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1CLOSING THE CARBON CYCLE 2016 | 28 ‐30 SEPT 2016 TEMPE, AZ, USA ELLEN B STECHEL
*ASU campus wide initiative on light inspired research for energy and
sustainability
Solar thermochemical syngas production: technology, scale, and economics
Closing the Carbon Cycle: Fuels from Air
Ellen B Stechel, presentingArizona State University
DEPUTY DIRECTOR, LightWorks*Professor of Practice, School
of Molecular Sciences
2CLOSING THE CARBON CYCLE 2016 | 28 ‐30 SEPT 2016 TEMPE, AZ, USA ELLEN B STECHEL
12 Research Institutions7 Time Zones3 Continents
7 Funded Projects8 Years3 Current
Sandia National Laboratories*, Georgia Institute of Technology, Bucknell UniversityColorado School of Mines, Stanford University,
Northwestern University, University of WisconsinGerman Aerospace Center (DLR); University of Adelaide; AU, CSIRO, Newcastle, AU
King Saud University, Saudi Arabia
Small but highly collaborative community
3CLOSING THE CARBON CYCLE 2016 | 28 ‐30 SEPT 2016 TEMPE, AZ, USA ELLEN B STECHEL
FOR IMMEDIATE RELEASEDecember 5, 2007Sandia’s Sunshine to Petrol project seeks fuel from thin airTeam to chemically transform carbon dioxide into carbon‐neutral liquid fuels
S2P was an $11.5M Project Oct ‘07 – Sept ‘10
4CLOSING THE CARBON CYCLE 2016 | 28 ‐30 SEPT 2016 TEMPE, AZ, USA ELLEN B STECHEL
MOx MOx‐ + /2 O2 1.Endothermic Reduction on Sun
MOx‐ + H2OMOx+ H22.Exothermic Re‐oxidation off Sun
MOx‐ + CO2MOx+ CO
Solar thermochemical CO2 and H2O splitting with redox active metal oxides
)(,221
)(,2
)( 2 gsrs OeO
)(2
)()(,2)(,2 gsgsr COOCOe
)(,22
)()(2)(,2 gsgsr HOOHe
Two step thermochemical cycle – repeat over and over indefinitelyNot consumed, but not a catalyst at first order
5CLOSING THE CARBON CYCLE 2016 | 28 ‐30 SEPT 2016 TEMPE, AZ, USA ELLEN B STECHEL
Energy in, Oxygen out> 1300 C
Metal oxide thermal redox chemistry
Endothermic Oxide
Reduction
Exothermic Oxide
ReoxidationRecuperate
Oxygen in, Energy out< 1100 C
H2 and/or COor Hot Air
H2O and/or CO2or Cool Air
Closes the cycle only if CO2 directly or indirectly comes from the air
Desert technology• Low Humidity• Doesn’t
require that the CO2 is dry.
6CLOSING THE CARBON CYCLE 2016 | 28 ‐30 SEPT 2016 TEMPE, AZ, USA ELLEN B STECHEL
Three interwoven story lines that are important to making this a viable technology
1. Materials:Define the potential for high performance
2. Solar Receivers & Reactors: Define and constrain the operating space
3. Systems: Define scale, economics, and the lifecycle
Materials, Reactors, and Systems Challenges to operationalize the cycle
7CLOSING THE CARBON CYCLE 2016 | 28 ‐30 SEPT 2016 TEMPE, AZ, USA ELLEN B STECHEL
• Mixed Ionic‐Electronic Conducting (MIEC) Perovskites or Fluorite oxides• Several properties of significance:
– High temperature stability and phase “stable”– Redox‐active (like charging a battery)– ABO3‐x ↔ ABO3‐x‐δ + δ/2 O2(g)
Fascinating class of materials
No major crystallographic phase change occurs during redox
Vacancies facilitate oxygen ion transport
Redox activity is continuous over a range of T and pO2
SOA is Ceria CeO2
Vacancy on anion latticeOxygen anion
A cationB cation
O2‐ ion can “hop” via vacancies
Like SrTiO3 – not redox active. SrMnO3
8CLOSING THE CARBON CYCLE 2016 | 28 ‐30 SEPT 2016 TEMPE, AZ, USA ELLEN B STECHEL
Particle ReductionTr=1500CpO2,r = 25 Pa
Particle ReoxidationTox=900C
Particle Coo
ling
Particle Coo
ling
RecuperationRecuperation
Sun Eject HeatEject Heat
Contours are Materials Specific5k Pascal, ‐22 k 8410‐21 up to ~4 AtmTref = 800C Pref=0.21 Atm
Operating Variables1. Reduction
Temperature, Tr2. Re‐oxidation
Temperature, Tox3. Reduction Partial
Pressure, pO2,r4. Excess H2O,
CeO2 Ce2‐ + 1/2 O2 (+1) H2O + Ce2‐ CeO2 + (H2O +H2)
Z=Ln[]Z=Ln[]
Contours of Constant pO2Contours of Constant pO2
=Ln[T/T
ref]
=Ln[T/T
ref]
9CLOSING THE CARBON CYCLE 2016 | 28 ‐30 SEPT 2016 TEMPE, AZ, USA ELLEN B STECHEL
Fitted response surfaces and derivatives determine enthalpy and entropy of incremental reaction
Slope determines ;
Negative of the slope
determines ;
Contours are for constant z() ~ ‐Log ()
CERIA CeO2‐ using Data from CALPHAD
½ Ln(p0/p
O2)
T0/TLn(T/T0)
10CLOSING THE CARBON CYCLE 2016 | 28 ‐30 SEPT 2016 TEMPE, AZ, USA ELLEN B STECHEL
Novel reactor designs to realize high efficiency design attributes
• Gen 1 counter‐rotating rings receiver/reactor recuperator CR5• Operational• Direct solar, Continuous flow, Internal recuperation, product
separation• Diver and Miller inventors
Gen 2: packed bed particle reactor
Solar HeatSolar Heat Mirrored Dish Tracks
the Sun and Focuses Heat into the Chamber
Alternate discs rotate in opposite
directions
O2
CO/H2
Ermanoski & SiegelErmanoski & Siegel
11CLOSING THE CARBON CYCLE 2016 | 28 ‐30 SEPT 2016 TEMPE, AZ, USA ELLEN B STECHEL
High efficiency solar thermochemical reactor for hydrogen production Gen 3
Planned Demo3 kW, 8 hours, or 86.4 MJ
> 3L H2 or 38.3 kJDOE FCTO Funded
Roadmap projection to <$2.30/kg
12CLOSING THE CARBON CYCLE 2016 | 28 ‐30 SEPT 2016 TEMPE, AZ, USA ELLEN B STECHEL
A Baseline Solar Fuels Plant: Identifying Opportunities To Economic Viability And Scale
Fluegas CO2 capturesystem SolarFuelPlant LiquidfuelsCO2Transport
100miles
SolarenergyFossilfuelElectricityn=20%
Heatn=45%
SolartoChemicaln=20%
Electricityn=37%
Heatn=86%
1000 bpd ~70MW fuel~ 8 km2 at target efficiency
64 MW Fuel PlantAssumed 20% Sun to Reactor Product
Sandia Nat’l Labs, U.WI, ASUSandia Nat’l Labs, U.WI, ASU
10000 kg H2/day = 16 MW (HHV)
300 Barrels/day = ~21 MW• “Small” Towers 21‐42 MWth
• 2500‐5000 kg H2/day (@20%)• 50 bbl/day (@12.5%)• 2300 GGE/day (@12.5%)
13CLOSING THE CARBON CYCLE 2016 | 28 ‐30 SEPT 2016 TEMPE, AZ, USA ELLEN B STECHEL
Life cycle analysis identifies most of the GHG footprint of production comes from capturing the CO2
Jiyong Kim, James E. Miller, Christos T. Maravelias, Ellen B. Stechel, Applied Energy 111 (2013) 1089–1098Jiyong Kim, James E. Miller, Christos T. Maravelias, Ellen B. Stechel, Applied Energy 111 (2013) 1089–1098
Sandia Nat’l Labs, U.WI, ASUSandia Nat’l Labs, U.WI, ASU
Kim, et al “Methanol production from CO2 using solar‐thermal energy: processdevelopment and techno‐economic analysis” Energy Environ. Sci., 2011, 4, 3122.
“Fuel production from CO2 using solar‐thermal energy: system level analysis” Energy Environ. Sci., 2012, 5, 8417.
14CLOSING THE CARBON CYCLE 2016 | 28 ‐30 SEPT 2016 TEMPE, AZ, USA ELLEN B STECHEL
Based on 12.5% end‐to‐end sunlight to fuel efficiency• Solar field learning: CSP industry• Fuel processing learning: Distributed GtL, BtL• Financing innovations for access to low cost of
money• Solar/Chemical interface: Learning from solar
reforming and gasification, resolving storage issues
$43.5/GJ; $5.75/GGE$156/MWh
$43.5/GJ; $5.75/GGE$156/MWh
$19/GJ, $2.50/GGE, $68/MWh$19/GJ, $2.50/GGE, $68/MWh
ASU & Sandia Nat’l LabsASU & Sandia Nat’l Labs
Roadmap to liquid hydrocarbon affordabilityLCOF
LevelizedCost of Fuel
15CLOSING THE CARBON CYCLE 2016 | 28 ‐30 SEPT 2016 TEMPE, AZ, USA ELLEN B STECHEL
Hydrogen production Gen 3
DLR.de • Chart 15
Stages1
2
34
H2O
H2/H2O
ErmanoskiWith DLR
~110 meters high3000 Suns 3MW/m2
3 windows per stage4 stagesNon‐optimized ~45% optical efficiency
16CLOSING THE CARBON CYCLE 2016 | 28 ‐30 SEPT 2016 TEMPE, AZ, USA ELLEN B STECHEL
Co‐production of H2 and electricity
• Electricity production can provide revenue and reduce cost of H2
• Ratio of hydrogen production and electricity varies with DNI
• Can also make clean water beyond what’s consumed
5
7
9
11
13
15
17
19
300 500 700 900Efficiency %
DNI (W/m2)
System
Hydrogen Contribution
With Vishnu Budama and Nate Johnson, ASU
17CLOSING THE CARBON CYCLE 2016 | 28 ‐30 SEPT 2016 TEMPE, AZ, USA ELLEN B STECHEL
CAPEX dominates the cost
• Biggest cost reduction opportunity per tower is the solar field• Next biggest opportunity comes from productivity increase
Reasonably high fidelity of CAPEX estimationInitial cost estimate $9.86/kg‐H2Realistic cost reductions
Increased H2 per tower, decreased electricity production, and reduced revenue per electrical unitUltimate estimate $2.11/kg‐H2
18CLOSING THE CARBON CYCLE 2016 | 28 ‐30 SEPT 2016 TEMPE, AZ, USA ELLEN B STECHEL
Land Are a
Solar C apacity
S ta te (109 m2) (T W) (G W) (mb/d)AZ 49.9 3.37 421 5.9C A 17.7 1.20 150 2.1C O 5.5 0.37 46 0.7N V 14.5 0.98 122 1.7N M 39.3 2.65 331 4.7T X 3.0 0.20 25 0.4U T 9.2 0.62 78 1.1
T otal 139.2 9.39 1,174 16.6
Fue l C apacity
• Global 5.0 mbpd aviation fuels or the equivalent of 350 GW energy flux (2009) and growing
• ~40 billion m2 land area
• Global 88.3 mbpd petroleum consumption or the equivalent of 6.3 TW energy flux (2011) and growing
• ~700 billion m2 < 0.5% global land area
Filters applied (Resource analysis by NREL and SNL):• Sites > 6.75 kwh/m2/day – 280 Watt/m2 ‐ ~2450
kWh/m2/yr• Exclude environmentally sensitive lands, major
urban areas, • Remove land with slope > 1%.• Assumes 25% packing density• Only contiguous areas > 10 km2 (675 MWprimary )
sufficient for ~1200 boe/day (at 12.5% sunlight to fuel efficiency)
139 billion m2 is 1.5% of total U.S. landSimilar to transportation infrastructure
Consider the scale at 12.5%
19CLOSING THE CARBON CYCLE 2016 | 28 ‐30 SEPT 2016 TEMPE, AZ, USA ELLEN B STECHEL
< 1000 1000 1500 2000 2300 2500 kWh/m2/yr
< 114 114 171 228 263 285 W/m2
< 2.74 2.74 4.11 5.48 6.30 6.85 kWh/m2/d
~ 25000 TW on land~ 600 TW exploitable solar or ~2.5% of land area
For Concentrating Solar, Probably >2400 kWh/m2/yr
Australia ~43 TW (>600 mbpd)
Middle East ~14 TW (190 mbpd)
Africa ~73 TW (1030 mbpd)
SW United States ~2.7 TW (38 mbpd)• Screened data from Trieb,
et al SolarPACES 2009, Berlin
If Land Utilization 12.5% 25% = ~ 3.1%
Australia ~43 TW (>600 mbpd)
Middle East ~14 TW (190 mbpd)
Africa ~73 TW (1030 mbpd)
SW United States ~2.7 TW (38 mbpd)• Screened data from Trieb,
et al SolarPACES 2009, Berlin
If Land Utilization 12.5% 25% = ~ 3.1%
Great potential in a number of regions in the world*
20CLOSING THE CARBON CYCLE 2016 | 28 ‐30 SEPT 2016 TEMPE, AZ, USA ELLEN B STECHEL
Sustainable FuelsSecure Energy
Special thanks to numerous colleagues especially Jim Miller, Tony McDaniel and Ivan Ermanoski at Sandia
Nate Siegel (Bucknel) and Rich Diver (ret), formerly SandiaNate Johnson, ASU
Peter Loutzenhiser, Georgia TechChristian Sattler, DLR
Gus Nathan, University of Adelaide, AU,Jim Hinkley, CSIRO, Newcastle, AU
Questions?