Progress and Development in Hydrogen Energy

Green Energy and Fuel Laboratory (GENFUEL)
Wei-Hsin Chen

Clean Energy and Fuel Laboratory
(GENFUEL)

December 26, 2013

Progress and Development in
Hydrogen Energy

A Vision of Hydrogen
Economy

3

1850: Onset of the
Industrial Revolution and a
large amount of coal used.
1900-1920: Transition to the
use of oil.
1970: Onset of the use of
natural gas and nuclear
power.
1990: Renewable energy
applied in the electricity
market.
2050: Hydrogen plays a
vital role on the use of
energy.
Trajectory of Primary Fuel Use
4
Lightest element in nature
Most abundant element in the universe
Highest power density (143 kJ /g
NG: 55.6 kJ /g
oil: 48.1 kJ /g
Normal boiling point (20.3 K)
Very low minimum ignition energy
(0.017mJ )
High dissipation and emission
Stored in hydrocarbons and water
Property of Hydrogen
5
Hydrogen
H
2
Oil refining
Methanol
synthesis
Fertilizer
Fuel
Desulfurization
Propellant
Semiconductor
Application of Hydrogen
6
Hydrogen Energy
Hydrogen is a promising fuel for solving energy
(security) and environment (global warming and air
pollution) challenges.

Unlike solar or wind energy, hydrogen can be stored
and used anywhere, acting as an energy carrier.

The development of hydrogen as an alternative fuel
to fossil fuels is very likely to become more and more
important in the future, especially for the
combination with CCS.

Progress of Hydrogen Energy

8
Initiation
On 18-21 March 1974, at the landmark Hydrogen
Miami Energy (THEME) Conference, a small group of
hydrogen romantics' got together. They said their
consensus aloud:
"The Hydrogen Energy System is an idea whose time
has arrived."
The International Association for Hydrogen Energy
(IAHE) was established and began in earnest to spread
information on hydrogen energy systems.
9
A Vision of Hydrogen Economy
Vision: Hydrogen is Americas clean energy choice. It
is flexible, affordable, safe, domestically produced,
used in all sectors of the economy, and in all
regions of the country.
10
Phase One (2000-2015)
Progress in technologies,
policies, and markets.
Phase Two (2010-2025)
Transitioning to the
marketplace
Phase Three (2015-2035)
Expansion of markets and
infrastructure
Phase Four (2025-2045)
Realization of the hydrogen
vision
Transition to the Hydrogen
Economy in USA
http://en.wikipedia.org/wiki/Hydrogen_economy
11
Hydrogen Economy
The hydrogen economy is a
proposed system of delivering
energy using hydrogen (energy
carrier).
12
Thee-Stage Hydrogen
Development

Structure of Hydrogen
Economy

14
Production Delivery Storage
Conversion End-use
Infrastructure
Basic research System analysis
Codes and standards Safety
Education, etc.
Structure of Hydrogen Economy
15
Hydrogen Production
Thermohemcial method
Electrochemcial method
Photobiological method
Photoelectrochemcial method

Hydrogen production is the first step for
the establishment of hydrogen economy
16
Thermochemical Method
Steam reforming
Partial oxidation
Authothermal reforming
Thermocatalytic decomposition of methane
Gasification
Pyrolysis

17
Electrochemcial Method
Electrolysis reaction

The efficiency of hydrogen generation is around
67%. Therefore, more energy will be consumed if
hydrogen is produced via electrolysis. In the future,
hydrogen generation from electrolysis can be
achieved from renewable energy (i.e. solar energy
or wind energy) or nuclear energy.
1.23V V
2
1
) ( 2 ) ( 2 ) ( 2
= +
g g l
O H O H
18
Photobiological Method
(Biohydrogen)
Photosynthesis
Fermentation
http://sciencereview.berkeley.edu/imageview.php?issue=6&
article=labscopes&image=bsr-biohydrogen
http://www.iet.uni-
duesseldorf.de/Photobiotechnology/photobiotech
nology_hauptseite.htm
Rhodobacter capsulatus
19
Photoelectrochemcial Reaction
Catalyst
p-GaAsn-GaAs
TiO
2
single crystal
ZrO
2
K
2
La
2
Ti
3
O
10

et al.
2 2
catalyst ,
2
2 2 O H O H
h
+
http://www.solarelectrode.com/solarcycle.html
Water splitting reaction
20
Approximately 17 percent of hydrogen is centrally
produced for sale and distribution in USA, and is
transported through pipelines or via cylinders and tube
trailers.
Similar to natural gas distribution, pipelines are used to
supply hydrogen to customers.
Hydrogen is also distributed via cylinders and tube
trailers that are transported by trucks, railcars, and
barges. For long-distance distribution of up to 1000
miles, hydrogen is usually transported as a liquid and
then vaporized for use on-site.
Hydrogen Delivery
21
Hydrogen Delivery
22
Hydrogen can be stored as a gas or liquid or in a
chemical compound using a variety of technologies.
Hydrogen Storage
23
Hydrogen Storage
Compact storage of hydrogen gas in
tanks is the most mature storage
technology, but is difficult because
hydrogen is the lightest element and has
very low density under normal
conditions.
Liquid hydrogen is stored in cryogenic
containers, which requires less volume
than gas storage. However, the
liquefaction of hydrogen consumes large
quantities of electric power, equivalent
to about one-third the energy value of
the hydrogen.
24
Hydrogen Storage
Hydrogen can be stored
"reversibly" and "irreversibly" in
metal hydrides.
In reversible storage, hydrogen is
stored in metals. When the
hydrogen needs to be used, it is
released from the hydride under
certain temperature and pressure
conditions, and the alloy is restored
to its previous state.
25
Hydrogen Storage
In irreversible storage, the material undergoes
a chemical reaction with another substance,
such as water, that releases the hydrogen from
the hydride. The byproduct is not reconverted to
a hydride.
heat 4H NaBO O 2H NaBH
2 2 2 4
+ + +
26
Hydrogen can be converted to energy via
traditional combustion methods or through
electrochemical processes in fuel cells.
Conversion
27
Hydrogen
Fuel cell
Hydrogen internal
combustion engine
Gas turbine
Hydrogen Conversion Devices
28
Hydrogen can be combusted in the same manner as
gasoline or natural gas. The benefit of using hydrogen
combustion over fossil fuel combustion is that it
releases fewer emissions water is the only main
byproduct.
No carbon dioxide is emitted, and nitrogen oxides,
produced by a reaction with the nitrogen in the air,
can be significantly lower than with the combustion of
fossil fuels.
Conversion
29
Hydrogen Internal Combustion
Engine (H
2
-ICE)
BMW hydrogen 7 Ford Focus C-MAX H
2
-ICE
30
Fuel cells utilize the chemical
energy of hydrogen to produce
electricity and thermal energy.
A fuel cell is a quiet, clean source
of energy. Water is the only by-
product it emits if it uses
hydrogen directly.
Since electrochemical reactions
generate energy more efficiently
than combustion, fuel cells can
achieve higher efficiencies than
internal combustion engines.
Fuel Cell
31
Hydrogen energy end-use applications include
stationary, transportation, and portable devices.
One application of hydrogen fuel cells is for
distributed generation (DG).
End Use Applications
Backup power systems
Stationary fuel cell systems
32
Fuel Cell Car

Current Development of
Hydrogen Energy

34
Transportation
Integration for electricity
Infrastructure
Current State of Hydrogen
Energy
35

Fuel Cell Bus
Clean Urban
Transportation for Europe
(CUTE)
36

Fuel Cell Bus in Iceland
ECTOS (Short for Ecological City TranspOrt System)
37
Honda fuel cell scooter Yamaha fuel cell scooter
Fuel Cell Scooter
38
Fuel Cell Submarine
Type 212, Germany
39
FutureGen-Integrated Hydrogen
On February 27, 2003, the federal government
announced FutureGen, a $1 billion initiative to
create a coal-based power plant focused on
demonstrating a revolutionary clean coal
technology that would produce hydrogen and
electricity and mitigate greenhouse gas emissions.
The FutureGen project was initiated in response to
the National Energy Policy of May 2001, which
emphasized the need for diverse and secure
energy sources that could largely be provided by
America's most abundant domestic energy
resource, coal.
40
Coal and Power Systems
FutureGen Clean Coal Projects
US DOE, 2008
"As technological advancements have been realized in
the last five years, we are eager to demonstrate CCS
(carbon capture and storage) technology on commercial
plants that when operational, will be the cleanest coal-
fired plants in the world."

Secretary of Energy Samuel Bodman
January 30, 2008
http://www.netl.doe.gov/technologi
es/ coalpower/futuregen/
41
FutureGen System
42
FutureGen 2 Project
43
http://www.carleton.ca/jmc/cnews/30012004/news/images/n4largeimage2.jpg
Hydrogen Highway in Canada
44
Hydrogen Highway in Canada
45
Hydrogen for Ironmaking
2 3 2
3 3 CO Fe CO O Fe + = +
O H Fe H O Fe
2 2 3 2
3 3 + = +
46
Innovative Ironmaking
ULCOS in European Union: UltraLow Carbon
dioxide(CO
2
) Steelmaking (50% reduction)

COURSE50 in J apan: CO
2
Ultimate Reduction
in Steelmaking process by innovative
technology for cool Earth 50 (30% reduction)

http://www.ulcos.org/en/about_ulcos/home.php
ULCOS of European Union
New blast furnace
New smelting reduction
New NG route to steel
Hydrogen steel
Electrolysis steel
Biomass steel
CO2 capture and storage (CCS)
Plasma blast furnace
47
Green Energy and Fuel Laboratory (GENFUEL) http://www.jisf.or.jp/course50/outline/index_en.html
COURSE50 of Japan
48
Green Energy and Fuel Laboratory (GENFUEL) Shttp://www.delkor.ec.europa.eu/home/newsevents/events/document_files/Session3/ession3_Hyen_Park.pdf
Hydrogen Strategy in POSCO,
South Korea
49
50
Hydrogen Powered Hindenburg
Very low minimum
ignition energy
(0.017mJ )
51
Hydrogen Safety
3 sec
1 min
1.5 min
High dissipation
and emission

Hydrogen Research at
GENFUEL

53
Water gas shift reaction (WGSR)
Steam reforming (SR)
Catalytic partial oxidation (CPO)
Autothermal reforming (ATR)
Thermal decomposition of methane (TDM)
Hydrogen Energy (1)
1492
1440
1388
1337
1285
1233
1181
1129
1077
1026
974
922
870
818
766
715
663
611
559
507
455
404
352
300
Temperature (K)
(c) 3 turns
54
Combination of solution loss reaction (SLR) and
steam gasification reaction (SGR)
Thermodynamic analysis of hydrogen production
Hydrogen separation and purification using Pd and
Pd-alloy membranes
Hydrogen Energy (2)
O
/C
ratio 0
0.25
0.5
0.75
1
S
/C
ra
rio
1
1.25
1.5
1.75
2
C
H
4
c
o
n
v
e
r
s
i
o
n
(
%
)
0
20
40
60
80
100
100
93
86
79
71
64
57
50
43
36
29
21
14
7
0
CH
4
conversion
750
0
C
500
0
C
250
0
C
55
High-Temperature Water
Decomposition
56
Steam Reforming
Steam reforming of natural gas:

Nowadays over 90% of hydrogen is generated from
the steam reforming of NG in USA.

Steam reforming of methanol:
2 2 2 3
3 CO H O H OH CH + +
mol kJ H CO H O H CH
R
/ 165 4 2
0
2 2 2 4
= + +
57
Microwave Reaction System
58
Microwave Reaction System
59
Microwave Reactor
0 ) ( = V
)] ) ( ( [
T
V V p V V

+ + =
( )
mw f p
Q T k T V C + =
( ) ( )
i i
c D c V =
0 ) ( = V
+ + = ) ) ( (
T
V V p V
K

( )
reaction mw eff p
Q Q T k T V C + + =
( ) ( )
i i i
R c D c V + =
Non-porous
Porous
H i E

r 0
=
E i H
r

0
=
0 = E
0 = H

60
Microwave Reactor
61
Partial Oxidation (POX)
Partial Oxidation (autothermal reaction)

Catalytic Partial Oxidation of Methane (CPOM)

2 2
2 2
H
m
nCO O
n
H C
m n
+ +
2 2 4
2
2
1
H CO O CH + +
62
Reaction Kinetics of
Methane CPO on Rh Catalyst
2 4
80
exp 10 119 . 2
10
O CH com
p p
RT
R
|
.
|
\
|

=
( )
O H CH sr eq O H CH sr
p p K p p
RT
T R
2 4 2 4
1
,
5 9
3 . 47
exp 10 0 . 1

|
.
|
\
|
=
( )
2 4 2 4
1
,
4 7
0 . 32
exp 10 0 . 7
CO CH cr eq CO CH cr
p p K p p
RT
T R

|
.
|
\
|
=

Methane combustion

Steam Reforming

CO
2
(dry) reforming
63
Reactor with Swiss-Roll Structure
(Heat Recirculation)
2

c
m
20 cm
2
0

c
m
Catalyst bed
Catalyst: rhodium (Rh)
1300
1255
1209
1164
1118
1073
1027
982
936
891
845
800
755
709
664
618
573
527
482
436
391
345
300
Temperature (K)
(a) 1 turn
1430
1381
1332
1283
1233
1184
1135
1086
1037
988
939
890
840
791
742
693
644
595
546
497
447
398
349
300
Temperature (K)
(b) 2 turns
1492
1440
1388
1337
1285
1233
1181
1129
1077
1026
974
922
870
818
766
715
663
611
559
507
455
404
352
300
Temperature (K)
(c) 3 turns
64
Catalytic Partial Oxidation of
Methane (CPOM)
Isothermal contours
at GHSV=10,000h
-1
65
Gas Concentration
Without heat recovery
With heat recovery
66
Autothermal Reforming
Autothermal reforming (Combination of SR and POX)
2 2 2 2 5 2
5 2 2 / 1 2 H CO O O H OH H C + + +
67
H
2
Yield
68
Water Gas Shift Reaction
Through WGSR, hydrogen can be produced from
water, while CO
2
can be enriched and captured.

2 2 2
CO H O CO H + +
69
Catalyst Observation
High-temperature catalyst
(HTC, SHT-4)
Low-temperature catalyst
(LTC, MDC-7)
Rotor speed (rpm)
G
r
a
v
i
t
y
(
G
)
0 300 600 900 1200 1500 1800 2100
0
20
40
60
80
100
120
140
160
180
200
220
240
260
280
300
Inner radius: 5.6cm
Outer radius: 7.3cm
Average radius: 6.45cm
70
g
R R f
mg
R R f m
F
F
out in out in
g
avg
) ( 2 ) ( 2
2 2 2 2
+
=
+
=

Gravitational Force
Gravitational force (G)=

The RPB can be operated
at the rotating speed of 0
1800 rpm, providing 0
233 times of gravitational
force on the basis of the
arithmetic mean radius.
71
CO Conversion
72
Thermocatalytic Decomposition of
Methane
2 4
2H C CH +
Pure hydrogen and nano-carbon can be obtained.

73
Thermocatalytic Decomposition of
Methane
74
Gasification
Gasification (from fossil fuels or biomass)

(Syngas)

2 2
2 2
H
m
nCO O
n
H C
m n
+ +
75
Syngas Formation
Gasification
(endothermic)
76
1
7
Feed Gas Exhaust Gas
Dense Metal Membrane
3
H
+
+ e
-

5
H
+
+ e
-

2
H
+

H
+

6
H
+

H
+

4
P
H
+
+ e
-

Pressure drop
H
2

O
2

CO
2

Solution-Diffusion Mechanism
1. Movement
2. Dissociation
3. Adsorption
4. Diffusion
5. Desorption
6. Combination
7. Movement
77
Membrane Tube
H
2

N
2

Inlet
Retentate side
Permeate side
H
2
-N
2
gas
mixture
78
Permeance Measurement System
I
J
Gas flow
Electrical signal
A
B
C
D
E
E
F
G
H
K
L
M
ROC patent (Reg. No. 099112755)
79
Concentration Polarization
( ) ( )
'

5 . 0 5 . 0 5 . 0 2
p r
n
p r
H
P P
l
K
P P K
A
m
= =
Sieverts law
80
Integrated System of Hydrogen
Energy
81
Performance of the Membrane Reactor

Progress and Development in Hydrogen Energy

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