Industrial Applications of Metal Hydrides
for Hydrogen Extraction, Storage and
Compression (HYDROTECH)
INTERNATIONAL SCIENCE AND TECHNOLOGY
AGREEMENTS: SOUTH AFRICA – NORWAY
Project # 180344
V.Linkov, M.Lototskyy (SA)
V.Yartys (NO)
Pretoria, 2010-09-20
Outline
• Background: Global energy challenge,
Hydrogen Economy and metal
hydrides (MH);
• Project results at a glance;
• Research results: summary
Pretoria, 2010-09-20
Global energy challenge
•Fossil fuels are the major part of the
actual balance of primary energy sources
•If the existent energy policy will be not
changed, the fraction of the hydrocarbon
fuels in the balance will steadily increase,
and by 2030 it will be as high as 90% of
the total growth of the energy
Renewables
consumption
6%
•The major part of this demand will be
compensated by oil, and ¾ of the oil will
be consumed by motor transport
Other
2%
Source: M.Haug,
Energy perspectives:
future energy
requirements and the
role for hydrogen, 1st
European Hydrogen
Energy Conference,
Grenoble, 2–5
September 2003
Nuclear
8%
Non-renewable – 94%
Fossil fuels – 84%
Coal
23%
Natural gas
24%Pretoria, 2010-09-20 Petroleum 37%
Fossil fuels challenge:
environment
•
•
•
•
Global warming (greenhouse effect)
Acid Rain
Pretoria, 2010-09-20
Smog
Etc.
• Necessity of the radical change in the energy policy towards
shortening of the consumption of the conventional
hydrocarbon energy carriers, viz. oil, natural gas and coal, is a
very actual problem. It touches upon the interests both
common to all mankind (climate and environment), and, also
economic and political ones for the countries importing the
hydrocarbon fuels. The solution of this problem is connected
to the necessity of:
– higher priority of the development and implementation of
energy-saving technologies;
– structural changes in the energy sector aimed to the
increase of the fraction of power production without
consumption of hydrocarbons and CO2 emissions into the
atmosphere.
Realisation of the Hydrogen Economy / Hydrogen Energy
Systems concept is the main pathway to change the energy
2010-09-20
infrastructurePretoria,
towards
desired direction
The Hydrogen Economy:
Vision and Challenges
¾H2 Separation
¾H2 Storage & Transportation
¾H2 Compression
¾H2 Purification
New hydrogen technologies are in a great demand
Pretoria, 2010-09-20
Metal Hydrides:
Key Properties and Applications
RE
a
H
Ni
M (s) + x/2 H2 (g) ↔ MHx (s) + Q;
(a)
M (s) + x H2O (l) + e– ↔ MHx (s) + OH– (l); (b)
H
Ni
b
T, oC 394
227
60
13
–23
–51
–73
LaNi5
MmNi4.5Al0.5
P, bar
100
127
Ti1.2Cr1.9Mn0.1
Zr0.7Ti0.3Mn2
Ca0.2Mm0.8Ni5
10
TiFe
1
Zr0.7Ti0.3CrFe
Mg
CaNi5
0.1
V0.85Ti0.1Fe0.05
LaNi4.5Al0.5
LaNi4.06Mn0.9
0.01
1.0
2.0
3.0
4.0
1000/T, K
Pretoria, 2010-09-20
9Hostmetal
metalmatrix
matrixaccommodates
accommodates
9Host
atomsininthe
theinterstitial
interstitialsites
sites
HHatoms
9Volumedensity
densityofofthe
the
9Volume
accommodatedHH atoms
atoms1.5-2.0
1.5-2.0
accommodated
timeshigher
higherthen
then for
forliquid
liquidHH2
times
2
9Fast
and
reversible
hydrogen
9Fast and reversible hydrogen
uptake/ / release
release
uptake
9Extremelywide
wideTT / / PPoperation
operation
9Extremely
ranges
ranges
9Significantheat
heateffects
effects
9Significant
9100%selectivity
selectivitytowards
towardsHH2
9100%
2
9Hactivation
activationby
byMH
MH
9H
9Significantvolume
volumechange
changeofofthe
the
9Significant
hostmetal
metalupon
uponhydrogenation
hydrogenation
host
Metal Hydrides:
Key Properties and Applications
RE
a
H
Ni
H
Ni
b
M (s) + x/2 H2 (g) ↔ MHx (s) + Q;
(a)
M (s) + x H2O (l) + e– ↔ MHx (s) + OH– (l); (b)
‰ Safe,
compact and technologically
T, oC 394 227 127 60
13 –23 –51 –73
flexible hydrogen
storage;
LaNi
P, bar
MmNi hydrogen
Al
‰ Thermally-driven
Ti Cr Mn
100
Zr Ti Mn
compression
(no moving parts);
‰ Efficient heat management,
Ca Mm Ni
10
possibility to utilise low-potential
TiFe
oC);
heat
(T<150
1
Ti CrFe
‰ Hydrogen
separation &Zrpurification
Mg
CaNi
(1-2 stages at near-ambient
0.1
V Ti Fe
conditions);
LaNi Al
LaNi Mn
‰0.01Catalysis;
‰ Electrochemical (NiMH batteries,
1.0
2.0
3.0
4.0
1000/T, K
fuel
cells);
‰ Powder metallurgy;
Pretoria, 2010-09-20
‰…
5
4.5
0.7
0.3
0.5
1.2
2
1.9
0.1
0.2
0.7
0.8
5
0.3
5
0.85
4.5
4.06
0.9
0.5
0.1
0.05
9Hostmetal
metalmatrix
matrixaccommodates
accommodates
9Host
atomsininthe
theinterstitial
interstitialsites
sites
HHatoms
9Volumedensity
densityofofthe
the
9Volume
accommodatedHH atoms
atoms1.5-2.0
1.5-2.0
accommodated
timeshigher
higherthen
then for
forliquid
liquidHH2
times
2
9Fast
and
reversible
hydrogen
9Fast and reversible hydrogen
uptake/ / release
release
uptake
9Extremelywide
wideTT / / PPoperation
operation
9Extremely
ranges
ranges
9Significantheat
heateffects
effects
9Significant
9100%selectivity
selectivitytowards
towardsHH2
9100%
2
9Hactivation
activationby
byMH
MH
9H
9Significantvolume
volumechange
changeofofthe
the
9Significant
hostmetal
metalupon
uponhydrogenation
hydrogenation
host
Project Objectives
• To establish the long-term and sustainable research
collaboration between the leading teams in Norway (NO) and
South Africa (SA) engaged in fundamental and applied
studies of metal hydrides (MH) focused on the development
of the efficient technologies for hydrogen recovery.
• The main goal is to strengthen the competence of NO and SA
R&D communities within the field of MH technologies to be
implemented in the environment friendly hydrogen energy
systems where a large global industrial market demand is
evidently foreseeable.
• Sub-goals of this project are:
–
–
–
to educate two SA PhDs complementing resources of their home
university by the top-level potential of Norwegian institutions in the
field;
to develop novel materials and engineering solutions for hydrogen
extraction from industrial gas streams, its compact and safe
storage and easy in operation supply to a consumer;
to propose novel approaches of utilisation of SA resources of
noble metals (incl. Pd) in high technologies.
Pretoria, 2010-09-20
Project participants:
• South Africa, SAIAMC / UWC:
–
–
–
–
–
Prof. V.Linkov, grant holder
Dr. M.Lototskyy, project manager
Dr. M.Williams
Mr. M.W.Davids
Ms. B.Ntsendwana (since 2009)
• Norway:
–
–
–
–
Prof. V.A.Yartys (IFE), grant holder & project manager
Prof. J.K.Solberg (NTNU)
Dr. J.P.Maehlen (IFE)
Dr. R.V.Denys (IFE)
Pretoria, 2010-09-20
Scope of activities
• Advanced surface-modified materials for
hydrogen separation and purification
• Novel Mg-based H storage materials
characterised by ultra-fast hydrogenation
kinetics
• Advanced characterisation of MH materials
for H separation / purification, storage and
compression; engineering solutions
Pretoria, 2010-09-20
Sharing the responsibilities
SAIAMC / UWC
IFE, NTNU
Surface modification of the core
materials
Study of activation properties of
the core and modified materials
and their sorption / desorption
performances at the operation with
H-containing gas mixtures
Development of the technologies
for the preparation of advanced
MH materials
Development of prototype H
separation / purification,
compression and storage systems
Selection / preparation of the core
materials
Structural characterisation
Morphological studies
H sorption properties
Training of SAIAMC students /
postdocs
Development of advanced
experimental facilities
Pretoria,
Visits: SA – NO (6 times,
5 2010-09-20
persons); NO – SA (3 times)
Research results
• A surface nanoengineering approach was developed to
enhance the hydrogenation ability and poisoning
tolerance of hydride-forming intermetallics;
• Novel nanostructured Mg-based H storage materials
characterised by ultra-fast kinetics of H absorption were
developed;
• In-depth characterisation of MH materials used for H
separation / purification, storage and compression was
carried out;
• Demonstration prototypes of MH systems for industrial
applications were developed;
• 14 international publications, incl. 4 research papers and
2 invited / keynote conference presentations were
issued. 5 research papers are waiting for the publication.
Pretoria, 2010-09-20
HCD results
• M.Williams, Palladium surface modified rare
earth metal based AB5 type hydride forming
materials, PhD degree granted, March 2009
• M.W.Dawids, Advanced Ti based AB and AB2
hydride forming materials, submission of the
PhD thesis is planned for June, 2011
• B.Ntsendwana, Advanced “low-temperature”
MH materials for LT-PEMFC Systems,
submission of the MSc thesis is planned for
November, 2010
Pretoria, 2010-09-20
Impact: new SAIAMC projects based on
the results of the collaboration
• ESKOM: development of MH H2 separation /
purification and compression systems;
• Department of Science and Technology, HFCT
RDI Program “HySA”, projects:
– KP2-S01: Metal Hydride Hydrogen Storage for LowTemperature PEMFC Power Systems;
– KP3-S02: On-Board Use of Metal Hydrides for Utility
Vehicles;
– KP3-S04: On-Board Hydrogen Storage;
– KP8-S02: Metal hydride integrated energy systems.
Pretoria, 2010-09-20
Research results
Summary
Pretoria, 2010-09-20
Mechanism of H2 – M
interaction
H2 gas
+
METAL
MOLECULAR H2
ADSORPTION
DISSOSIATION (H2 = 2 H)
AND CHEMISORPTION
α-SOLID SOLUTION
H/M < 0.1
DIFFUSION
+ H2
HYDROGENATION
β-HYDRIDE PHASE
ATOMIC H
H/M > 1
Pretoria, 2010-09-20
Problem
H2 gas
+
METAL
MOLECULAR H2
ADSORPTION
DISSOSIATION (H2 = 2 H)
AND CHEMISORPTION
SENSITIVE TO ACTIVE IMPURITIES
α-SOLID SOLUTION
(SURFACE POISONING)
H/M < 0.1
DIFFUSION
+ H2
HYDROGENATION
β-HYDRIDE PHASE
ATOMIC H
H/M > 1
Pretoria, 2010-09-20
Solution: surface modification
Substrate
Metal deposition
Flu
Substrate
.
et
M
ori
na t
ion
MH substrate:
AB5, AB
po
de
Metal deposition:
Pd (+ Ni, Cu, Pt)
n
tio
si
Substrate
/F
o
lu
rin
n
io
at
Fluorination:
HF (+ NiF2)
Substrate
Substrate
Pretoria, 2010-09-20
Substrate
Advanced surface-modified MH materials
¾Main funding – ESKOM, characterisation within
the SA-NO project;
¾New surface engineering technologies for
modification of powdered H storage alloys have
been developed at SAIAMC (one SA patent
granted and one international pending) :
Dynamics of H
¾Total introduction of 0.5–1 wt.% Pd results in an
increase of the H absorption rate by ~2 orders of
magnitude
¾The surface-modified materials may be applied in
highly-selective H2 extraction and purification
processes
absorption
(AB5, P=5 bar, T=20 oC, no preactivation):
1 – non-modified;
2 – Pd (conventional plating);
3 – Pd (advanced);
4 – F+Pd (advanced).
2
H/AB5
9 Surface functionalization with aminosilanes +
electroless deposition of Pd (Pt)
9 Fluorination + surface functionalization with
aminosilanes + electroless deposition of Pd
3
5
4
4
2
4
3
3
2
1
1
0
0.0 0.2 0.4 0.6 0.8
5
10
15
20
Time (hours)
• Williams M., PhD. Thesis, University of Western Cape, 2009
• Williams M, Lototsky M.V, Nechaev A.N, Linkov V.M, Yartys V.A, Li Q, Proc. NATO Adv. Research Workshop on Using Carbon Nanomaterials in
Clean-Energy Hydrogen Systems, Sudak, Crimea, Ukraine, September 22-28, 2007, Springer, 2008, pp. 625-636
• Williams M, Nechaev A.N, Lototsky M.V, Yartys V.A, Solberg J.K, Denys R.V, Pineda C, Li Q, Linkov V.M (2009), Materials Chemistry and Physics,
115 (1): 136-141.
• Williams M., Lototsky M.V., Linkov V.M., Nechaev A.N., Solberg J.K., Yartys V.A. (2009), Int. J. Energy Research, DOI: 10.1002/er.1609
• Lototskyy M., Williams M., Yartys V.A., Invited lecture at International Symposium on Metal – Hydrogen Systems / MH2010, Moscow, 19-23 July, 2010
Pretoria, 2010-09-20
25
Performance: H2 + admixtures
AB5 / unmodified
1.2
AB5 / F / Pd
Pure H2
H2 + 10% CO2 + 10% N2 + 5% CH4
H2 + 0.25% CO2 + 0.45% N2 + 0.05% CH4 + 40 ppm CO
1.0
Pure H2
H2 + 10% CO2 + 10% N2 + 5% CH4
H2 + 0.25% CO2 + 0.45% N2 + 0.05% CH4 + 40 ppm CO
1.2
Rate [Ncm /(g*s)]
0.8
3
3
125 Ncm /g
0.8
3
140 Ncm /g
3
Rate [Ncm /(g*s)]
1.0
0.6
0.4
3
0.6
122 Ncm /g
0.4
3
50 Ncm /g
3
0.2
100 Ncm /g
0.2
3
117 Ncm /g
0.0
0.0
0
40
80
120
160
400
time [seconds]
600
800
1000
0
20 40 60 80 100 120 140
200
300
400
500
600
time [secomds]
¾ Surface modification of AB5-type MH material results in the significant improvement of
its poisoning tolerance towards CO2 and, especially, trace amounts of CO presenting in
the feeding gas;
¾ As distinct from the unmodified material exhibiting gradual deterioration of H
absorption capacity in the course of ABS/DES cycling at the presence of CO, the
surface-modified material is stable at the same conditions during, at least, 10–15 cycles;
Pretoria,
2010-09-20of the surface-modified MH materials
¾ Our preliminary results have proven
the feasibility
in efficient hydrogen separation from CO2- and CO-containing gas mixtures.
New Mg-based MH nanocomposites
3.5
TEQ=ΔH / [R ln(P) + ΔS ]
700
3.0
650
2.5
600
Mg / 35 V
2.0
Ts
550
500
1.5
450
1.0
400
0.5
350
300
0.0
250
0.0
0.1
0.2
0.3
0.4
2 4 6 8 10
Time [minutes]
In situ SR XRD studies of phase
transformations during hydrogenation
of Mg / 35V composite at T0=100 °C
under 12.5 bar H2:
I. BCC (A) → VH0.5 (B)
II. VH0.5 → VH0.7 (B)
Mg (C) → MgH2 (D)
(III). VH0.7 → VH2 (T< 100 oC; P> 10
bar)
T [K]
wt.% H
o
T0=23 C; P=26 bar)
Synchrotron diffraction: SNBL, ESRF,
Grenoble: experiments carried out by IFE
using specially developed in situ setup
• Hydrogenation
completes in 5–60
seconds and is
accompanied by a
significant heat
release
• Sample temperature,
Ts, approaches
equilibrium value
(Mg ↔ MgH2) for
the operating H2
pressure
• Mechanism of phase
transformations was
found from in situ SR
XRD studies (Swiss
– Norwegian
beamline, Grenoble,
France)
D
D
D
C
A
C
• Lototsky M.V., Denys R.V., Yartys V.A. (2009), Int. J.
Energy Research, DOI: 10.1002/er.1604
Pretoria, 2010-09-20
C
B
Prototype 60 L H2 / h MH microcompressor
H2 @ PH
LT MH
(AB2)
Compression
element: heating /
cooling block
Check valves
Q @ TL
Q @ TH
Q @ TH
Q @ TL
HT MH
(AB5)
H2 @ PL
•Main funding – ESKOM, materials
development & characterisation
within the SA-NO project
•2 stages (I – AB5; II – AB2)
•PL ~ 5–10 bar; PH=200 bar
•TL ~ 15–25 oC; TH~120 oC
•Permanent operation
•Water cooling
•Electric (option - steam) heating
•Assembled & tested (March 2009)
•Original solutions as to the layout
are being verified
•Development of the 10 m3 H2/h MH
compressor is underway
Two SA patents granted
Pretoria, 2010-09-20
Prototype water-cooled MH hydrogen
storage unit for a LT PEMFC application
•Main funding – HySA Systems (KP2-S01), material development & characterisation
within the SA-NO project;
•Total weight 22 kg, incl. 12 kg of La0.85Ce0.15Ni5 H storage alloy;
•Storage capacity 1.56 m3 H2 STP;
•Can provide > 2 hours of full-load operation of a 1 kW LT PEMFC-stack.
Pretoria, 2010-09-20
Thank you
Pretoria, 2010-09-20