20131226 progress and development in hydrogen energy(1)
TRANSCRIPT
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Green Energy and Fuel Laboratory (GENFUEL)
Wei-Hsin ChenClean Energy and Fuel Laboratory
(GENFUEL)
December 26, 2013
Progress and Development in
Hydrogen Energy
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A Vision of HydrogenEconomy
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Green Energy and Fuel Laboratory (GENFUEL)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 gasand nuclear
power.
1990: Renewable energy
applied in the electricitymarket.
2050: Hydrogenplays a
vital role on the use of
energy.
Trajectory of Primary Fuel Use
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Lightestelement in natureMost abundantelement in the universeHighestpower density (143 kJ/g
NG: 55.6 kJ/goil: 48.1 kJ/g
Normal boiling point (20.3 K)Very low minimum ignition energy
(0.017mJ)High dissipation and emissionStored in hydrocarbonsand water
Property of Hydrogen
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HydrogenH2
Oil refining
Methanolsynthesis
FertilizerFuel
Desulfurization
Propellant
Semiconductor
Application of Hydrogen
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Hydrogen Energy
Hydrogen is a promising fuel for solving energy(security) and environment (global warming and airpollution) challenges.
Unlike solar or wind energy, hydrogen can be storedand 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 moreimportant in the future, especially for thecombination with CCS.
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Initiation
On 18-21 March 1974, at the landmark HydrogenMiami Energy (THEME) Conference, a small group ofhydrogen romantics' got together. They said theirconsensus 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.
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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.
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Phase One(2000-2015) Progress in technologies,policies, and markets.
Phase Two(2010-2025) Transitioning to themarketplacePhase Three(2015-2035) Expansion of markets and
infrastructurePhase Four(2025-2045) Realization of the hydrogenvision
Transition to the Hydrogen
Economy in USA
http://en.wikipedia.org/wiki/Hydrogen_economy
http://en.wikipedia.org/wiki/Hydrogen_economyhttp://en.wikipedia.org/wiki/Hydrogen_economy -
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Hydrogen Economy
The hydrogen economyis a
proposed system of deliveringenergy using hydrogen (energycarrier).
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Thee-Stage Hydrogen
Development
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Structure of HydrogenEconomy
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Production Delivery Storage
ConversionEnd-use
Infrastructure
Basic research System analysis
Codes and standards Safety
Education, etc.
Structure of Hydrogen Economy
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Hydrogen Production
Thermohemcial methodElectrochemcial method
Photobiological method
Photoelectrochemcial method
Hydrogen production is the first step forthe establishment of hydrogen economy
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Thermochemical Method
Steam reforming
Partial oxidation
Authothermal reforming
Thermocatalytic decomposition of methane
Gasification
Pyrolysis
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Electrochemcial Method
Electrolysis reaction
The efficiency of hydrogen generation is around67%.Therefore, more energy will be consumed ifhydrogen is produced via electrolysis. In the future,
hydrogen generation from electrolysis can beachieved from renewable energy(i.e. solar energyor wind energy) or nuclear energy.
1.23VV
2
1)(2)(2)(2 =+ ggl OHOH
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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
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Photoelectrochemcial Reaction
Catalyst
p-GaAsn-GaAs
TiO2single crystalZrO2K2La2Ti3O10et al.
22
catalyst,
2 22 OHOHh
+
http://www.solarelectrode.com/solarcycle.html
Water splitting reaction
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Approximately 17 percent of hydrogen is centrallyproduced for sale and distribution in USA, and istransported through pipelinesor via cylindersand tubetrailers.
Similar to natural gas distribution, pipelines are used tosupply hydrogen to customers.
Hydrogen is also distributed via cylinders and tubetrailers that are transported by trucks, railcars, andbarges. For long-distance distribution of up to 1000miles, hydrogen is usually transported as a liquidandthen vaporizedfor use on-site.
Hydrogen Delivery
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Hydrogen Delivery
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Hydrogen Storage
Compact storage of hydrogen gas intanks is the most mature storagetechnology, but is difficult becausehydrogen is the lightest elementand has
very low densityunder normalconditions.
Liquid hydrogen is stored in cryogeniccontainers, which requires less volume
than gas storage. However, theliquefaction of hydrogen consumes largequantities of electric power, equivalentto about one-thirdthe energy value of
the hydrogen.
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Green Energy and Fuel Laboratory (GENFUEL)24
Hydrogen Storage
Hydrogen can be stored"reversibly" and "irreversibly" inmetal hydrides.
In reversible storage, hydrogen is
stored in metals. When thehydrogen needs to be used, it isreleased from the hydride undercertain temperature and pressure
conditions, and the alloy is restoredto its previous state.
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Green Energy and Fuel Laboratory (GENFUEL)25
Hydrogen Storage
In irreversible storage, the material undergoesa chemical reaction with another substance,such as water, that releases the hydrogen from
the hydride. The byproduct is not reconverted toa hydride.
heat4HNaBOO2HNaBH 2224 +++
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Green Energy and Fuel Laboratory (GENFUEL)26
Hydrogen can be converted to energy viatraditional combustion methodsor throughelectrochemical processes in fuel cells.
Conversion
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Green Energy and Fuel Laboratory (GENFUEL)27
Hydrogen
Fuel cell
Hydrogen internalcombustion engine
Gas turbine
Hydrogen Conversion Devices
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Hydrogen can be combusted in the same manner asgasoline or natural gas. The benefit of using hydrogencombustion over fossil fuel combustion is that itreleases fewer emissionswater is the only main
byproduct.No carbon dioxideis emitted, and nitrogen oxides,produced by a reaction with the nitrogen in the air,can be significantly lowerthan with the combustion of
fossil fuels.
Conversion
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Hydrogen Internal Combustion
Engine (H2-ICE)
BMW hydrogen 7 Ford Focus C-MAX H2-ICE
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Fuel cells utilize the chemicalenergyof hydrogen to produceelectricity and thermal energy.
A fuel cell is a quiet, cleansourceof energy. Water is the only by-product it emits if it useshydrogen directly.
Since electrochemical reactionsgenerate energy more efficientlythan combustion, fuel cells canachieve higher efficienciesthaninternal combustion engines.
Fuel Cell
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Green Energy and Fuel Laboratory (GENFUEL)31
Hydrogen energy end-use applications includestationary, transportation, and portable devices.
One application of hydrogen fuel cells is fordistributed generation (DG).
End Use Applications
Backup power systems
Stationary fuel cell systems
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Fuel Cell Car
http://1.bp.blogspot.com/_9EG7LXCqPiY/SFciSholJbI/AAAAAAAAFWU/OA3zEhxlmGw/s1600-h/Honda+CFX+Clarity+(8).jpghttp://www.inhabitat.com/2007/11/27/transportation-tuesday-honda-fcx-clarity/ -
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Current Development ofHydrogen Energy
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Transportation
Integration for electricityInfrastructure
Current State of Hydrogen
Energy
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Fuel Cell Bus
Clean Urban
Transportation for Europe
(CUTE)
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Fuel Cell Bus in Iceland
ECTOS(Short for Ecological City TranspOrt System)
http://www.ectos.is/en/icelandic_new_energy/implementing_hydrogen -
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Honda fuel cell scooter Yamaha fuel cell scooter
Fuel Cell Scooter
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Fuel Cell Submarine
Type 212, Germany
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Green Energy and Fuel Laboratory (GENFUEL)39
FutureGen-Integrated Hydrogen
On February 27, 2003, the federal governmentannounced FutureGen, a $1 billion initiative tocreate a coal-based power plantfocused ondemonstrating a revolutionary clean coaltechnologythat would produce hydrogen andelectricity and mitigate greenhouse gas emissions.The FutureGen project was initiated in response tothe National Energy Policy of May 2001, which
emphasized the need for diverse and secureenergy sources that could largely be provided by
America's most abundant domestic energyresource, coal.
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Green Energy and Fuel Laboratory (GENFUEL)40
Coal and Power Systems
FutureGen Clean Coal Projects
US DOE, 2008
"As technological advancements have been realized inthe last five years, we are eager to demonstrate CCS
(carbon capture and storage) technologyon commercialplants 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/
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FutureGen System
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FutureGen 2 Project
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Green Energy and Fuel Laboratory (GENFUEL)43http://www.carleton.ca/jmc/cnews/30012004/news/images/n4largeimage2.jpg
Hydrogen Highway in Canada
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Hydrogen Highway in Canada
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Green Energy and Fuel Laboratory (GENFUEL)45
Hydrogen for Ironmaking
232
33 COFeCOOFe +=+
OHFeHOFe 2232 33 +=+
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Green Energy and Fuel Laboratory (GENFUEL)46
Innovative Ironmaking
ULCOS in European Union: UltraLow Carbondioxide(CO2) Steelmaking (50% reduction)
COURSE50in Japan: CO2Ultimate Reductionin Steelmaking process by innovativetechnology for cool Earth 50(30% reduction)
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http://www.ulcos.org/en/about_ulcos/home.php
ULCOS of European Union
New blast furnaceNew smelting reduction
New NG route to steelHydrogen steelElectrolysis steelBiomass steel
CO2 capture and storage (CCS)Plasma blast furnace
47
http://www.ulcos.org/en/about_ulcos/home.phphttp://www.ulcos.org/en/about_ulcos/home.php -
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Green Energy and Fuel Laboratory (GENFUEL) http://www.jisf.or.jp/course50/outline/index_en.html
COURSE50 of Japan
48
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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
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Hydrogen Powered Hindenburg
Very low minimumignition energy(0.017mJ)
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Hydrogen Safety
3 sec
1 min
1.5 min
High dissipationand emission
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Hydrogen Research atGENFUEL
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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
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Steam Reforming
Steam reforming of natural gas:
Nowadays over 90%of hydrogen is generated fromthe steam reforming of NG in USA.
Steam reforming of methanol:
2223 3 COHOHOHCH ++
molkJHCOHOHCH R /165420
2224 =++
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Microwave Reaction System
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Microwave Reaction System
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Microwave Reactor
0)( = V
)])(([ TVVpVV
++=
( ) mwfp QTkTVC +=
( ) ( )ii cDcV =
0)( = V
++= ))((
TVVpVK
( ) reactionmweffp QQTkTVC ++=
( ) ( ) iii RcDcV +=
Non-porous
Porous
HiE
r0=
EiH r
0=
0= E
0= H
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Microwave Reactor
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Partial Oxidation (POX)
Partial Oxidation (autothermal reaction)
Catalytic Partial Oxidation of Methane (CPOM)
2222H
mnCOO
nHC mn ++
224 221 HCOOCH ++
R ti Ki ti f
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Reaction Kinetics of
Methane CPO on Rh Catalyst
24
80exp10119.2 10 OCHcom pp
RTR
=
( )OHCHsreqOHCHsr ppKppRT
TR2424
1
,
59 3.47exp100.1
=
( )2424
1
,
47 0.32exp100.7 COCHcreqCOCHcr ppKppRT
TR
=
Methane combustion
Steam Reforming
CO2(dry) reforming
R t ith S i R ll St t
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Reactor with Swiss-Roll Structure
(Heat Recirculation)
2cm
20 cm
20cm
Catalyst bed
Catalyst: rhodium (Rh)
Catalytic Partial Oxidation of
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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
693644
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
404352
300
Temperature (K)
(c) 3 turns
64
Catalytic Partial Oxidation of
Methane (CPOM)
Isothermal contoursat GHSV=10,000h-1
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Gas Concentration
Without heat recovery
With heat recovery
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H2Yield
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Water Gas Shift Reaction
Through WGSR, hydrogen can be produced fromwater, while CO2can be enriched and captured.
2 2 2CO H O CO H + +
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Catalyst Observation
High-temperature catalyst(HTC, SHT-4)
Low-temperature catalyst(LTC, MDC-7)
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Green Energy and Fuel Laboratory (GENFUEL)
Rotor speed (rpm)
Gravity(G)
0 300 600 900 1200 1500 1800 21000
20
40
60
80
100
120
140
160
180
200
220
240
260
280
300
Inner radius: 5.6cm
Outer radius: 7.3cm
Aver age radiu s: 6 .45c m
70
g
RRf
mg
RRfm
F
Foutinoutin
g
avg )(2)(22222 +
=+
=
Gravitational Force
Gravitational force (G)=
The RPB can be operatedat the rotating speed of 01800 rpm, providing 0233 times of gravitationalforce on the basis of thearithmetic mean radius.
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CO Conversion
Th t l ti D iti f
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Thermocatalytic Decomposition of
Methane
24 2HCCH +
Pure hydrogen and nano-carbon can be obtained.
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Gasification
Gasification (from fossil fuels or biomass)
(Syngas)2222H
mnCOO
nHC mn ++
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Syngas Formation
Gasification
(endothermic)
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Membrane Tube
H2
N2Inlet Retentate side
Permeate side
H2-N2gas
mixture
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Green Energy and Fuel Laboratory (GENFUEL) 78
Permeance Measurement System
I
J
Gas flow
Electrical signal
A
B
C
D
E E
F
G
H
K
LM
ROC patent (Reg. No. 099112755)
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Green Energy and Fuel Laboratory (GENFUEL) 79
Concentration Polarization
( ) ( )' 5.05.05.02 prnprH
PPl
KPPK
A
m==
Sieverts law
Integrated System of Hydrogen
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Integrated System of Hydrogen
Energy
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Performance of the Membrane Reactor