Ge#ng to Know You

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What is your background?

Physical sciences or engineering Geology Policy or economics Something else

Outline

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ARPA-E Background ARPA-E CCUS Investment Overview Gas SeparaBons Fundamentals CCUS State-of-the-Art Examples of ARPA-E Projects A Word on CO2 UBlizaBon

ARPA-E Mission

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Evolution of ARPA-E

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2007RISING ABOVETHE GATHERING STORM PUBLISHED

2007AMERICA COMPETES ACT SIGNED

2009AMERICAN RECOVERY & REINVESTMENTACT$400M Appropriated

2011FY2011 BUDGET$180M Appropriated

2012FY2012 BUDGET$275M Appropriated

2013FY2013 BUDGET$265M Appropriated

Creating New Learning Curves

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What Makes an ARPA-E Project?

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BRIDGE Translates science into breakthrough technology Not researched or funded elsewhere Catalyzes new interest and investment

IMPACT High impact on ARPA-E mission areas Credible path to market Large commercial application TRANSFORM Challenges what is possible Disrupts existing learning curves Leaps beyond todays technologies

TEAM Comprised of best-in-class people Cross-disciplinary skill sets Translation oriented

Technology Acceleration Model

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ARPA-E CO2 Separation Programs/Projects

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27%

19% 13%

24%

13% 4%

Funding by Technology Solvents

Membranes

Sorbents

Phase Change

Chemical Looping

Enhanced Oil Recovery (EOR)

OPEN 2009 5 projects, $13.3 M

2009 2014

IMPACCT 15 projects, $39.9 M

2010 2014

OPEN 2012 2 projects, $3.0 M

2013 2016

Focused Programs

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Transportation Energy Technologies

Stationary Energy Technologies

Solar ADEPT

REMOTE

RANGE

MOVE

PETRO

Electrofuels

BEETIT

GRIDS

IMPACCT

GENI

ADEPT

METALS SBIR/STTR REACT AMPED HEATS

BEEST

FOCUS

SWITCHES

Development Pipeline: ARPA-Es Role

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Gas separation fundamentals/theory

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Minimum thermodynamic work for separation of species into streams

= = + In an isothermal and isobaric environment, minimum work for separation is equal to negative of difference in Gibbs free energy of separated final streams For an ideal gas mixture, partial molar Gibbs free energy for each gas is: /= +(/)

Source: Carbon Capture, Jennifer Wilcox

Gas separation fundamentals (contd)

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Total Gibbs free energy of an ideal gas mixture is therefore:

= / Minimum work required to go from state 1 to states 2 and 3 is associated with free energy difference between product and reactant states getting to GA, GB, and GC

Leading to minimum work required:

/= +(/)

Source: Carbon Capture, Jennifer Wilcox

Minimum Work of Separa9on Required

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Minimum Work for Separation

Published'in'APS'Report,'Feasibility'of'DAC'with'Chemicals'(2011)''Source: APS Report: Feasibility of DAC with Chemicals (2011)

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Source: Carbon Capture, Jennifer Wilcox

Real systems = more energy than thermodynamic minimum Second law efficiency: n = Wmin / Wreal

Depending on technology, concentration, purity, etc. work is required to regenerate tech,

compress CO2, etc.

ACTUAL work depends on unit operations / extent of

efficiencies.

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Image courtesy RTI International

State of the Art: Amine Capture

How its done today: amine solvents

16 Image credits: RTI International, NETL

mass transfer, kinetics lower CAPEX

.: 2 mole amine / mol CO2

but, watch dHabs

CO2 pressure with minimal heat lower compression load lower parasitic steam use

Costs of CCUS

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Transport Capture Storage Compression

80% Capital Cost

Energy required for CO2 separation, in parasitic load %

Herzog, et al., Advanced Post-Combustion CO2 Capture, Clean Air Task Force (2009)

Ideal CO2 Capture Material

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0

5000

10000

15000

20000

0 20 40 60 80 100 120

Rat

e C

onst

ant (

M-1

s-1

)

Heat of Reaction (kJ/mol)

OH-

MEA

DEA

Piperazine

High Reaction Rate

Moderate Binding Energy

Ideal Material

Source: APS Report: Feasibility of DAC with Chemicals (2011)

FOA-1 & IMPACCT: Categories and Projects

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Membranes Porifera Carbon nanotube membrane $1.2M

United Technologies Research Center

Facilitated transport w/ synthetic catalyst $1.9M

University of Kentucky Solvent/membrane hybrid process $2M

Georgia Tech MOF/polymer composite membranes $1M

University of Colorado Gelled ionic liquid-based membranes $3.9M

Sorbents Lehigh University Electric field desorption $0.5M

Texas A&M Stimuli-responsive MOFs $1M

MIT Electrochemical sorbent regeneration $1M

LBNL High-throughput MOF discovery $3.9M

ORNL Ionic liquids on hollow fiber support $0.8M

New Types of Membranes

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New chemistries: gelled ionic liquids

Ultra-thin, defect-free layers

Flue gas from coal plant CO2

CO2 N2 N2 N2 CO2 Clean gas out

CO2 out

Membrane

Towards 10,000 GPU with high selec9vity

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High-Throughput Adsorbent Discovery!Selectivity!

Sample Number"

0.15

bar

CO 2

capa

city (

mm

ol/g)

"

50 C"

Capacity!

H2NHNH2N

NH2

H2NN N

N

NH

HN

H2NHN

NH2

NNH2H2N

H2N

NH

HN

Rapid adsorbent discovery via high-throughput variation of metal-organic framework components" Alkylamine functionality endows metal-organic frameworks with high capacity, selectivity, and H2O tolerance"

Amine-grafted metal-organic frameworks reduce the amount of energy required to separate CO2" Fast kinetics and unusual adsorption process allow for rapid cycling with a 100 C adsorption temperature"

Frameworks with Appended Alkylamines!

MEA Baseline!

mmen-Mg2(dobpdc)!

Isobaric CO2 Adsorption!

High-temperature Cycling! Regeneration Energy!

Isothermal CO2 Adsorption!

25 C "40 C"50 C"75 C"

FOA-1 & IMPACCT: Categories and Projects

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Solvents / Catalysts Nalco pH-swing process $1.7M

Codexis Direct evolution of enzymes $4.6M

LLNL Enzyme analogues and encapsulation $3.6M

Columbia University Catalytic enhancement of silicate weathering $1.3M

RTI Non-aqueous solvents $2.5M

Phase Change GE Global Research Liquid to solid phase change materials $3.7M

Notre Dame University Phase changing ionic liquids $2.6M

Alliant Tech Systems Supersonic capture duct $2.7M Sustainable Energy Solutions

Cryogenic process $5.3M

Chemical Looping Ohio State University Syngas looping process $7.1M

Cryogenic / phase change processes

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AlternaBve route: take advantage of CO2s physical properBes (based on temperature and pressure) to separate out as solid SBll requires energy

Can avoid direct contact chemical processes

Source: Carbon Capture, Jennifer Wilcox

Supersonic Duct for CO2 Separa9on

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Supersonic duct

Cryogenic Carbon Capture

Electrochemical Separa9on (ASU OPEN 2012)

ARPA-E Examples in Carbon Dioxide U9liza9on

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A Few Words on CO2 U9liza9on

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UBlizaBon for chemicals is a daunBng task Worldwide, emissions from coal = 13 gt/yr, petrol = 11 gt/yr, gas = 6 gt/yr Top 5 chemicals would miBgate 2.5% of worldwide CO2 generated Chemical World (Mt) Market Size Sulfuric Acid 199.9 Nitrogen 139.6 Ethylene 112.6 Oxygen 100 Lime 283

Geologic formation Worldwide storage capacity (Gt CO2)

Deep saline aquifers 1,000-10,000 * Depleted oil/gas fields 200-900 Unmineable coal beds 100-300

Source: Carbon Capture, Jennifer Wilcox

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