Opportunities & challenges in electrochemical CO2utilization using a PEM

electrolyzerKendra Kuhl

Opus 12

kendra@opus-12.com

INPUTS: CO2

,

WATER,

ELECTRICIT Y

ELECTROCHEMICAL

CO2

REDUCTION

(ECO2R)

OUTPUTS: PRODUCTS

THAT DROP INTO

EXIS TING SUPPLY

CHAINS

Our solution: a platform technology that recycles CO2 back into chemicals and fuels

CO2

FUELS &

CHEMICALS

PUREO

2

ELECTRICITY

H2

O

1 2 3

F O U N D I N G

T E A M

Team: Uniquely positioned to bring this product to market.

N I C H O L A S F L A N D E R S , C E O

MS E-IPER, Stanford

Work Experience: COO/CFO

Levo

McKinsey CleanTech practice

D R . K E N D R A K U H L , C T O

PhD in Chemistry, Stanford

Post doc, SLAC

Research: Transition metal catalyzed

CO2 electroreduction, reactor

design

D R . E T O S H A C A V E , C S O

PhD in Mechanical Eng, Stanford

Research: Modified gold catalysts

for CO2 electroreduction, reactor

design

S I C H A O M A , S E N I O R C H E M I S T

PhD in Chemistry,

University of Illinois

Urbana-Champaign

Research: ECO2R ethylene

catalysis, reactor design

G E O R G E L E O N A R D , S E N I O R C H E M I S T

BS Chemistry, Carnegie Mellon

Work Experience: CO2 catalysis,

reactor design - Liquid Light

D A N I E L D I A Z , C H E M I S T

MS Material Science,

University of Michigan

Work Experience: Silicium

BS Mechanical Engineering

Olin College of Engineering

Work Experience: Alteros

A N N I E Z E N G , E N G I N E E R

Cyclotron Road Plug

4

www.cyclotronroad.org

Water Oxidation (Anode) Eο

1.23 V

Overall Reaction:

O OHC Energy OH CO 2zyx22

)e 4(H O O2H -

22

OnH OHC )e m(H CO 2zyx

-

2

Fuels & Chemicals

ECO2R can also be thought of as “reverse combustion”

Split into electrochemical half reactions:

Determines minimum energy required for ECO2R to various products

CO2 Reduction (Cathode)

~0 V

Challenges

Carbon-based compounds are good fuels because they are high in energy

Burning hydrocarbons releases energyand carbon dioxide

CO2

To convert carbon dioxide into chemicals and fuels, must add energy

back into the system

Inefficiencies in both directions

Thermodynamics

carbon dioxide +

water16 compounds

Kuhl, Cave, Jaramillo, et al. Energy Environ. Sci., 2012, 5, 7050-7059

Selectivity

• Academic reactor designs often not suitable for commercial applications

• New electrochemical reactor design is hard

Reactor Design

Sichao Ma, Paul Kenis et al.

Yogi Surendranath et al.

Olga Baturina et al.ACS Catal. 2014, 4, 3682−3695

Kuhl, Cave, Jaramillo, et al. Energy Environ. Sci., 2012, 5, 7050-7059

Source: Jen Wilcox, Praveen Bains, Colorado School of Mines

CO2 Availability

Opportunity

2.001.50

-2.15-2.88

1.482.07

Sugarcane to C2H4 ECO2R CA grid ECO2R coal w/ CCS

kgCO2e/kgC2H4

Ethane ECO2R windNaptha

GHG emissions per kg of ethylene produced

kg CO2e / kg C2H4

Source: NREL, Braskem, Wikipedia (CO2 intensity data), team analysis

1 ECO2R emissions intensity based on 55% total energy efficiency of conversion

GHG emissions reduction depends on source of electricity

Source: Electric Power Monthly, EIA, March 2016

New renewables coming online

[Source: 2013 Wind Technologies Market Report, DOE-EERE (2014)]

Natural Gas

2 cents/kWh

Cost of renewables is dropping

Our Approach

COM M ERCIAL PEM WATER ELECTROLYZER OPUS 12 PEM CO2

ELECTROLYZER

Opus 12 has developed a breakthrough drop-in solution that enables us to use existing PEM

architecture. This significantly reduces scale-up risk and capital costs.

Innovations in Opus 12’s

new cathode catalyst layer:

• Metal nanoparticle

catalysts

• Novel polymer

materials

• Anode unchanged

We are converting a commercial-scale water electrolyzer into a CO2 electrolyzer.

By integrating into a

PEM electrolyzer, we

capture all of the benefits

of an existing industrial

reactor design, while

significantly reducing

scale-up risk

• Commercial readiness – deployed around the world for

decades

• Fast ramp times – enables use of intermittent low-cost

electricity (modern systems can integrate directly with a

wind turbine)

• Low capex, thanks to years of commercial development and

mild operating conditions

• Modularity and scalability –allows for integration with CO2

sources of diverse volumes

• High current density, leading to a small footprint

• Operational simplicity – no need for specialized operators

on site

Advantages of PEM reactor architecture

250kW Stack

We are the first group in the world to integrate CO2-converting catalysts into a PEM electrolyzer.

1 M W C O M M E R C I A L P E M

H 2 S Y S T E M

Opus 12’s drop-in component converts PEM H2 electrolyzersinto CO2 electrolyzers, allowing us to take advantage of decades of advances in PEM technology.

Image: Proton OnSite M Series 1 MW PEM water electrolyzer

Our ECO2R conversation performance: like 37,000 trees…

…6 4 F O O T B A L L

F I E L D S O F

D E N S E F O R E S T

I N A S U I T C A S E -

S I Z E D R E A C T O R

Source: Hydrogen Production Cost from PEM Electrolysis. DOE Hydrogen and Fuel Cells Program Record 14004

Source: Five considerations for large-scale hydrogen development. Proton Onsite.

Source: II.D.1 PEM Electrolyzer Incorporating an Advanced Low-Cost Membrane. Giner, Inc. DOE Contract Number: DE-FG36-08GO18065

Years of engineering have reduced capital costs

Wh

ole

sa

le p

rice

Technology Development Time

+ Market Size

High Margin Entry Market

Fuels & Commodity Chemicals

Modular, scaleable design allows us to go after high margin markets first

Our efforts are focused on improving four key technical performance metrics that impact overall system economics

1 2

3 4

The percent of the electrical current through the system that goes to producing the desired product.

The amount of current (proportional to the amount of product made) per electrode area

How long the electrochemical reactor runs without a loss in energy efficiency or current density.

The thermodynamic minimum voltage divided by the actual voltage.

Product selectivity Voltage efficiency

Current density Lifetime

The metrics that matter for cost-effective ECO2R:

Selectivity (CurrentEfficiency)

Voltage Efficiency Current Density Lifetime

CO2 Electrolyzer Water Electrolyzer

>90%100%

55%60-80% 1 A/cm2

1.5 A/cm2 50,000 hrs50,000 hrs

Performance of water electrolyzers vs CO2 electrolyzertargets

• CO2 utilization is not easy

• But offers a large opportunity

• Opus 12’s approach overcomes key challenges

Summary

Nicholas Flanders

Etosha Cave

George Leonard

Daniel Diaz

Sichao Ma

Annie Zheng

Scientific Advice:

Tom Jaramillo, Stanford

Jen Wilcox, Stanford

Brian Bartholomeusz, Stanford

Mike Tucker, LBNL

John Newman, UC Berkeley

Adam Weber, LBNL

Nate Lynd, UT Austin

Mark Warner, Warner Advisors

Ilan Gur, Cyclotron Road

Kathy Ayers, ProtonOnsite

Thank you for your attention

Energy & Mass Balance

Carbon Monoxide

Ethanol Ethylene

175 gal

4.2 MWh

636 kg

1.6 MWh

318 kg

4.2 MWh

One ton of CO2 =

Minimum energy per ton of CO2 =

=Combined with H2

to make 150 gallons of

renewable diesel

=2900 miles driven

by average American car

=13 hrs of generation

by average wind turbine at Altamont

Pass

=<1 hr of generation

by a modern offshore wind

turbine

=~1.5 months of

generation by typical residential solar

system

=CO2 sequester in

polyethylene plastic

O2

1 CO CO 22 Overall Reaction:

Energy of Rxn Calculation:

= ΔfG(Products)-ΔfG(Reactants)

= ΔfG(CO)+1/2*ΔfG(O2)-ΔfG(CO2)

= -137.15 kJ/mol+1/2*0 kJ/mol-394.36 kJ/mol

= +257.21 kJ/mol (positive value indicates that this is the amount of

energy needed for the reaction to occur. Erxn = -1.33V)

= 0.0032 kWh/liter @ STP for a 100% efficient process

= 2.55 kWh/ kg

(0.071 kWh/mol)*(1 mol/22.4 L)

= 0.071 kWh/mol

ΔrxnG(CO2CO)

Calculation of CO2 to CO thermodynamics

O2

1 )e/ 2(H OH 2

-

2

OH CO )e/ 2(H CO 2

-

2 Cathode:

Anode:

2O CH O2H CO 2422 Overall Reaction:

Energy of Rxn Calculation:

= ΔfG(Products)-ΔfG(Reactants)

= ΔfG(CH4) + 2*ΔfG(O2) – [ΔfG(CO2) – 2*ΔfG(H2O)]

= -50.7 kJ/mol + 2*0 kJ/mol - (-394.36 kJ/mol + 2*-273.1 kJ/mol)

= +818 kJ/mol (positive value indicates that this is the amount of

energy needed for the reaction to occur)

= 0.010 kWh/liter (= 14.2 kWh/kg) @ STP for a 100% efficient process

(0.23 kWh/mol)*(1 mol/22.4 L)

= 0.23 kWh/mol

ΔrxnG(CO2C2H4)

Calculation of CO2 to Methane thermodynamics

3O HC O2H 2CO 24222 Overall Reaction:

Energy of Rxn Calculation:

= ΔfG(Products)-ΔfG(Reactants)

= ΔfG(C2H4) + 3*ΔfG(O2) – [2*ΔfG(CO2) + 2*ΔfG(H2O)]

= 68.3 kJ/mol + 3*0 kJ/mol - (2*-394.36 kJ/mol + 2*-273.1 kJ/mol)

= +1,331 kJ/mol (positive value indicates that this is the amount of

energy needed for the reaction to occur)

= 0.017 kWh/liter (= 13.2 kWh/kg) @ STP for a 100% efficient process

(0.37 kWh/mol)*(1 mol/22.4 L)

= 0.37 kWh/mol

ΔrxnG(CO2C2H4)

Calculation of CO2 to Ethylene thermodynamics

23.9 kWh/gal

1325.4 kJ/mol

CO (gas) Ethanol (liquid) Ethylene (gas)

47.8 kWh/gal

523 kg

175 gal

4.2 MWh

0.0032 kWh/L

257.21 kJ/mol

0.0064 kWh/L

636 kg

510 kL

1.6 MWh

0.017 kWh/L

1331.14 kJ/mol

0.033 kWh/L

318 kg

255 kL

4.2 MWh

Energy/mole of

product

Energy @ 100%

efficiency

Energy @ 50%

efficiency

Mass of product per

ton of CO2

Volume of product

per ton of CO2

All calculations at STP

Energy per ton of

CO2 converted to

given product @

100% efficiency

1,080 kg364 kg 1,080 kgkg of O2

per ton of CO2

Energy and mass balance for major products

Methane (gas)

0.010 kWh/L

818.0 kJ/mol

0.020 kWh/L

364 kg

510 kL

5.2 MWh

1,455 kg

PREPARED FOR DISCUSSION | 47