thermochemical syngas production: scale, and economics · pdf file29.09.2016 ·...

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


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


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


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


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.


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


• 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


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]


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)


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


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


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%)


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.


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


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


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


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


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%


< 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*


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?

thermochemical syngas production: scale, and economics · pdf file29.09.2016 ·...

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