The 21st Century Frontier
과 학 기 술 부
21세기 프론티어연구개발사업
21st Century Frontier R&D Program
APPLICATION OF NANOTECHNOGY
ON HYDROGEN PRODUCTION AND
STORAGE IN KOREA
April 26~27, 2007
Jong Won Kim
Director
Hydrogen Energy R&D Center
http://www.h2.re.kr
4th US-Korea NanoForum, Honolulu, USA, April 26-27, 2007
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Hydrogen Energy R&D Center
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The 21st Century Frontier
Outline
I.
Hydrogen Economy- Vision
II.
Technical barrier
III.
Current R&D activities related
to nanotechnology
IV.
Conclusions
4th US-Korea NanoForum, Honolulu, USA, April 26-27, 2007
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Hydrogen Energy R&D Center
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The 21st Century Frontier
1. Hydrogen economy-vision
Hydrogen Economy
Nuclear
Wind
Solar
Biomass
Hydrogen storage/transportation/distribution
Water
Electrolysis
Bus
Infrastructure
Photochemical/
Thermochemical/
Biological H2
Production
Distributed Power
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Ship
Vehicle
Residential
Mobile
Submarine
Hydrogen Energy R&D Center
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The 21st Century Frontier
2. Technical barriers
Production/
Utilization
Amounts
~ 1% TPES
(Total Primary
Energy supply)
Raw materials
~95% fossil fuel
(NG etc)
Utilization
*Oil refinery (desulfurising, reforming)
*Chem.Ind.: Ammonia, fertilizer, methanol
*Metal Industry *Food( Fat, oil)
*welding
*Electronics
*cryogenic
*Electric generator-cooling
User
About 50million tons
~ 5% electrolysis
~ 45% petroleum
~40% Chem. Ind.
~15% others
<35% sales
>65% self-consumption
Domestic
Domestic 0.97
0.97 million
million ton
ton
Trade
48
thousand
ton*
Trade 48 thousand ton*
* Source: Bongjin Kim et al: “The status of domestic hydrogen production, consumption and distribution”, Trans. Of the Korea
Hydrogen and New Energy Society, 16(4)391-399(2005)
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The 21st Century Frontier
3-1 current R&D activities
Summary of Hydrogen & Fuel Cell R&D program
Table 1. Hydrogen & Fuel Cell R&D program in Korea
Program
21st Frontier Program (Hydrogen Energy R&D Center)
(www.h2.re.kr)
National RD&D Organization for hydrogen and fuel cell
(www.h2fc.or.kr)
Nuclear Hydrogen Development and Demonstration
Project (NHDD)
(www.hydrogen.re.kr)
Korea IGCC RDD&D Organization
(www.igcc.or.kr)
Sponsor
Period
MOST
2003-2013
MOCIE
2003-
MOST
2004-2021
MOCIE
2006-2014
MOCIE: Ministry of Commerce, Industry and Energy
MOST : Ministry of Science and Technology
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The 21st Century Frontier
3-1 current R&D activities
HERC
(Hydrogen Energy R&D Center)
Role
- Developing the National Hydrogen Energy R&D Program
* 21st Century Frontier Program
R&D Period
01 Oct. 2003 ~ 31 March 2013 (10
9.5 years for 3 phases)
R&D Fund
Total 90 million US dollars
(Government : 80 million dollars, Industry : 10 million dollars)
Sponsoring Ministry
Ministry of Science & Technology, Republic of Korea
Source: www.h2.re.kr
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The 21st Century Frontier
3-1 current R&D activities
National RD&D Organization for Hydrogen and Fuel cell
Exclusive
Evaluation
Committee
Ministry of Commerce,
Industry and Energy
(New & Renewable Energy Center)
Steering
Committee
National RD&D Organization
for Hydrogen and Fuel Cell
International
Collaboration
(IEA, IPHE)
Subcommittee
Hydrogen
Infra
Industrial/
Commercial/
Residential
Fuel Cell
Transportation
Fuel Cell
Portable
Fuel Cell
Monitoring
(Validation
Demonstration)
Established in 2003 to expedite the commercialization of hydrogen
hydrogen and fuel cell technology.
„ Propose the vision for hydrogen economy in Korea.
„ Develop a national plan, road maps and action plans to create a new industry.
„ Coordinate and manage RD&D programs supported by government.
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The 21st Century Frontier
3-1 current R&D activities
Nuclear Hydrogen Development and Demonstration Project
• To build 200MWth class VHTR and to produce 20 thousand tons of
hydrogen .
¾ Period : 2004 – 2021 (18years)
¾ Budget : ~ US$ 1.0 Billion (under discussion)
Cooler
PCU
Compressor
H2
H2
Recuperator
TBN
I-S Process
HTES
AC/DC Converter
O2
H2SO4 Decomposition
1000oC
Electrolyser
H2
970oC
H2SO4
SO2+H2O
H2+
H2O+
O2
+
½O2
H2SO4 Evaporator
HX
O2
VHTR
IHX
HI Decomposition
2HI
H2
+
+
I2
Condenser
Separator
H2+
H2O+
O2
H2SO4
2HI
H2+
H2O
I2
+
SO2+H2O
+
H2O
Bunsen Reaction
H2O
H2O
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Source: www.hydrogen.re.kr
Hydrogen Energy R&D Center
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III. -3 IGCC Project
The 21st Century Frontier
3-1 current R&D activities
□ Korea IGCC RDD&D organization
MOCIE
(New and Renewable
Energy Center)
Korea IGCC RDD&D
Organization
- Launched on 22nd December, 2006
- In the year 2014, 300MW IGCC
plant will be constructed
and operated
- 599.2 billion won (Government 165.2) .
*MOCIE; Ministry of Commerce, Industry and Energy
1st subdivision
(Heavy industry,
Research Institute)
Design of
Gasification plant and
process
2nd subdivision
(Power company,
construction
company)
Design, manufacture
and construction of
demonstration plant
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3rd subdivision
(Power company,
Research Institute)
4th subdivision
(Research Institute
and University)
Operation of
demonstration plant
Localization of unit
process
Hydrogen Energy R&D Center
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The 21st Century Frontier
3-1 current R&D activities
R&D Activities in the Phase II (HERC)(2006-2009)
Hydrogen Production
Action type
NG steam reforming for hydrogen station
Biological hydrogen production
Thermo-chemical hydrogen production
Photocatalytic and photochemical hydrogen production
Water electrolysis using PEM and THE
(AR/DE)
(BR/AR/DE)
(BR/AR/DE)
(BR/AR/DE)
(BR/AR/DE)
(Mid)
(Long)
(Long)
(Long)
(Long)
(BR/AR/DE)
(BR/AR/DE)
(BR/AR/DE)
(Long)
(Long)
(Long)
Hydrogen Storage
Hydrogen storage using metal hydrides
Hydrogen storage using nano-structured materials
Hydrogen storage using chemical hydrides
Hydrogen Utilization
Linear power/generation system of hydrogen combustion (AR/DE)
Hydrogen sensor
(AR/DE)
(Long)
(Long)
Supporting Project
Measurement techniques for hydrogen storage materials
Policy and technology assessment
BR: basic research, AR: applied research, DE: demonstration
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Hydrogen
Energy
R&D
Center
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The 21st Century Frontier
II. Current R&D Activities
Biological Hydrogen Production
3-2. current R&D activities
related to nanotechnology
™ R & D Objectives
-Scale-up and optimization of fermentative H2
production process and development of bio-mimetic
H2 production system
▶ Fermentative bioreactor scale : > 500 L
▶ Fermentative H2 productivity : 15 Nm3 H2/day/m3
▶ H2 productivity by bio-mimetic system : 40 L H2/kg
protein/hr
Project Manager: Dr. Kim, MiMi-Sun,
[email protected]
™ Recent publications:
Int.J.Hydrogen Energy,31(2006)812-816
Int.J.Hydrogen Energy,31(2006)121-127
Korea Patent 2005-0032480
Bioreactors for photosynthetic and fermentative H2 production
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The 21st Century Frontier
3-2. current R&D activities
related to nanotechnology
Nanotechnology and Biological hydrogen production
Flow direction
•
•
Introducing nano-size membrane to
bioreactor for enhancing hydrogen
production
Adjusting the pore size(40,100nm) for long
term operation
L
Membrane
bioreactor (working
vol. 2.4 L) using
PVDF hollow-fiber
G
B
F
H
K
F
M
J
E
B
I
B
B
N
C
A
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The 21st Century Frontier
3-2. current R&D activities
related to nanotechnology
Production
Yield
(A)
12
2.5
2.0
1.5
8
1.0
4
0.5
0
0.0
3
100
Glucose
Biomass
80
60
40
2
(B)
1
20
0
0
10.3
6.7
4.0
4.0
HRT (h)
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3.0
2.5
Cell (g/L)
MBR
(A)
100 nm pore-size
40 nm pore-size
(B)
100 nm pore-size
40 nm pore-size
2.0
1.5
1.0
0.5
0.0
Pressure across membrane
2
(kgf/cm )
CSTR
Biomass (g/L)
Glucose removal (%)
H2 production rate
(L H2/L/day)
16
H2 yield (mol/mol glucose)
Hydrogen production using membrane bioreactor at 60oC
0.5
0.4
0.3
0.2
0.1
0.0
0
5
10
15
20
25
30
Time (day)
Hydrogen Energy R&D Center
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The 21st Century Frontier
3-2. current R&D activities
related to nanotechnology
Schematic diagram of bio-mimetic H2 production system
R&D Contents:
e-
H2O
sun
O2
e-
e-
2 H+
Electron donor/carrier
(photosystem, microorganism)
Biopolymer immobilization
System integration
organics
eCO2
H2
hydrogenase
o
separation/purification
o
microorganism modification
Genome sequencing
photo-sensitizer (chlorophyil)
microorganism
Proteomes
hydrogenase
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The 21st Century Frontier
3-2. current R&D activities
related to nanotechnology
Photocatalytic and Photoelectrochemical Hydrogen Production Technology
™ R&D Objectives
- Development of the system for 3% solar light conversion
efficiency (@AM 1.5) utilizing solar light-sensitizing
photocatalyst
- System establishment for PEC cell of 7% efficiency
™ Content of R&D Activities
Solar light
Designed & controlled photocatalyst
- Highly active water splitting photocatalysts- material
design
- Tandem-type photoelectrochemical cell modules
- PEC cell of 7% efficiency
- Photo/Biocatalyst
- Q-sized photocatalysts and mesoporous media
- Layered Perovskite and Composite Photocatalysts
KRICT, KIER, KIST, POSTECH, Nanopac
h+
e-
H2O or H+
Enzyme
Sensitizer
PEC
related
Mechanism
System
design
Waste
resources
Reactor
design
H2 + (1/2 O2 or Red)
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If any question, contact: Dr. Moon,SangMoon,Sang-Jin
[email protected]
Hydrogen Energy R&D Center
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The 21st Century Frontier
3-2. current R&D activities
related to nanotechnology
Nanotechnology and sensor
z Enhancement of gas sensitivity using ceramic nano particles
with high surface area
• Semiconductor type hydrogen sensor
- measure the change of resistance of semiconducting material (such as SnO2, In2O3,
TiO2 etc) according to the adsorption of hydrogen gas. Nano sized semi-conducting
material could enhance the sensitivity.
• Catalytic combustion type sensor
- nano sized supporting material could enhance the sensitivity of sensor
Chi-Hwan Han et. al, "Micro-bead of nano-crystalline F-doped SnO2 as a sensitive hydrogen gas sensor", Sensors & Actuators B,
2005, 109, 264-269.
Chi-Hwan Han et. al, "Enhancement of H2-sensing Properties of F-doped SnO2 Sensor by Surface Modification with SiO2",
Sensors, 2006, 6, 492-502.
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3-2. current R&D activities
related to nanotechnology
Enhancement of sensitivity using nano materials
•
•
Linearity of sensitivity of ceramic
hydrogen sensor using nano particle
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Enhancement of sensitivity of
catalytic combustion type
hydrogen sensor using nano
particle or nano rod of Pd/TiO2,
Pt/TiO2
Hydrogen Energy R&D Center
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The 21st Century Frontier
Pressurized hydrogen storage vessel
3-2. current R&D activities
related to nanotechnology
TYPE
3
Process design and analysis
Filament winding and
solidification
Proto type vessel
TYPE
4
Analysis using finite element method
liner
Storage vessel after coating process
Tucsan using a high pressure vessel
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The 21st Century Frontier
3-2. current R&D activities
related to nanotechnology
PE-Clay nano composite
liner
: gas interrupting characteristic
-> increased to 30% than its
predecessors
liner thickness
-> could be reduced.
Fig. Gas Permeability of the nanocomposites for
various clay contents
7% clay-> the tensile modulus
increased about 49%
the tensile strength
increased about 15% as
compared with pure
polyethylene.
Source: Joong-Hee Lee et al, “Properties of polyethylene-layered silicate nanocomposites
prepared by melt intercalation with a PP-g-MA compatibilizer”, Composite Science and
Technology (2005))
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The 21st Century Frontier
3-2. current R&D activities
related to nanotechnology
Effective hydrogen storage capacity < Target
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The 21st Century Frontier
3-2. current R&D activities
related to nanotechnology
Nanotechnology and Alanate
•
•
•
Alanate- complex metal hydride with more than 5 wt% effective hydrogen storage capacity
decomposition temperature of alanate
Introducing nano sized particles
–
–
generating nanocrystallites through ball-milling
introducing the titanium nanoparticle as a catalyst
Ball-milling LiAlH4 and Li3AlH6 causes "the formation of a fine grain size below 20 nm
(Chen et al.,2001)
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The 21st Century Frontier
3-2. current R&D activities
related to nanotechnology
Lithium alanate system
DSC and TG curves of Li3AlH6 with and without catalysts
•
Li3AlH6 -> 3 LiH + Al +3/2 H2
Amount of hydrogen released from Li3AlH6
during thermal decomposition at 150oC as a
function of time
•
Y.W.Cho et al, Thermal decomposition of Li3AlH6 with TiAl3 catalyst, catalysis today (Feb.2007)
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Hydrogen
Energy
R&D
Center
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The 21st Century Frontier
Carbon base nanomaterials
3-2. current R&D activities
related to nanotechnology
Raw
(a)
Graphitized
(b)
Ball milled
(c)
Acid
treat
ed
(d)
Surface Modified ACFs
FluorinatedACF15
ACF15
Fluorinated
Nidoped
dopedACF15
ACF15
Ni
PVdF based Carbon Nanofiber
Hydrogen storage site of carbon nanotube
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fullerene
Hydrogen Energy R&D Center
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The 21st Century Frontier
3-2. current R&D activities
related to nanotechnology
Nanotechnology and carbon base materials
- High surface materials with nano pore for high hydrogen
storage capacity
- Nanopore exposition- surface oxidation at high temperature.
2400
2
2
Specific surface area (m /g)
2011 m /g
1800
1200
600
0
2
314 m /g
VGNFs
Porous GNFs
Carbon nanofiber with surface area about 300 m2/g could be changed to multipore
nanofiber with high surface area ( >2000 m2/g ) through a series of oxidation processes
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The 21st Century Frontier
3-2. current R&D activities
related to nanotechnology
Metal nanoparticle loading
- introduction of metal nano particles in order to control hydrogen adsorption sites
- introducing metal particles with controlled size- current density and time using
electrolysis and non-electrolysis
Carbon fiber
Metal nano particle
Introduction of Ni nanoparticle to the nanofiber surface using electrolysis and non-electrolysis
•
Y.S,Lee et al, “The adsorption properties of surface modified activated carbon fibers for
hydrogen storages”, catalysis today (Feb.,2007)
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The 21st Century Frontier
4. conclusions
•
•
•
•
We have investigated various
materials including MOF, organoporous nanomaterial, inorganic
materials based on molecular
modeling and we attempted to
improve surface functionality of
those materials.
But the hydrogen storage capacity
is still low at moderate condition.
We will investigate the mechanism
for the adsorption of hydrogen on
nanoporous material.
we will setup the virtual screening
protocol for the nanoporous
materials.
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(a)
FeBTBC: Fe4O2(BTB)8/3
MOF-5 : Zn4O(BDC)3
(b)
Contour Maps
Zn(dhBDC): Zn2O2(BDC)
of electrostatic potentials
; (a) IRMOF-1, (b) IRMOF-3
Hydrogen Energy R&D Center
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The 21st Century Frontier
4. conclusions
Think Together!
• There are lots of hurdles to hydrogen
production and storage
• Nanotechnology will help to overcome
those barriers.
™ There is nothing either good or bad. But thinking make it so.
™ Value is always every where!
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