electrochemical pathways towards carbon-free … · sadoway gcep carbon management in manufacturing...
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ELECTROCHEMICAL PATHWAYS
TOWARDS
CARBON-FREE
METALS PRODUCTION
Department of Materials Science
& Engineering
Massachusetts Institute of Technology
Cambridge, Massachusetts
Donald R. Sadoway
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
The message
The road to sustainability is paved
with advanced materials.
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
problems with metals extraction
� steelmaking makes CO2 �
2 FeO + C = 2 Fe + CO2
(� kg C / kg Fe) x 1.2 billion tonnes
� sundry HAPs including Mn & Pb,
polycyclic organics, benzene, & CS2
� unfavorable by-products �
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
Why is metal production so dirty?
� many processes are over
100 years old
� attitude then of indifference
towards the environment
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
Why is metal production so dirty?
“Where there’s smoke, there’s money.”
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
We’re all just temporarily visiting this planet
Towards sustainability
� Green technology
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ELECTROCHEMICAL PATHWAYS
TOWARDS
CARBON-FREE
METALS PRODUCTION
Department of Materials Science
& Engineering
Massachusetts Institute of Technology
Cambridge, Massachusetts
Donald R. Sadoway
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
Where do metals come from?
� occur naturally as compounds
� beneficiated � high-purity feed
� reducing agents: H, C, M, e-
� options for sustainability?
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
beyond the blast furnace
extreme form of molten salt electrolysis
� molten oxide electrolysis:
where pure oxygen gas is the by-product
�����
� most metals are found in nature as oxides
� “like dissolves like”
� e- is the best reducing agent
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world capacity: ~40 million tons/year
aluminum produced by electrolytic reduction of Al2O3
decompose Al2O3 dissolved in Na3AlF6 (T = 960°C)
� liquid Al (-) and CO2 (+)
� find an inert anode & molten oxide electrolyte
Charles Martin Hall, USAPaul Héroult, France
1886
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
(FeOx) � Fe(l) + � O2
iron
iron
green ironmaking: cell schematic
x
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
Technology Needs: dateline 2050
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
Technology Taxonomy: Reducing Agents
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
Environmental Impact & Energy Savings
kg
CO
2/t
ls
GJ n
et
en
erg
y
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
Environmental Impact & Energy Savings
� CO2 emissions reduced from 1750 kg/tonne liquid steel
for benchmark blast furnace technology
to 345 kg/tonne liquid steel: a five-fold reduction
� 90 g CO2/kWh for generation of electric power
� equivalent energy consumption: MOE vs benchmark
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
Other Benefits
tonnage oxygen
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
scientific and technical challenges
� molten oxides of transition metals exhibit
electronic conduction
� inert anode operable at temperatures as
high as 1700°C in an oxide melt
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
some of the relevant engineering science:
� electrical conductivity measurements
� transference number measurements
� voltammetry � process kinetics
� electrolysis testing
�
�
�
�
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
conductivity measurements
� inventing two new techniques for aggressive
melts at high temperatures:
� moveable coaxial cylinders
� 4-point crucible
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
moveable coaxial cylinders
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
effect of FeO addition: � = �(T, c)
-2.5
-2.0
-1.5
-1.0
-0.5
0
50 52 54 56 58 60 62
105/T (K)
S1
20%
5%
10%
15%
1.000
0.606
0.367
0.223
0.135
0.082
1727 1650 1579 1513 1451 1394 1340
T(ºC)
� /
S c
m-1
ln �
/ S
cm
-1
1425
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
FeO greatly raises conductivity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18
� / S
cm
-1
T = 1425ºC
XFeO in S1
� = 2.0766 XFeO + 0.0897
R2 = 0.9796
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
regression of conductivity data
y = x
R2 = 0.8918
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.10 0.20 0.30 0.40 0.50
� = - 0.138 - 0.361*SiO2 + 1.186*FeO + 0.917*(FeO+MgO+CaO)
� / S
cm
-1
T = 1425ºC
0
� = � ai*X
i
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electrochemistry at white heat
CaO - MgO - SiO2
T = 1575°C
scan rate = 50 mV s-1
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electrochemistry at white heat
CaO - MgO - SiO2
T = 1575°C
scan rate = 50 mV s-1
--- supporting electrolyte
--- 5 wt% FeO
add 5% FeO to
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
electrolytic production of molten iron:
cathode: Mo
anode: Pt
electrolyte:
CaO - MgO - SiO2
feed: FeO
crucible: Mo
reactor tube: Al2O3
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
constant-current electrolysis at 1575oC
current density: ~1 A cm-2
iron
electrolyte
Mo crucible
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
more electrolytic production of molten iron:
iron
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SEM and EDX analysis
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oxygen generation on the moon
by molten oxide electrolysis:
� sustaining human life
� rocket propellant
let’s now raise our sights
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Oxygen Extraction From Regolith
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University of Michigan April 4, 2008 Sadoway
Lab-scale Cell for Regolith Electrolysis
water chiller (for cell cap)
Ar in
Ar out
potentiostat and
impedance spectrometer
furnace power supply
hot zone
Ar bubblers
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University of Michigan April 4, 2008 Sadoway
Lab-scale Cell for Regolith Electrolysis
water chiller (for cell cap)
Ar in
Ar out
potentiostat and
impedance spectrometer
furnace power supply
hot zone
Ar bubblers
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
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University of Michigan April 4, 2008 Sadoway
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University of Michigan April 4, 2008 Sadoway
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
O2 evolution rate vs. optical basicity
i = FAk°CO2-e-�F�/RT
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
O2 evolution rate vs. optical basicity
i = FAk°�e-�F�/RT
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
cyclic voltammetry in titanates at 1550ºC
WE: Mo
RE: Ti
CE: Mo
supporting electrolyte
melt containing TiO2
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WE: Ti
RE: Ti
CE: Mo
cyclic voltammetry in titanates at 1550ºC
supporting electrolyte
melt containing TiO2
Cu
rre
nt
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
electrolytic production of liquid titanium
frozen electrolyte
titanium puddle
Mo crucible
cathode: Mo
anode: C
current density �1 A/cm2
T = 1725°C (above m.p. of Ti)
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
analysis of metal pool indicates titanium
CP titaniumtitanium
made by theSadowayProcess
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
what have we learned?
� deposition of Fe, Ti, Ni, & Cr in oxide melts
from oxide feedstock
� very high current densities are sustainable
� 5 A cm-2 observed; maybe higher!
c.f. 0.7 A cm-2 in Hall-Héroult cell
� 15� productivity of aluminum smelting
� capable of tonnage productivity
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
what else have we learned?
� first evidence of inert anode
� carbon-free metal making with tonnage
industrial oxygen as by-product
� full realization of the concept of
molten oxide electrolysis
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
workshop questions
� How would low- or zero-cost CO2
sequestration change the game, and
what barriers to separating and capturing
carbon would remain?
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
workshop questions
� If carbon-free or carbon-neutral energy
carriers were cost competitive with
current feedstocks, what technical and
economic challenges would prevent the
switch to those fuels?
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
workshop questions
� What are the opportunities for disparate
industries to collaborate on carbon
management?
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
workshop questions
� How can industry's specialized
knowledge of process engineering and
material handling address the grand
challenge of reducing carbon emissions?
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
workshop questions
� What are the research priorities in your
area of investigation and why?
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
workshop questions
� What barriers exist to successful
research and what breakthroughs are
needed?
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
workshop questions
What are the opportunities for
fundamental, academic research to
develop pathways for technologies to
overcome the barriers?
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
workshop questions
Where do you feel that a contribution by
a project such as GCEP could have the
most impact?
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GCEP Carbon Management in Manufacturing Industries April 15, 2008 Sadoway
towards carbon-free metallurgy
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The End