroleum equivalent
k-bbl
Synfuel electric energy as ratio to current demand
Conventional Electric Load
4,119,388 47% of Capacity
1,801,874
1x 470 GW
US Crude Oil Imports
3,580,694
2x 940 GW
US Crude & Refined Imports
4,726,994 $720k/min @ $80/bbl
2.6x 1,220 GW
US Crude Oil Refinery Inputs
5,361,287 3.0x 1,410 GW
US Crude & Refined Refinery Inputs
6,277,893 3.5x 1,650 GW
http://tonto.eia.doe.gov/dnav/pet/pet_sum_snd_d_nus_mbbl_a_cur.htm "http://www.eia.doe.gov/cneaf/electricity/epa/epates.html "
Grid stability restricts wind to ~ 1/6 of load and requires costly reserve "
Liquid Hydrocarbon Energy Density and Value
• Energy Density – Diesel 42 MJ/kg, 0.86 kg/liter – Hydrogen at 690 bar (10,000 psi) Z=1.43
– 4.4 MJ/liter (min. work of compression is 10-12% of LHV)
• Established markets for liquid fuels – Highly developed infrastructure – Existing vehicle fleet – US demand, 6.3 billion bbl/yr, > $500 billion/yr
• Liquid fuels command a premium – Negative value for CO2 to $ 85/ton of C for crude oil
Electrochemical Technologies
Renewable Energy + Carbon dioxide Recycle at
~ 100% Efficiency à Synthesis Gas
One Technology - Multiple Modes Of Operation
Fuel
Solid Oxide Stack Module
Electricity
Steam + Electricity Hydrogen (High Purity)
CO2 & Steam + Electricity
Syngas (CO + H2
NG Biogas Diesel JP-8 Coal
Co-electrolysis Reaction Paths
H2O + 2e- → H2 + O2- (electrolysis of steam) kinetics favored [1] CO2 + 2e- → CO + O2- (electrolysis of CO2) kinetics slower [2] CO2 + H2 ↔ CO + H2O (reverse water gas shift ) kinetics fast [3] Reverse shift reaction: CO2 + ⇑ H2 <==> CO + ⇓ H2O As steam is consumed and H2 produced, the RWGSR converts CO2 to CO
[1]
[2] [3]
[1]
Scale up & Demonstration
• 18 kW Steam Electrolyzer (Ceramatec Stacks tested at Idaho National Labs.)
720 Cell System Hydrogen Production: 5.7 Nm3/hr !
Technical Challenges
• Air electrode delamination • Chromium poisoning • Seal challenge (back pressure from
product collection) • High steam corrosion of metal
interconnect
Electrolysis Stack Stability Progress
Recent SOEC Stacks Meet Life2me Targets
19
ASR Limit for 40,000 hr life2me target
Steam supply failure
Molten Salt Electrolysis
• Demonstrated at Weizmann Inst., Israel (5000 A cell) • Operating Principle & Efficiency – same as SOEC • Near term scale up possible
2
2
CO in
O out
anode cathode
CO out
-2-23 2OCO2CO +→+ −e
-23
-22 COOCO →+
32CO Liofmelt
2-2 O2
12O →− −e
Cell voltage: 1.05±0.05V Current density: 100 mA/cm2
No Degradation in 700hr test
Thermal neutral voltage: 1.46V/cell Faradaic efficiency: 100 % Thermodynamic efficiency: 100%
Reformation Process for Syngas Generation
Stranded Natural Gas Biogas (Anaerobic Digester)
Landfill Gas
Reformation
• Low Power Plasma – Plasma is a continuously renewing catalyst – Low Electric Power Consumption
• ~ 1 to 2% of heating value of fuel • < 8% heat of reformation
– Sulfur tolerant
Plasma Head"
Low Power Plasma: Liquid/Gas Fuel Reformation • 1
• Large reformer – Can process 100 thousand
standard cubic feet/day of Natural Gas (~3000 m3/day)
– > 1 MWthermal
– Can reform liquid fuels – Sulfur tolerant
Reformer scale-up
10 TPD Biomass Gasification Reformer + Gasifier
* Large reformer * To reform residual tars/oil from 10 TPD biomass
gasifier
Synfuels Historical Perspective
• Fischer-Tropsch Synthesis – First commercial plant in Germany, 1936 – Continuous commercial operation in South Africa since 1955
• Secunda plant is CTL • Also operate GTL
– Shell GTL in Malaysia – Newer plant in Qatar (Oryx)
– Primarily large scale CTL & GTL • Syngas production cost ~5/6 of total • Syngas conversion cost ~1/6 of total
– $80 to $120/bbl (depends on electric rate, tax credit)
Challenge: Produce a small scale plant at same cost per bpd capacity as large plant
Ceramatec Laboratory Syngas Facility Two stage oil free syngas compressor
with syngas drying system. Discharge pressure 150-200 psig
Inter-stage tank 240 gallon
Two 500 gallon, 800 psig syngas tanks; 7200 SCF capacity
Final stage oil free compressor. Discharge pressure 800 psig
Ceramatec Laboratory FT System
Capacity: 3 to 4 liters/day Single tube FT reactor 42.7mm ID, 2.0 m length, ~2.9 liters Backpressure regulaHon system, 20-‐30 barg High pressure mass flow controllers (low/high range) Temperature controllers for reactor and collecHon system Hot and cold product collecHon vessels Recycle pump & Cooling system
Ceramatec FT Product From 1-1/2” Reactor
• Production rates up to 4 liter/day
• 2200 hour run
• FT 46.5 MJ/kg, diesel 46 MJ/kg, 40 MJ/kg B100 FAME
• Cetane 60.2 by ASTM D613
Compressor Scale up
• Capacity equivalent to 2 bpd of FT liquid
Pre-pilot Plant Scale up
4” Reactor Tube - Fischer Tropsch Skid!Capacity: 0.25 bpd (40 liters/day)!
Novel Design Features
• Major FT Challenge – Heat removal from exothermic process – Necessitates use of small reactor tubes
• Ceramatec Approach – Dual cooling loop – Internal heat transfer – Allows the use of larger tubes – 100 mm diameter reactor tested – Allows capital cost reduction
FT Demonstration
30 liters/day FT Production Demonstrated"
FT Product Analysis
33!
0
5
10
15
20
5 10 15 20 25 30 35
%C
N
Carbon Number
081913 090613 091013 091613 091813 091213 091313 100113 100313 100213 093013 092613 092513 092413 092313 092013
30 days of continuous operation showed stable performance"
Pilot Plant Layout (10 bpd ~ 1,600 liters/day)
100 bpd preliminary reactor concept developed"
The Electrolytic Synfuel Solution • Electrolysis efficiency – 100% in practice • Process negates RE shortcomings
– Intermittency – Stranded due to limited transmission reach & capacity
• Efficient, concentrated, RE storage technology – 36 MJ/liter – 21-26 MW-days storage in a 10,000 gallon tank trailer
• Utilize all carbon content in BTL, CTL, & CC sys • FT needs 20 bar comp. vs. 700 bar H2 FCV • Product compatible with existing dist. & vehicles
– 20 to 50 years to retire existing fleet
FT Process
• Syngas from other methane sources can be used – Biomass based
• Design options for capital cost reduction • Operating strategies for cost reduction
Thank You!
