20131226 Progress and Development in Hydrogen Energy(1)

8/12/2019 20131226 Progress and Development in Hydrogen Energy(1)

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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
http://www.thebestlinks.com/Image__3A__Apollo5_on_pad.jpg.htmlhttp://tw.wrs.yahoo.com/_ylt=A8tUxwM_Xs9H1gwBOzRt1gt./SIG=1f7e17gp7/EXP=1204858815/**http:/tw.search.yahoo.com/search/images/view?back=http%3A%2F%2Ftw.search.yahoo.com%2Fsearch%2Fimages%3Fei%3DUTF-8%26fr%3Dslv8-msgr%26p%3DFertilizer%26fr2%3Dtab-web&w=600&h=450&imgurl=www.luxme.com%2Fproductsample%2FFertilizer.jpg&rurl=http%3A%2F%2Fwww.luxme.com%2Fproductsample%2Ftubularproduct3.htm&size=68.6kB&name=Fertilizer.jpg&p=Fertilizer&type=jpeg&no=4&tt=130,488&oid=9d2f3a076c511164&ei=UTF-8http://tw.wrs.yahoo.com/_ylt=A8tUxxjpXc9HQoIB_Hlt1gt./SIG=1g8u7agbd/EXP=1204858729/**http:/tw.search.yahoo.com/search/images/view?back=http%3A%2F%2Ftw.search.yahoo.com%2Fsearch%2Fimages%3Fp%3Dmethanol%26ei%3DUTF-8%26fr%3Dslv8-msgr%26fl%3D0%26x%3Dwrt&w=180&h=161&imgurl=www.thebestlinks.com%2Fimages%2Fthumb%2Fe%2Fec%2F180px-Methanol_struktur.png&rurl=http%3A%2F%2Fwww.thebestlinks.com%2FMethanol.html&size=20.1kB&name=180px-Methanol_struktur.png&p=methanol&type=png&no=7&tt=23,970&oid=ff823319848ed216&ei=UTF-8http://images.google.com.tw/imgres?imgurl=http://www.ceilcoteapc.com.sg/images/semiconductor.gif&imgrefurl=http://www.ceilcoteapc.com.sg/markets.htm&h=500&w=500&sz=65&hl=zh-TW&start=1&tbnid=GrpacXdnjzu5lM:&tbnh=130&tbnw=130&prev=/images?q%3Dsemiconductor%26gbv%3D2%26svnum%3D10%26complete%3D1%26hl%3Dzh-TW%26rls%3DGGLG,GGLG:2005-36,GGLG:zh-TWhttp://images.google.com.tw/imgres?imgurl=http://www.europavalve.com/images/oil-refinery-crop2.jpg&imgrefurl=http://www.europavalve.com/contact-us.htm&h=1116&w=1348&sz=113&hl=zh-TW&start=4&um=1&tbnid=EuHDtcWSY6Z2YM:&tbnh=124&tbnw=150&prev=/images?q%3Doil%2Brefinery%26svnum%3D10%26um%3D1%26complete%3D1%26hl%3Dzh-TW%26rls%3DGGLG,GGLG:2005-36,GGLG:zh-TW%26sa%3DN


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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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8/81Green Energy and Fuel Laboratory (GENFUEL)8

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.



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.



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



Hydrogen Economy

The hydrogen economyis a

proposed system of deliveringenergy using hydrogen (energycarrier).



Thee-Stage Hydrogen

Development


13/81Green Energy and Fuel Laboratory (GENFUEL)

Structure of HydrogenEconomy



Production Delivery Storage

ConversionEnd-use

Infrastructure

Basic research System analysis

Codes and standards Safety

Education, etc.

Structure of Hydrogen Economy



Hydrogen Production

Thermohemcial methodElectrochemcial method

Photobiological method

Photoelectrochemcial method

Hydrogen production is the first step forthe 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 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



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
http://images.google.com.tw/imgres?imgurl=http://sciencereview.berkeley.edu/articles/issue6/labscopespix/bsr-biohydrogen.jpg&imgrefurl=http://sciencereview.berkeley.edu/imageview.php?issue%3D6%26article%3Dlabscopes%26image%3Dbsr-biohydrogen&h=450&w=600&sz=63&hl=zh-TW&start=3&um=1&tbnid=Dey_hUy2kcZuGM:&tbnh=101&tbnw=135&prev=/images?q%3Dbiohydrogen%26svnum%3D10%26um%3D1%26complete%3D1%26hl%3Dzh-TW%26rls%3DGGLG,GGLG:2005-36,GGLG:zh-TW%26sa%3DN



19

Photoelectrochemcial Reaction

Catalyst

p-GaAsn-GaAs

TiO2single crystalZrO2K2La2Ti3O10et al.

22

catalyst,

2 22 OHOHh

+

http://www.solarelectrode.com/solarcycle.html

Water splitting reaction



20

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



21

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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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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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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Hydrogen can be converted to energy viatraditional combustion methodsor throughelectrochemical processes in fuel cells.

Conversion


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Hydrogen

Fuel cell

Hydrogen internalcombustion engine

Gas turbine

Hydrogen Conversion Devices
http://tw.wrs.yahoo.com/_ylt=A8tUxwkmyUtHez0BszBt1gt./SIG=1gkar7su8/EXP=1196235430/**http:/tw.search.yahoo.com/search/images/view?back=http%3A%2F%2Ftw.search.yahoo.com%2Fsearch%2Fimages%3Fp%3Dhydrogen%2Binternal%2Bcombustion%2Bengine%26ei%3DUTF-8%26fr%3Dyfp%26x%3Dwrt&w=235&h=230&imgurl=www.visionengineer.com%2Fenv%2Fbmw_h2engine.jpg&rurl=http%3A%2F%2Fwww.visionengineer.com%2Fenv%2Falt_fuel.php&size=24kB&name=bmw_h2engine.jpg&p=hydrogen+internal+combustion+engine&type=jpeg&no=6&tt=187&oid=224ba267f15b623c&ei=UTF-8http://tw.wrs.yahoo.com/_ylt=A8tUzIuBTR1H9z4AKhNt1gt./SIG=1hj1udntd/EXP=1193189121/**http:/tw.search.yahoo.com/search/images/view?back=http%3A%2F%2Ftw.search.yahoo.com%2Fsearch%2Fimages%3Fei%3DUTF-8%26fr%3Dslv8-msgr%26p%3Dfuel%2520cell%26fr2%3Dtab-web&w=200&h=193&imgurl=205.168.79.27%2Fhydrogenandfuelcells%2Ffuelcells%2Fimages%2Fballard_fuel_cell_01440.jpg&rurl=http%3A%2F%2F205.168.79.27%2Fhydrogenandfuelcells%2Ffuelcells%2Fbasics.html&size=13.8kB&name=ballard_fuel_cell_01440.jpg&p=fuel+cell&type=jpeg&no=7&tt=99,976&oid=52faaf8a54661406&ei=UTF-8http://tw.wrs.yahoo.com/_ylt=A8tUxxLnyEtHvHoAIjJt1gt./SIG=1gm2a8hoq/EXP=1196235367/**http:/tw.search.yahoo.com/search/images/view?back=http%3A%2F%2Ftw.search.yahoo.com%2Fsearch%2Fimages%3Fei%3DUTF-8%26p%3Dhydrogen%2Bgas%2Bturbine%26xargs%3D0%26pstart%3D1%26fr%3Dyfp%26b%3D21&w=218&h=167&imgurl=www.sealseastern.com%2Fimages%2Fsimages%2FTurbine.jpg&rurl=http%3A%2F%2Fwww.sealseastern.com%2FHigh-Pressure-Seals.htm&size=10.6kB&name=Turbine.jpg&p=hydrogen+gas+turbine&type=jpeg&no=23&tt=87&oid=f455c45d44aed616&ei=UTF-8


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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
http://tw.wrs.yahoo.com/_ylt=A8tUxhRRfUlHQDQAoQht1gt./SIG=1hia3vd78/EXP=1196084945/**http:/tw.search.yahoo.com/search/images/view?back=http%3A%2F%2Ftw.search.yahoo.com%2Fsearch%2Fimages%3Fei%3DUTF-8%26p%3Dhydrogen%252C%2Bspace%2Bshuttle%26xargs%3D0%26pstart%3D1%26fr%3Dyfp%26b%3D21&w=172&h=124&imgurl=www.technewsworld.com%2Fimages%2Frw834107%2Fatlantis.jpg&rurl=http%3A%2F%2Fwww.technewsworld.com%2Frsstory%2F57724.html&size=8.7kB&name=atlantis.jpg&p=hydrogen%2C+space+shuttle&type=jpeg&no=37&tt=170&oid=17eed09e3993fde0&ei=UTF-8&src=p


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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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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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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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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
http://www.transitbc.com/fuelcell/fleet.cfm


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Hydrogen for Ironmaking

232

33 COFeCOOFe +=+

OHFeHOFe 2232 33 +=+


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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

49


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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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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

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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Green Energy and Fuel Laboratory (GENFUEL) 65

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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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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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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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

Documents

20131226 Progress and Development in Hydrogen Energy(1)