Production of Synthesis Gas by

High-Temperature Electrolysis of
H2O and CO2 (Coelectrolysis)

www.inl.gov

Carl Stoots
Idaho National Laboratory

Sustainable Fuels from CO2, H2O, and Carbon-Free Energy

Columbia University, New York, May 4, 2010

Why High Temperature Electrolysis (HTE) at INL?

INL is US lead nuclear energy laboratory
Nuclear power has significant excess
generating capacity
But, nuclear power is only used for
electrical power generation
Water splitting / hydrogen production via
nuclear power could:
Utilize excess generating capacity
via load leveling
Relieve the pressure on natural gas
for hydrogen production
Provide raw materials and GHGfriendly energy for synthetic fuels
production
Diversify uses for nuclear power
Extension to coelectrolysis leverages our
much larger program studying high
temperature H2O electrolysis
Energy Information Administration / Annual Energy Review 2008

However, as will be discussed later, high temperature electrolysis is also synergistic

with intermittent renewables such as wind or solar.
Stoots, Sustainable Fuels, May 4 2010

History of INL HTE Program

DOE Nuclear Hydrogen Initiative (NHI) founded 6 years ago
Goal -- demonstrate commercial-scale production of hydrogen
using:
Advanced nuclear energy (non-carbon emitting)
Water splitting technology (sustainable)
High temperature (energy efficient)
Three processes developed in parallel

SI Process

Hybrid Sulfur Process

HTE Process

INL lead lab for HTE

Stoots, Sustainable Fuels, May 4 2010

Program Status
NHI program conducted a down-selection last summer
HTE identified as most promising technology
Considered most robust
Reversible (produce H2 or electricity)
Steam and Steam/CO2 electrolysis
NASA BSC Stack
DOE-NE should focus on the continued development of HTE
INL HTE now funded through Next Generation Nuclear Plant (NGNP) program
Historically we have concentrated on designs from Ceramatec Inc.
With increasing interest in H2 production, we have tested more designs from other vendors

Rolls Royce Fuel Cell Systems

Typical Ceramatec SOEC Stack

St. Gobain

MSRI
Stoots, Sustainable Fuels, May 4 2010

INL HTE Program Description

Bench Scale Experiments
CFD Simulation
Scale-Up
System Modeling

720 cells, 15 kW

Stoots, Sustainable Fuels, May 4 2010

electricity,
heat

Coelectrolysis

H2O + CO2 H2 + CO + O2
Coelectrolysis reduces H2O and CO2 simultaneously
Motivation:
Syngas can be feedstock for methane or synthetic liquid fuel production
Coelectrolysis syngas production to synfuel utilization can be carbon-neutral if:
non-CO2 emitting energy source is used (nuclear, wind, etc.)
CO2 source is from biomass
Actively being studied by INL, Risoe, and Ceramatec
INL coelectrolysis funding << steam electrolysis

Stoots, Sustainable Fuels, May 4 2010

Coelectrolysis
Coelectrolysis is not well understood
- Multiple reactions
Steam electrolysis

Figure of merit representing net effect of

all loss mechanisms in cell / stack

Reverse Shift Reaction (RSR)

CO2 + H2 CO + H2O
CO2 electrolysis?
Our Area Specific Resistance (ASR) measurements indicate:
ASRcoelectrolysis ~ ASRH2O
ASRdry CO2 > ASRH2O
-Seems that:
H2O consumed in electrochemical reaction
CO2 consumed in RSR
- While it is possible to produce syngas by separately electrolyzing steam and CO2, there are
significant advantages to electrolyzing steam and CO2 simultaneously
Lower cell resistance (lower ASR)
Reduced possibility of further reduction of CO to C

Stoots, Sustainable Fuels, May 4 2010

Coelectrolysis Testing Apparatus

Stoots, Sustainable Fuels, May 4 2010

Stack Performance:
Electrolysis vs. Coelectrolysis
14

CO Electrolysis
2
2
ASR
~ 3.84 !cm

Stack Operating Voltage (V)

13

CO2

12

Tests #20, 21, 22 (sequential tests)

Same stack
800 C operating temperature

11
H O Electrolysis
2
2
ASR
~ 1.36 !cm
H2O
H O/CO Coelectrolysis
2
2
2
ASR
~ 1.38 !cm

10
9

H2O/CO2

8
7
6

10
15
Stack Current (A)

20

25

Dry CO2 ASR significantly higher than steam ASR

Stack performance same for steam electrolysis or coelectrolysis
Explanation (as stated earlier):
H2O consumed in electrochemical reaction
CO2 consumed in RSR
Stoots, Sustainable Fuels, May 4 2010

Typical Coelectrolysis Stack Results

20
Inlet CO

Mole % (Dry Basis)

15

Experimental Results
Model Results

10

CO

Stepwise DC potential sweeps

At zero current (no electrolysis)
CO2, H2 consumed
Reverse shift reaction
CO produced
Yield of syngas increased linearly with current
Good agreement with INL-developed
coelectrolysis model

Inlet H

CO
Inlet CO
0

4
6
8
10
Electrolysis Current (A)

12

Stoots, Sustainable Fuels, May 4 2010

Extensions of Coelectrolysis
100
80

INL studying hybrid energy systems

Linked electrolysis to natural gas, methanol, and DME production

2
2

Test 5, Stack Inlet

Test 5, Stack Outlet
Test 5, Methanation Outlet

20
0

Net Reaction
CO2 + 2H2O CH4 + 2O2
Tests performed by Ceramatec for INL

Test 4, Stack Inlet

Test 4, Stack Outlet
Test 4, Methanation Outlet

CO + 3H2 CH4 + H2O

CO

40

Test 3, Stack Inlet

Test 3, Stack Outlet
Test 3, Methanation Outlet

Methanation

CO

Test 2, Stack Inlet

Test 2, Stack Outlet
Test 2, Methanation Outlet

Tubular reactor
Ni catalyst

CH

60

Test 1, Stack Inlet

Test 1, Stack Outlet
Test 1, Methanation Outlet

Electrolysis cell

Methanation of coelectrolysis products

Water splitting
4H2O 4H2 + 2O2
RSR
CO2 + H2 CO + H2O

= Synthetic Methane,
Liquid Methanol,
DME
Stoots, Sustainable Fuels, May 4 2010

Navy Synfuel Program at Ceramatec Inc.

Salt Lake City, Utah
Syngas from coelectrolysis is
Compressed
Stored for batch processing
Converted to liquid hydrocarbons via Fischer-Tropsch

Oil fraction
Water fraction

Stoots, Sustainable Fuels, May 4 2010

General Comments About Coelectrolysis

0.4
0.4

0.3

0.2

current density, A/cm2

0.1

-0.1

-0.2

-0.3

reaction
ohmic
net

fuel cell electrolysis

2

heat flux, W/cm

0.2

thermal neutral
voltage
0

open-cell
potential
-0.2
-0.4

-0.6

-0.8

-1

operating voltage, V

-1.2

-1.4

Open cell potentials for H2O and CO2 electrolysis are about same (~0.9 V)
Thermal neutral voltage
Voltage at which endothermic heats of reaction balance ohmic heating

Isothermal and adiabatic operating point

Operation at Vtn minimizes thermal stresses
Vtn,CO2 > Vtn,H2O, therefore Vtn,coelectrolysis > Vtn,H2O
Coelectrolysis at Vtn,coelectrolysis will have greater current throughput than same cell at
steam electrolysis Vtn,H2O
Stoots, Sustainable Fuels, May 4 2010

Electrolysis vs. Coelectrolysis?

Assume your desired goal is to convert H2O/CO2 to FT liquid using electrolysis
electricity
H 2O

Steam Electrolysis

H 2O
Electrolysis

H2, H2O

FT Reactor /
Shift Reactor

FT Liquid

CO2
electricity

Coelectrolysis

H 2O
CO2

H2O/CO2
Coelectrolysis with RSR

Syngas

FT Reactor

FT Liquid

Steam Electrolysis:
1. RSR occurs in FT reactor, RSR endothermic heat requirement can take
advantage of heat rejected by FT reactor.
Coelectrolysis:
1. Higher Vtn for coelectrolysis means coelectrolysis at Vtn,coelectrolysis will produce
more H2 than steam electrolysis at Vtn,H2O
2. Reaction kinetics for RSR are better at elevated temperature of electrolysis
cell electrode.
Ignoring other considerations, steam electrolysis could be more logical choice for
medium temperature Fe catalysts while coelectrolysis more logical for low
temperature Co catalysts

Stoots, Sustainable Fuels, May 4 2010

Why Electrolytic Synfuels?

Electrolysis efficiency
Energy storage density (~10x greater energy storage density)
Fits in existing distribution infrastructure
Potentially no added CO2 emissions
Reduced work of compression
Recycling CO2: conversion of
Low value carbon (CO2 - $55/ton Norway C tax)
High Value Carbon
Natural Gas $444/ton carbon
Crude Oil $888/ton carbon (@$100/bbl)
Refined Fuel (pre-tax) ~$1000/ton carbon
Synergy with intermittent energy sources

Stoots, Sustainable Fuels, May 4 2010

Near-Term Coelectrolysis Deployment Strategy

High temperature coelectrolysis has fast startup / shutdown times (ramping)
makes it an attractive match for intermittent energy sources (wind, solar, etc.)
Load leveling
One could consider existing off-peak excess generating capacity as an
intermittent source as well
Electrolyzer can also supply electricity to help meet peak demand
Large economic incentives to meet variable energy demands and
Operate existing plants at maximum output
Capture and utilize carbon rather than store (CO2 recycling)
Develop energy storage / conversion technologies

Stoots, Sustainable Fuels, May 4 2010

One Technology Multiple Modes of Operation

Solid Oxide Stack Module
NG
Biogas
Diesel
JP-8
Coal

Fuel

Syngas

Electricity

CO2 & Steam

+ Electricity

Hydrogen
Steam +
Electricity (High Purity)
& Oxygen
Stoots, Sustainable Fuels, May 4 2010

Sounds Wonderful Whats the Problem?

Economic projection
assuming $50/MW-hr electric power costs
assuming SOFC system capital costs of $400/kW (DOE
SECA targets)
coelectrolysis is not competitive with current $70/bbl oil
but may be if oil prices once again climb above $130/bbl
implementation of some sort of carbon emissions cost
would further close the gap by $10-$20/bbl.
Cell performance degradation
Not commercially ready technology
SOFCs have achieved performance degradation values <
1% / 1000 hours
SOEC degradation rates much higher
Improving SOEC durability is focus of INL research

Stoots, Sustainable Fuels, May 4 2010

Wrap-up of Coelectrolysis Technology

High efficiency while using power from a diverse mix
Nuclear
Renewables (Wind, Solar, etc.)
Biomass
Conventional fossil-fuel-based power generation
Synergies enabling greater penetration of renewable energy in generation mix
Enables CO2 recycling
Converts a low-value carbon form (CO2) to a high-value carbon form (syngas/synfuel)

Stoots, Sustainable Fuels, May 4 2010

Thank you!

Stoots, Sustainable Fuels, May 4 2010

Supplemental Why High Temperature

Stoots, Sustainable Fuels, May 4 2010