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Catalysis Today
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Review
A R T I C L E I N F O
A B S T R A C T
Article history:
Currently, hydrogen is primarily used in the chemical industry, but in the near future it will become
a signicant fuel. There are many processes for hydrogen production. This paper reviews the
technologies related to hydrogen production from both fossil and renewable biomass resources
including reforming (steam, partial oxidation, autothermal, plasma, and aqueous phase) and pyrolysis.
In addition, electrolysis and other methods for generating hydrogen from water, hydrogen storage
related approaches, and hydrogen purication methods such as desulfurization and water-gas-shift are
discussed.
2008 Elsevier B.V. All rights reserved.
Contents
1.
2.
3.
4.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Fuel processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.
Hydrocarbon reforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.1.
Hydrocarbon reforming reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.
Desulfurization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.
Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4.
Plasma reforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.5.
Aqueous phase reforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.6.
Ammonia reforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Non-reforming hydrogen production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.
Hydrogen from biomass. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.1.
Biomass gasication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.2.
Biological hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.
Hydrogen from water. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.1.
Electrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.2.
Thermochemical water splitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.3.
Photoelectrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
244
246
246
246
248
248
248
250
250
251
251
251
251
254
254
256
256
257
258
1. Introduction
* Corresponding author. Tel.: +1 509 373 1473; fax: +1 509 376 3108.
E-mail address: jd.holladay@pnl.gov (J.D. Holladay).
0920-5861/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.cattod.2008.08.039
The U.S. light vehicle eet is over 225 million, traveling over 7
billion miles a day, and consuming 8 million barrels of oil a day
[14]. Despite being the 3rd largest oil producer in the world, the
Nomenclature
APR
ATR
BEAMR
CPOX
DBD
DOE
Eap
Eg
fd
DH
DHc
HDS
I
IPEC
MEC
pqH2
PEM
POX
P/R
PrOx
Rex
SOEC
SOFC
Dt
VOC
WGS
245
Fig. 1. Fuel processing of gaseous, liquid, and solid fuels for hydrogen production.
246
2. Fuel processing
Fuel processing technologies convert a hydrogen containing
material such as gasoline, ammonia, or methanol into a hydrogen
rich stream. Fuel processing of methane is the most common
hydrogen production method in commercial use today. Most
hydrocarbon fuels contain at least some amount of sulfur which
poisons the fuel processing catalyst. This presents perhaps the
biggest challenge to reforming. As a result, desulfurization will also
be discussed. In addition, hydrocarbon reforming, plasma reforming, aqueous reforming, and pyrolysis will also be presented.
(1)
(2)
Partial oxidation
2.1. Hydrocarbon reforming
DH 193:2 kJ mol1
(3)
(4)
Autothermal reforming
Cm Hn 12mH2 O 14mO2 mCO 12m 12nH2
DH 0
(5)
(6)
DH hydrocarbon dependent
2CO C CO2
(7)
DH 172:4 kJ mol1
CO H2 C H2 O
(8)
(9)
Water-gas-shift
CO H2 O CO2 H2
DH 41:1 kJ mol1
CO2 H2 CO H2 O RWGS
(10)
(11)
CO oxidation
CO O2 CO2
DH 283 kJ mol1
1
(12)
(13)
Table 1
Comparison of reforming technologies (adapted from [1517])
Technology
Advantages
Disadvantages
Steam reforming
Autothermal reforming
Partial oxidaiton
Technology
Oxygen/
carbon ratio
Minimum
temperature
to avoid coke
formation (8C)
POx
ATR
SR
ATR
SR
1
1
1
2
2
1180
1030
950
575
225
247
248
2.3. Pyrolysis
Pyrolysis is another hydrogen-producing technology where the
hydrocarbon is decomposed (without water or oxygen present)
into hydrogen and carbon [52]. Pyrolysis can be done with any
organic material [5356] and is used for the production of
hydrocarbons [55,56] and carbon nanotubes and spheres [57,58].
Since no water or air is present, no carbon oxides (e.g., CO or CO2)
are formed, eliminating the need for secondary reactors (WGS,
PrOx, etc.). Consequently, this process offers signicant emissions
reduction. However, if air or water is present, for example the
materials have not been dried, and then signicant CO2 and CO
emissions will be produced. Among the advantages of this process
are fuel exibility, relative simplicity and compactness, clean
carbon by-product, and reduction in CO2 and CO emissions
[52,54,56,5966]. The reactions can be written in the following
form [52]:
Cn Hm ! nC 12mH2
DH hydrocarbon dependent
(14)
249
n CO n H2 DHH2
n fuel DHfuel P elec
(15)
Table 3
Plasma Reformer Efciencies (adapted from [74])
Technology
Fuel
Experimental Conditions
Chemical Reaction
Air Ratio
S/C
H2
CO
CO2
CH4
Diesel
Iso-octane
Iso-octane
Diesel
Hexane
ATR
ATR
POx
POx
SR
0.4
0.28
0.25
0.25
1.8
1
23
46
22
23.5
66
17
16
15
23
25
6.2
16
2
0.1
4
1.2
3
0.03
Reformate
Temperature (K)
Efciency, n
10001300
9001100
1200
1200
?
85
55
9
9
?
250
Fig. 4. (A) Reaction pathways for aqueous reforming of oxygenated hydrocarbons. (B) Summary of thermodynamic and kinetic considerations for aqueous phase reforming
(Copyright Elsevier [2]).
where nCO and nH2 are the molar ows of carbon monoxide and
hydrogen, respectively, which when multiplied by the lower
heating value of hydrogen (DHH2 ) is the energy in the outlet stream
(assuming all the carbon monoxide is converted to carbon dioxide
in a WGS reactor). The outlet energy is divided by the input energy
(nfuel is the molar ow of the fuel multiplied by the lower heating
value of the fuel, DHfuel, plus electric power for the plasma
generation, Pelec) to nd the efciency. Of the cases investigated, a
gliding arc non-thermal plasma appeared to be the most efcient
(Table 3).
2.5. Aqueous phase reforming
Aqueous phase reforming (APR) is under development to
process oxygenated hydrocarbons or carbohydrates to produce
hydrogen [2,68,8297]. These reactors often operate at pressures
up to 2530 MPa and temperatures ranging from 220 to 270 8C.
The reforming reactions are rather complex (see the reaction
pathways for hydrogen production from oxygenated hydrocarbons
in Fig. 4a), but can be summarized to follow the reaction pathways
in Eq. (1) for reforming followed by Eq. (10) for the WGS [86]. Most
research to date has been focused on supported Group VIII
catalysts, with Pt-containing catalysts having the highest activity.
Even though they have lower activity, nickel based catalysts have
been evaluated due to nickels low cost [86]. The advantages of APR
reactors include elimination of the need to vaporize water and
feedstock which eliminates a system component and also enables
fuels that cannot be vaporized such as glucose to be processed
without rst degrading them. APR occurs at low temperatures
which favors WGS to increase the hydrogen yield while suppressing CO. Thus the reforming and WGS occur in a single step
eliminating multiple reactors (Fig. 4b) [2]. The advocates of this
technology claim that this technology is more amiable to
efciently and selectively converting biomass feedstocks to
hydrogen. Aqueous feed concentrations of 1060% were reported
for glucose and glycols [98,99]. Catalyst selection is important to
avoid methanation, which is thermodynamically favorable, along
with Fischer Tropsch products such as propane, butane, and
hexane [2,88,89]. Rozmiarek [99] reported an aqueous phase
DH 92:4 kJ mol1
(16)
251
252
253
Table 4
Biomass waste that is readily utilized for bio-hydrogen production [132,156]
Biomass material
Comments
Must by hydrolyzed to glucose or maltose, followed by conversion to organic acids and nally hydrogen
Must be nely ground and go through delignication, then it is processed as starch
May require pretreatment for removal of undesirables and for nutritional balancing, then it is processed as starch
May require pretreatment, the converted to organic acids and nally converted to hydrogen
3.1.2.3. Photo-fermentative processes. Photo-fermentative processes, also called photosynthetic bacterial hydrogen production,
capitalize on the nitrogenase functionality of purple nonsulfur bacteria to evolve hydrogen. In this process light harvesting
pigments such as chlorophylls, carotenoids, and phycobilins
scavenge light energy which is transferred to membrane reaction
centers similar to those in photolytic organisms (algae). Sunlight
converts water into protons, electrons, and O2 [20]. The nitrogenase catalyst is used to react the protons and electrons with
nitrogen and ATP to make ammonia, hydrogen and ADP [20]. Since
oxygen inhibits the nitrogenase, cyanobacteria separate nitrogen
xation and oxygen generation either spatially or temporally [20].
In nature the bacteria use the hydrogen by-product to fuel other
energy requiring processes via the uptake hydrogenase enzyme.
Therefore, researchers are trying to genetically modify the bacteria
to suppress this enzyme [20]. The process is done in decient
nitrogen conditions using primarily infrared light energy and,
preferably, reduced organic acids although other reduced compounds can be used [132,135,156]. The advantages of this process
are that oxygen does not inhibit the process, and that these
bacteria can be used in a wide variety of conditions (i.e. batch
processes, continuous cultures, and immobilized in carrageenan,
agar gel, porous glass, activated glass, or polyurethane foam)
[132,135,156]. The disadvantages are the limited availability of
organic acids, the nitrogenase enzyme is slow, the process requires
a relatively high amount of energy, and hydrogen re-oxidation
[135,156]. To increase the nitrogenase activity and decrease the
energy requirements, the proper ratio of carbon to nitrogen
nutrients must be maintained. Enzyme engineering approaches are
under development to decrease the nitrogenase sensitivity to high
levels of nitrogen nutrients. In addition, hydrogen re-oxidation is
being addressed by microengineering to deactivate hydrogenase
enzymes in the bacteria. The hydrogenase enzymes recycle the
hydrogen produced by the nitrogenase to support cell growth.
Finally, photosynthetic organisms are not efcient as solar
collectors, collecting on average (over day and night) an energy
ow of approximately 100200 W/m2 [20]. Current efciency is
approximately 1.9% [9,20]. The theoretical limit for this technology
is 68% according to the U.S. DOE [9].
3.1.2.4. Microbial electrolysis cells. Microbial aided electrolysis
cells (MEC), also called bioelectrochemically assisted microbial
reactor (BEAMR), use electrohydrogenesis to directly convert
biodegradable material into hydrogen [162164]. The MEC is a
modied microbial fuel cell. In a microbial fuel cell, exoelectrogens
(special microorganisms), decompose (oxidize) organic material
and transfer electrons to the anode. The electrons combine at the
cathode, after traveling through an external load, with protons and
oxygen forming water. A MEC operates in anaerobic state (no
oxygen at the cathode) and an external voltage is applied to the cell
rather than generated by it. The added energy is required since
acetate substrate decomposition is not spontaneous under
standard conditions [162164]. Hydrogen production occurs at
the cathode via Eq. (17).
2H 2e ! H2
(17)
h Pn
1 IEap
nHydrogen DHc;Hydrogen
Dt I2 Rex Dt nsubstrate DHc;substrate
(18)
where I is the current, Eap the applied voltage, Dt(s) the time
increment for n data points measured during the batch cycle, and
Rex is an external resistance which was 10 V by Call and Logan
[162]. Using Eq. (18), the efciency was raised from 23% with a gas
diffusion membrane and 53% with a Naon membrane to 76% in
the membraneless reactor [162]. Under these conditions a
hydrogen production rate of 3.12 m3 H2/(m3 reactor day) [162].
However, the methane production rates also increased to an
average of 3.5% methane in the production gas [162]. To control the
methanogensis in these reactors, strategies involving intermittent
draining and air exposure or in situ air-sparging have been
proposed [162]. However, these strategies will result in more
complex systems with signicantly increased operations and
maintenance requirements, translating into more expensive
systems. In addition to methane suppression, continuous operation, decreasing the pH, operating under carbon limited conditions,
increasing the microorganisms tolerance to impurities, and
examining other feedstocks are all issues to be addressed.
3.1.2.5. Multi-stage integrated process. Multi-stage hydrogen production has been implemented to maximize the hydrogen
production from the feed [156]. Initially, the process consisted of
two stages, dark fermentation followed by photo fermentation
[156], but three or even four stages have since been proposed in
different congurations (Fig. 7) [9]. In this process, the biomass
material is rst fed to a dark fermentation reactor where the
bacteria decompose the feedstock to hydrogen and an organic acid
rich efuent. Since the efuent has organic acids in it, this
eliminates the challenge of developing a supply of organic acids
for the photo-fermentative process. Since the photo-fermentative
process uses primarily infrared light, the sunlight is rst ltered
through a direct photolysis reactor where the visible light is utilized,
but the infrared light is not [9]. The forth stage is the use of a
microbial electrolysis cells which produces hydrogen, not electricity
254
[9]. This cell utilizes the same organic acids, but does not require
light. Therefore, it can operate during the night or other times of low
light [9]. The efuent from the rst stage contains ammonia, which
inhibits the second stage, so some dilution and neutralization to
adjust the pH to 7 is required prior to feeding it to the second stage
[156].
Integration of multiple processes produces signicant challenges for the reactor engineering, system design, process control,
and operation and maintenance. The challenges with the coproduction of hydrogen and oxygen from photolytic hydrogen
production include:
Photosynthetic and respiration capacity ratio. Green algae and
cyanobacteria become anaerobic when their photosynthesis/
respiration (P/R) capacity ratio is 1 or less. Under such anaerobic
conditions, photosynthetic water oxidation produces H2 instead
of starch, and the oxygen evolved by photosynthesis is consumed
by respiration, to produce CO2. Currently, this process is achieved
by nutrient deprivation, with the drawback that the resulting P/
R 1 ratio is achieved by partially decreasing the quantum yield
of photosynthesis. Alternative mechanisms to bring the P/R ratio
to 1 need to be investigated, particularly those methods that
focus on achieving a P/R ratio of 1 without changing the quantum
yield of photosynthesis. Two further issues will need to be
investigated under these conditions: (1) rate limitations due to
the non-dissipation of the proton gradient and (2) the ability of
the culture to take up a variety of exogenous carbon sources
under the resulting anaerobic conditions [9].
Co-culture balance. To extend the adsorption spectrum of the H2photoproducing cultures to the infrared (700900 nm), the
possibility of co-cultivating oxygenic photosynthetic organisms
with anoxygenic photosynthetic bacteria that absorb light in the
visible (400600 nm), thus potentially competing with green
algae for these latter wavelengths. Strategies need to be devised
to either maintain the appropriate biomass ratio of the two
organisms as suspensions in the same cultures. The competition
Table 5
Hydrogen production rate of different types of bio-hydrogen processes (adapted from [9,132,162])
Bio-hydrogen system
Direct photolysis
Indirect photolysis
Photo-fermentation
WGS
Dark fermentation
MEC
Multi-stage
1707
337
747
1.24
114.75
21
255
(22)
Cathode:
4H 4e ! 2H2
(23)
DH 288 kJ mol1
(19)
Cathode:
2H2 O 2e ! H2 2OH
(20)
Overall:
H2 O ! H2 12O2
DH 288 kJ mol1
(21)
Fig. 8. Energy demand for water and steam electrolysis (Copyright Elsevier [174]).
256
T 630 C
(24)
(25)
T 400 C
T 550 C
T 870 C
(26)
(27)
(28)
(29)
(30)
2HBr ! Br2 H2
(31)
2H2 O I2 SO2 ! I2 H2
(32)
ZnO/Zn [185]:
ZnO ! Zn 12O2
T 1800 C
Zn H2 O ! ZnOs H2
T 475 C
(33)
(34)
257
258
Table 6
Technology summary table
Technology
Steam reforming
Partial oxidation
Autothermal reforming
Plasma reforming
Aqueous phase reforming
Ammonia reforming
Biomass gasication
Photolysis
Dark fermentation
Photo fermentation
Microbial electrolysis cells
Alkaline electrolyzer
PEM electrolyzer
Solid oxide electrolysis cells
Thermochemical water splitting
Photoelectrochemical water splitting
Feed stock
Hydrocarbons
Hydrocarbons
Hydrocarbons
Hydrocarbons
Carbohydrates
Ammonia
Biomass
Sunlight + water
Biomass
Biomass + sunlight
Biomass + electricity
H2O + electricity
H2O + electricity
H2O + electricity + heat
H2O + heat
H2O + sunlight
Efciency
a
7085%
6075%a
6075%a
985%b
3555%a
NA
3550%a
0.5%c
6080%d
0.1%e
78%f
5060%g
5570%g
4060%h
NA
12.4%i
Maturity
Reference
Commercial
Commercial
Near term
Long term
Med. term
Near term
Commercial
Long term
Long term
Long term
Long term
Commercial
Near term
Med. Term
Long term
Long term
[31]
[31]
[31]
[74]
[99]
[9,20,127]
[161]
[9,135]
[9,20]
[162]
[20,159]
[20,159]
[127]
[159,186]
NA = not available.
a
Thermal efciency, based on the higher heating values.
b
Based on Eq. (15) and does not include hydrogen purication.
c
Solar to hydrogen via water splitting and does not include hydrogen purication.
d
Percent of 4 mol H2 per mole glucose theoretical maximum.
e
Solar to hydrogen via organic materials and does not include hydrogen purication.
f
Overall energy efciency including the applied voltage and energy in the substrate. It does not include hydrogen purication.
g
Lower heating value of hydrogen produced divided by the electrical energy to the electrolysis cell.
h
High temperature electrolysis efciency is dependent on the temperature the electrolyzer operates at and the efciency of the thermal energy source. For example, SOEC
operating from advanced high temperature nuclear reactors may be able to achieve up to 60% efciency [127]. If thermal energy input is ignored, efciencies up to 90% have
been reported [127].
i
Solar to hydrogen via water splitting and does not include hydrogen purication.
References
[1] O. Yamada, Thin Solid Films 509 (2006) 207211.
[2] R.R. Davda, J.W. Shabaker, G.W. Huber, R.D. Cortright, J.A. Dumesic, Applied
Catalysis B: Environmental 56 (2005) 171186.
[3] U.S. Department of Energy Hydrogen, Fuel Cells and Infrastructure Technologies
Program, Hydrogen Posture Plan, U.S. Department of Energy, 2006.
[4] U.S. Department of Energy EIA, http://www.eia.doe.gov/neic/brochure/gas06/
gasoline.htm, U.S. Government, 2007.
[5] V.M. Aroutiounian, V.M. Arakelyan, G.E. Shahnazaryan, Solar Energy 78 (2005)
581592.
[6] W.J. Piel, Fuel Processing Technology 71 (2001) 167179.
[7] E. Yuzugullu, Record 5017: Air Quality and Population, U.S.D.o. Energy, U.S.
Department of Energy, 2006.
[8] S.C. Davis, S.W. Diegel, Transportation Energy Data Book, 25th ed., Oak Ridge
National Laboratory, 2006.
[9] U.S. Department of Energy Hydrogen, Fuel Cells and Infrastructure Technologies
Program, Multi-Year Research, Development and Demonstration Plan, U.S.
Department of Energy, 2007.
[10] R. Farrauto, S. Hwang, L. Shore, W. Ruettinger, J. Lampert, T. Giroux, Y. Liu, O.
Ilinich, Annual Review of Materials Research 33 (2003) 127.
[11] D.L. King, K.P. Brooks, C.M. Fischer, L. Pederson, G. Rawlings, S.V. Stenkamp, W.
TeGrotenhuis, R. Wegeng, G.A. Whyatt, in: Y. Wang, J.D. Holladay (Eds.), Microreactor Technology and Process Intensication, ACS, Washington DC (2005) pp.
119128.
[12] J. Rostrup-Nielsen, in: I.T. Horvath (Ed.), Encyclopedia of Catalysis, Wiley Interscience, (2003) 4.
[13] C.S. Song, Catalysis Today 77 (2002) 1749.
[14] M.W. Twigg (Ed.), Catalyst Handbook, Wolfe Publishing Ltd., London, 1989.
[15] D.J. Wilhelm, D.R. Simbeck, A.D. Karp, R.L. Dickenson, Fuel Processing Technology 71 (2001) 139148.
[16] J. Holladay, E. Jones, D.R. Palo, M. Phelps, Y.-H. Chin, R. Dagle, J. Hu, Y. Wang, E.
Baker, Materials Research Society SymposiumProceedings, Miniature Fuel
Processors for Portable Fuel Cell Power Supplies, Materials Research Society,
Boston, MA, United States, (2003), pp. 429434.
[17] R.M. Navarro, M.A. Pena, J.L.G. Fierro, Chemical Reviews 107 (2007) 39523991.
[18] K. Geissler, E. Newson, F. Vogel, T.-B. Truong, P. Hottinger, A. Wokaum, Physical
Chemistry Chemical Physics 3 (2001) 289293.
[19] G. Hoogers, Fuel Cell Technology Handbook, CRC Press, Boca Raton (2003) pp. 515-23.
[20] B. Srensen, Hydrogen and Fuel Cells Emerging Technologies and Applications,
Elsevier Academic Press, New York, 2005, p. 450.
[21] P. Pietrogrande, M. Bezzeccheri, in: L.J.M.J. Blomen, M.N. Mugerwa (Eds.), Fuel
Cell Systems, Plenum Press, New York (1993) pp. 121156.
[22] M. Krumpelt, T.R. Krause, J.D. Carter, J.P. Kopasz, S. Ahmed, Catalysis Today 77
(2002) 316.
[23] A.M. Adris, B.B. Pruden, Canadian Journal of Chemical Engineering 74 (1996) 177.
[24] A.Y. Tonkovich, S. Perry, Y. Wang, W.A. Rogers, D. Qui, Y. Peng, Chemical
Engineering Science 98 (2004) 575581.
[25] Y. Wang, Y. Chin, R.T. Rozmiarek, J. Watson, A.L.Y. Tonkovich, Catalysis Today 98
(2004) 575581.
[26] J.R. Rostrup-Nielsen, Journal of Catalysis 31 (1973) 173.
[27] J. Wei, E. Iglesia, Journal of Physical Chemistry B 188 (2004) 4094.
[28] H. Song, L. Zhang, U.S. Ozkan, Green Chemistry 9 (2007) 686694.
[29] H. Song, L. Zhang, R.B. Watson, D. Braden, U.S. Ozkan, Catalysis Today 129 (2007)
346354.
[30] J.R.H. Ross, in: M.W. Roberts, J.M. Thomas (Eds.), Surface and Defect Properties of
Solids, Chemical Society, London (1974) 34.
[31] K. McHugh, Hydrogen Production Methods, MPR Associates Inc., 2005,, p. 41.
[32] D.L. Timm, Z.I. Onsan, Catalysis Review 43 (2001) 3184.
[33] K.L. Hohn, L.D. Schmidt, Applied Catalysis A: General 211 (2001) 5368.
[34] J.J. Krummenacher, K.N. West, L.D. Schmidt, Journal of Catalysis 215 (2003)
332343.
[35] L. Pino, V. Recupero, S. Beninati, A.K. Shukla, M.S. Hegde, P. Bera, Applied
Catalysis A: General 225 (2002) 6375.
[36] J.D. Holladay, Y. Wang, E. Jones, Chemical Reviews 104 (2004) 47674789.
[37] M. Krumpelt, Fuel Processing Session Summary, Baltimore, MD, 1999.
[38] R.J. Bellows, Technical Challenges for Hydrocarbon Fuel Reforming, DOE, Baltimore, MD, 1999.
[39] F. Joensen, J.R. Reostrup-Neilsen, Journal of Power Sources 105 (2002) 195
201.
[40] W.E. TeGrotenhuis, D.L. King, K.P. Brooks, B.J. Golladay, R.S. Wegeng, in: J.P.
Baselt, U. Eul, R.S. Wegeng (Eds.), Optimizing Microchannel Reactors by TradingOff Equilibrium and Reaction Kinetics Through Temperature Management,
AICHE, New Orleans, LA, 2002, p. 18.
[41] K.P. Brooks, J.M. Davis, C.M. Fischer, D.L. King, L.R. Pederson, G.C. Rawlings, V.S.
Stenkamp, W. TeGrotenhuis, R.S. Wegeng, G.A. Whyatt, in: Y. Wang, J.D. Holladay
(Eds.), Microreactor Technology and Process Intensication, ACS, Washington,
DC (2005) pp. 238257.
[42] J. Patt, D.J. Moon, C. Phillips, L. Thompson, Catalysis Letters 65 (2000) 193195.
[43] B.D. Chandler, A.B. Schabel, L.H. Pignolet, Journal of Catalysis 193 (2000)
186198.
[44] S. Hilaire, X. Wang, T. Luo, R.J. Gorte, J. Wagner, Applied Catalysis A 215 (2001)
271.
[45] S. Zhao, R.J. Gorte, Catalysis Letters 92 (2004) 75.
[46] I.V. Babich, J.A. Moulijn, Fuel 82 (2003) 607631.
[47] C. Song, X. Ma, Applied Catalysis B: Environmental 41 (2003) 207238.
[48] C. Song, Catalysis Today 86 (2003) 211263.
[49] X.-Z. Yu, Z.-G. Dong, X.-Q. Ren, J. Wang, Y.-R. Wang, Ranliao Huaxue Xuebao/
Journal of Fuel Chemistry and Technology 33 (2005) 372378.
[50] P.T. Burnett, G.A. Huff, V.R. Pradhan, M. Hodges, J.A. Glassett, S.G. McDaniel, P.
Hurst, The European Rening Technology Conference, Rome, Italy, 2000.
259
[90] G.W. Huber, J.W. Shabaker, S.T. Evans, J.A. Dumesic, Applied Catalysis B: Environmental 62 (2006) 226235.
[91] J.M.L. Penninger, M. Rep, International Journal of Hydrogen Energy 31 (2006)
15971606.
[92] J.W. Shabaker, J.A. Dumesic, Industrial and Engineering Chemistry Research 43
(2004) 31053112.
[93] J.W. Shabaker, G.W. Huber, R.R. Davda, R.D. Cortright, J.A. Dumesic, Catalysis
Letters 88 (2003) 18.
[94] J.W. Shabaker, D.A. Simonetti, R.D. Cortright, J.A. Dumesic, Journal of Catalysis
231 (2005) 6776.
[95] J.D. Taylor, C.M. Herdman, B.C. Wu, K. Wally, S.F. Rice, International Journal of
Hydrogen Energy 28 (2003) 11711178.
[96] M.B. Valenzuela, C.W. Jones, P.K. Agrawal, Energy and Fuels 20 (2006) 1744
1752.
[97] F. Xie, X. Chu, H. Hu, M. Qiao, S. Yan, Y. Zhu, H. He, K. Fan, H. Li, B. Zong, X. Zhang,
Journal of Catalysis 241 (2006) 211220.
[98] R.D. Cortright, L. Bednarova, Hydrogen Generation from Biomass-Derived Carbohydrates via Aqueous Phase Reforming (APR) Process, in: J. Milliken (Ed.), U.S.
Department of Energy Hydrogen Program FY2007 Anual Progress Report, U.S.
Department of Energy, Washington DC, 2007, pp. 5659.
[99] B. Rozmiarek, in: J. Milliken (Ed.), Hydrogen Generation from Biomass-Derived
Carbohydrates via Aqueous Phase Reforming Process, U.S. Department of Energy,
Washington, DC, 2008, p. PD-6.
[100] L.R. Arana, S.B. Schaevitz, A.J. Franz, M.A. Schmidt, K.F. Jensen, Journal of
Microelectromechanical Systems 12 (2003) 600611.
[101] T.V. Choudhary, D.W. Goodman, Catalysis Today 77 (2002) 6578.
[102] R. Metkemeijer, P. Achard, Journal of Power Sources 49 (1994) 271282.
[103] A. Wojcik, H. Middleton, I. Damopoulos, J. Van Herle, Journal of Power Sources
118 (2003) 342348.
[104] C.J. Call, M.R. Powell, M. Fountain, A.S. Chellappa, in: S. Pan (Ed.), AmmoniaBased Hydrogen Generation for Portable Power, The Knowledge Foundation,
Washington, DC, 2001.
[105] B. Chachuat, A. Mitsos, P.I. Barton, Chemical Engineering Science 60 (2005)
45354556.
[106] K. Gardner, Portable Fuel Cells for Military Applications, Washington, DC, 2001.
[107] L.P. Magellan, Magellan, http://www.magellanlp.com/, 2008.
[108] F.A. Uribe, T.A. Zawodzinski, The Effects of Fuel Impurities on PEM Fuel Cell
Performance, Electrochemical Society, San Francisco, CA, 2001 (Abs. 339).
[109] H.L. Chum, R.P. Overend, Fuel Processing Technology 71 (2001) 187195.
[110] J.A. Satrio, B.H. Shanks, T.D. Wheelock, AIChE Annual Meeting Conference
Proceedings, Application of combined catalyst/sorbent on hydrogen generation
from biomass gasication, American Institute of Chemical Engineers, New York,
NY, United States/Austin, TX, United States, (2004), pp. 297301.
[111] P. Lu, Z. Xiong, T. Wang, J. Chang, C. Wu, Y. Chen, Taiyangneng Xuebao/Acta
Energiae Solaris Sinica 24 (2003) 758764.
[112] H. Jacobsen, Angewandte ChemieInternational Edition 43 (2004) 1912
1914.
[113] G. Chen, X. Lv, Q. Li, N. Deng, L. Jiao, in: Proceedings of the ASME Turbo Expo
2004, Production of hydrogen-rich gas through pyrolysis of biomass in a twostage reactor, American Society of Mechanical Engineers, New York, NY, United
States/Vienna, Austria, (2004), pp. 711721.
[114] G. Weber, Q. Fu, H. Wu, Developments in Chemical Engineering and Mineral
Processing 14 (2006) 3349.
[115] S. Vasileiadis, Z. Ziaka-Vasileiadou, Chemical Engineering Science 59 (2004)
48534859.
[116] D.B. Levin, H. Zhu, M. Beland, N. Cicek, B.E. Holbein, Bioresource Technology 98
(2007) 654660.
[117] A. Wood, Chemical Week 164 (2002) 30.
[118] M. Asadullah, S.-I. Ito, K. Kunimori, M. Yamada, K. Tomishige, Environmental
Science and Technology 36 (2002) 44764481.
[119] M.F. Demirbas, Energy Sources 28 (2006) 245252.
[120] A. Demirbas, Fuel 80 (2001) 18851891.
[121] N. Canter, Tribology and Lubrication Technology 60 (2004) 1415.
[122] A. Demirbas, M.F. Demirbas, Energy Sources 25 (2003) 317329.
[123] A. Demirbas, Progress in Energy and Combustion Science 30 (2004) 219230.
[124] B. Bagchi, J. Rawlston, R.M. Counce, J.M. Holmes, P.R. Bienkowski, Separation
Science and Technology 41 (2006) 26132628.
[125] J.R. Paterek, Industrial Bioprocessing 27 (2005) 5.
[126] X. Hao, L. Guo, Huagong Xuebao/Journal of Chemical Industry and Engineering
(China) 53 (2002) 221228.
[127] National Academy of Science, The Hydrogen Economy: Opportunities, Costs,
Barriers, and R&D Needs, National Academies Press, Washington, DC, 2004.
[128] J. Wills, Fuel Cell Review 2 (2006) 2326.
[129] Y.-T. Fan, Y.-H. Zhang, S.-F. Zhang, H.-W. Hou, B.-Z. Ren, Bioresource Technology
97 (2006) 500505.
[130] C. Jo-Shu, S.Y.S.Y. Wu, L. Chi-Neng, C. Jian-Sheng, International Journal of
Hydrogen Energy 30 (2005) 13751381.
[131] M. Cai, J. Liu, Y. Wei, Environmental Science and Technology 38 (2004) 3195
3202.
[132] D.B. Levin, L. Pitt, M. Love, International Journal of Hydrogen Energy 29 (2004)
173185.
[133] H.N. Gavala, I.V. Skiadas, B.K. Ahring, G. Lyberatos, Water Science and Technology 52 (2005) 209215.
[134] S.K. Khanal, W.-H. Chen, L. Li, S. Sung, Water Environment Research 78 (2006)
110117.
260