by Pamela Peerce-Landers
Hydrogen may be an attractive replacement for fossil fuels. It can be made from renewable and
sustainable resources and its product is water. Its use permits countries to reduce their dependence
on imported oil, lessen greenhouse gas emissions and improve air quality. Over 40 nations have
active programs including Argentina, Australia, Brazil, Canada, China, the 28-member EU and
countries within it, Iceland, India, Japan, Korea, New Zealand, Switzerland, Taiwan, the United States
and Venezuela. Although sometimes hydrogen may not be cheaper than the fossil fuel it replaces,
individual decisions on its adoption will weigh the strategic and environmental benefits with economics
and other local factors.
I will summarize and critique a recent review on hydrogen research, review the results of process
simulations of some renewable hydrogen production methods and then consider the medium- and
long-term roles for hydrogen.

Review of Research on Hydrogen Production, Storage and Detection

Dutta recently reviewed hydrogen research with a focus on its use as a fuel for cars and portable
electronics. All production methods discussed use renewable or sustainable feeds and energy
sources. I have categorized them by feedstock below.
Examples Mentioned
Current Disadvantages
splitting using solar

4-step process using SO2
or nuclear energy for
and NH3 with ZnO & other
Uses abundant solar
Sunny days required for
metal oxide catalysts
solar concentrators
Uses abundant solar
Power source needed on
Photovoltaic splitting
cloudy days
Not discussed.
Not discussed.
Water splitting by
microalgae, in particular,

1. Low photochemical
reinhardtii and
Uses only water &
2. Serious inhibition of
hydrogenase by O2
Hyvolution Project. 2
stage fermentation of

sugar beets, molasses,
and dark fermentation
barley straw & thick juice.
after 2015.
Not discussed.
Not discussed.
1. Bacterial activity
fluctuated 50% over daily

Photofermentation of
temp range vs. activity at
acetate by bacteria,
Can make hydrogen even
constant temp.
Rhodobacter capsulatus
in winter in Ankara.
2. H2 yield just 15% of theory.
3 biodiesel production
residues: bioglycerol,

Abundant supply of
Catalyzed steam
cheap bioglycerol from
Waste Biomass
mixtures & bioalcohols.
biodiesel production.
Not discussed.
Residues from biodiesel
Energy recovery
production: lipid-extracted
important to development
microalgal biomass
of microalgal biodiesel
residues (LMBR's)
Not discussed.
Low temperature
catalyzed gasification
Feedstock: fowl manure
Uses waste for feed
Not discussed.
1. Yields pure (100%) H2
and clean water using

inexpensive Ni catalyst.
2. Low energy
Urea from urine
Not discussed.
production of H2 from

Very high H2 recovery
organic waste
efficiency from waste
Not discussed.
Cheese whey
Uses waste for feed
Not discussed.
Abundant supply of
hydrogen sulfide in
decomposition of H2S
Use of CdS nanoparticles
natural gas plants &
as catalyst
Not discussed.
Source: S. Dutta, “A review on production, storage of hydrogen and its utilization as an energy resource,” Journal of Industrial and Engineering Chemistry, (2013). As Dutta notes, hydrogen storage is key to mobile applications. Ideally, the storage system is lightweight and inexpensive. Solid storage systems must be able to quickly take up and release hydrogen and function for many cycles. The following table summarizes various storage schemes: H2 Uptake
Storage State
Class of Material
Current Disadvantages
1. Low energy density
by volume.
2. Large tanks.
3. High pressure (350-

Compressed Hydrogen
Hydrogen (H2)
Instant availability
700 bars)
1. Energy intensive
cryogenic storage
2. Weight of container

1. Instant availability 3. Losses due to
2. High storage

venting when not in
Liquid Hydrogen
1. High capacity
2. Lightweight
3. Inexpensive 1. Sluggish kinetics
4. Thin films operate

2. Even with thin films,
Magnesium Hydride
at room temperature
full desorption takes 20
Metal Hydrides
5.0 to 7.7%
and low pressure
Calcium Hydride
Not discussed.
Insufficient capacity
Sodium hydride (NaH)
Not discussed.
Insufficient capacity
Metal catalysts
supported on activated

4-fold better than
Nickel Catalysts
carbon alone
Low capacity
Magnesium rich Mg-Y-
Ni alloys with 18R-type
long period stacking
ordered phases and

very fine YH2 particles
Not stated.
Improved kinetics
Not discussed.
1. Strong H2

Boron nitride
2. High thermal &
Capacities about half
Boron compounds
nanotubes (BNNT's)
2.5 to 3.0%
chemical stability
that desired
1. Gaseous boranes in

Ammonia borane
H2 toxic & could
interfere with fuel cell
Up to 19.6%.
7.8% based on
2. AB regeneration
AB and water.
High capacity
done off vehicle.
1. Hydrogen in water
1. Metal catalyst
also converted to H2
doubling H2 yield.
aggregate, reducing
2. High purity
activity, but use of
supports can alleviate
3. NaBH4 solutions
this problem.
Sodium borohydride
very stable, non-
2. NaBH4 regeneration
toxic & non-
expensive and done off
1. Insufficient stability.
Li-N-H system
2. High desorption
involving lithium
nitride, lithium imide,
3. Potential NH3
lithium hydride and
evolution poisons fuel
Nitrogen compounds
lithium amide
High capacity
Metal organic
Insufficient capacity at
MIL-53 and MIL-101
Not discussed.
ambient temperatures
with 1, 2 and 4 wt%
2.7 to 3.0%
Not discussed.
1. Bio-renewable
2. Low adsorption

1. Adsorption requires
Pyrolyzed Chicken
energy suggests
low temperatures
easy recovery
2. Insufficient capacity
Source: S. Dutta, “A review on production, storage of hydrogen and its utilization as an energy resource,” Journal of Industrial and Engineering Chemistry, (2013). For a minimum driving range of 300 miles (500 km.), the U.S DOE's 2017 targets for low pressure hydrogen storage are: 4. Start time to full flow (at 20oC/-20oC): 5. Operational cycle life (1/4 tank to full): Although a few of the above solid storage systems satisfy the gravimetric density requirement, none meet the kinetic or cycle life standards. Because hydrogen is flammable in concentrations of 4 to 74% in air and prone to leak through containment materials due to its small size, safety requires sensitive, reliable leak detectors. The ideal sensor is quantitative, has a low detection limit, responds and recovers rapidly, is highly selective for hydrogen and minimally affected by cold, moisture and contaminants. Odorants are out because they interfere with fuel cells. The detection methods mentioned were: Specific
Sensing Method
Material Class
1. Helps maintain H2
selectivity in humid

1. Response and recovery sluggish
vs. uncoated sensor, taking up to 8
2. Change in resistance
minutes at 65% humidity.
metal oxide
greatest of 3 coated
2. Decrease in resistance less than
uncoated sensor.
1. Helps maintain H2
1. Response to low levels of H2 in
selectivity in humid
dry environments very sluggish.
2. Decrease in resistance less than
2. Fast recovery
uncoated sensor.
1. Helps maintain H2
selectivity in humid
2. Fast recovery & much

faster reponse than Cytop-
coated sensor in dry
Decrease in resistance less than
uncoated sensor.
Not discussed
Not discussed
Heat of Combustion
Metal catalyst
Pd/Pt catalyst
Not discussed
Not discussed
Acoustic Wave
Not discussed
Not discussed

Not discussed
Not discussed
Source: S. Dutta, “A review on production, storage of hydrogen and its utilization as an energy resource,” Journal of Industrial and Engineering Chemistry (2013). The hydrophobic Fluoropel-coated indium oxide-doped tin oxide sensor was the most successful resistance sensor mentioned. However, the humidity exceeds 65% at times in many places. Additional work is required at 95% humidity. Dutta's focus was mainly academic. Costs, yields and disadvantages were not always mentioned. Reference was made to various hydrogen programs, pilots, e.g. power-to-gas and process simulation, but no details were provided. Commercialization of hydrogen from renewables, practical solid storage and sensors are well advanced. Water electrolysis accounts for about 4% of hydrogen production. In 2005, Sigurvinsson and Werkoff estimated the total cost of producing hydrogen by alkaline electrolysis in 4 countries for a plant capacity of 11,500 tons H2/yr. The countries were France, Iceland, Norway and the US. The estimates ranged from 1.6 to 5€/kg H2 depending on the cost of electricity which varied from 1 to 2.5€/kg H2. Electricity cost was the highest in the US. Current gasoline prices in these 3 European countries are 6-10€/gal. Since a kg of H2 is equivalent to a gallon of gasoline, when coupled with low cost electricity, water electrolysis can produce hydrogen at prices competitive with gasoline in Europe. Ballard offers biomass-to-fuel cell systems which it claims are competitive with diesel generators for power in remote areas, having a payback period of about 3 years. Regarding solid storage, McPhy Energy has overcome MgH2's kinetics problems. It sells commercial storage systems based on a nanostructured MgH2 graphite composite. Additives accelerate hydrogen adsorption and desorption. It has sold systems in Europe and Japan and is supplying equipment to store more than 1 ton of hydrogen for the INGRID project in Puglia, Italy. Practical hydrogen sensors are not far off. In 2010, researchers at Oak Ridge (ORNL) reported the development of a microcantilever-based hydrogen sensor using a nanostructured Pd/Ag alloy which met most of the DOE's requirements for automotive use. As of May, 2013, this technology had not been commercialized. Performance
ORNL Sensor Performance
Sensitivity Range
<0.1% to >4%
0.01-10 %
Survivability Limit
Linear reponse to 100% H2
Automotive: < 3 sec
Reponse Time
Stationary: < 30 sec
Automotive: < 3 sec
Recovery Time
Stationary: < 30 sec
Automotive: -40 to 125oC
Temperature Range
Stationary: -20 to 50oC
Automotive: 62-107 kPa
Pressure Range
Stationary: 80-110 kPa
Automotive: 0-95%
0-100%, little response to
Ambient Relative Humidty Range
Stationary: 20-80%
changes in humidity
Interferent Resistance
No false positives
Power Consumption
< 1 Watt
0.2-0.5 watts
Operating Temperature
Room temperature
Room temperature
Automotive: 6000 hrs.
Demonstrated for more than
Stationary: >5 yrs.
12 months
Automotive: 5-10%
Accuracy & Repeatability
Stationary: 10%
Source: ORNL Fact Sheet, “Optical Hydrogen Sensors for H2 Storage Systems
ORNL is also working on optical sensors that don't use Pd.
Element One has commercialized visual, reversible leak detection coatings for use in stationary
applications coupled with electronic sensors. The color change pinpoints the source of the leak.
Companies and governments need information on costs, yields, trade-offs, advantages and
disadvantages for decision-making. There are two ways to obtain these data: computer simulations
and actual demonstrations. The former is ideal for screening candidate processes, the latter for
obtaining actual operating data and experience.
Review of Process Simulations of Hydrogen Production from Renewable Sources

An Austrian team conducted process simulations to evaluate various hydrogen production methods.
The minimum purity for the hydrogen product was 99.97%, fuel cell quality. The reference technology
was steam reforming of natural gas. I have listed the other process below by feedstock.
Plant Modelled
Simulation Scenarios
Natural gas (NG)
Steam reforming
OMV oil refinery
26 million kg
Reference technology
Norsk Hydro 5040
Alkaline water electrolysis electrolyzer
382,000 kg
Decentralized plant
Stuart IMET 1000

47,000 kg
Centralized plant for local refueling
Steam reforming using
Biogas from
1. Unpurified biogas fed to on-site,
O instead of air to keep
fermentation of
decentralized, scaled-down NG
51-62% CH
maize, potato peels
N from interfering with
Bruck an der 429,000 kg for
or biowaste
33-43% CO
H2 purification
biogas plant
Leitha, Austria maize
2. Biogas used as fuel & heat source.
88-90% CH
Same as above except CO removed
1-1.6% CO
from feed.
1. Centralized plant.
2. Feed upgraded to natural gas quality
and fed to grid.
Fast Internally
1. Tar-free gas fed to on-site,
decentralized, scaled-down NG
gasification of
Fluidized Bed for Güssing,
wood chips
Steam reforming
915,000 kg
2. Gas used as fuel & heat source.
Same as above except CO removed
from feed using scrubber.
1. Centralized plant.
2. Feed upgraded to natural gas quality

and fed to grid.
Hydrolyzed mash of Dry wt% glucose
maize (M) or potato & starch: 52%
Coupled dark &
Assume 80%
2. Vacuum to limit H level which
peels (PP)
(PP), 100% (M)
Theoretical layout None
394,000 kg
for both steps inhibits microbial activity
Coupled dark
80% in dark
Dry wt% glucose
fermentation and biogas
Hydrolyzed mash of & starch: 52%
fermenter to make CH -
70% in biogas 1. Decentralized.
potato peels
(PP), 100% (M)
Theoretical layout None
202,000 kg
2. Heat & electricity made in gas engine.
1. Decentralized.
2. Heat made in gas boiler

1. Decentralized.
2. CO removed. Gas fed to on-site

steam reformer
Source: A. Miltner, et. al., Journal of Cleaner Production, 18, S52-61 (2010). Conventional steam reforming of natural gas was the most energy efficient process based on both the lower heating value (LHV) of the dry raw materials and the total energy in: 0.78 MW H2/MW raw material in and 0.8 MW H2/MW total energy in, respectively. The efficiency for alkaline electrolysis was 0.62 MW H2/energy in. It was assumed that electricity for electrolysis came from a sustainable source. Since water has no LHV, when comparing the various renewable processes studied, all efficienies below are in MW H2/MW total energy in. Of the bio-processes, steam reforming of biogas from the fermentation of maize was the best. The range for the 3 scenarios was 0.49-0.53, increasing with the purity of the biogas. Potato peels were a close second. The energy efficiency for biowaste was only 0.2. The energy efficiency for steam reforming gas from wood chips was about 20% lower than for biogas from maize or potato peels. Interestingly, energy efficiencies for the coupled dark/photofermentation of biomass sugars and starch were only about 10% lower than for centralized steam reforming of gas from wood chips, all being in the range of 0.3. However, as the authors noted, these processes were penalized by not using, or not being able to use, any of the gas or residues to self-supply heat as was done in the biogas fermentation schemes, suggesting these efficiencies could be improved. Of the renewable technologies, alkaline electrolysis was the most energy efficient, besting processes
using biofeedstocks by 20-60%. It also eliminates any conflict between using land for food vs.
feedstock. However, a sustainable, reliable source of cheap power is needed for electrolysis to be
economical. Though 50% less energy efficient in terms of the hydrogen produced, wood chips are
appealing because they are waste.
Pilots of Hydrogen Production from Renewable Sources
The EU has just 2% of the world's reserves of natural gas. So, producing hydrogen from renewables
is of interest. In 2007, there were 123 hydrogen demonstration plants in EU countries—27% of those
in Germany. Although much has likely been learned, key information like the total cost of hydrogen
production is too sensitive to publish.
In April, 2012, Idex started up a pilot in Japan with a daily capacity of 7,200 Nm3 hydrogen from 15 dry
tons of wood chips. The government provided 71% of the 2.1 billion yen needed to build the facility.
BMW and the South Carolina Research Authority (SCRA) shared the cost of a $1 million pilot to study
the feasibility of producing hydrogen from landfill gas to fuel BMW's Spartenburg fleet of material
Medium-Term Roles for Hydrogen (Within 15 Years)

For 2011, the IEA reported the breakdown of global energy use was: 19% electricity generation, 30%
transportation and 51% heating. Medium-term, hydrogen can play significant roles in generating
electricity and powering vehicles.
Generating hydrogen using wind, solar and geothermal energy can help manage the grid. Stored
hydrogen can be fed to fuel cells (HFC's) to produce electricity in times of peak use. There are many
power-to-gas pilots operating today.
Remote and backup power are attractive applications. Some hydrogen systems require a site visit
only once every 5 years making them ideal alternatives to diesel generators in remote areas. India is
installing 65,000 base transceiver stations (BTS) annually. China has approved fuel cells for its BTS's.
Because they are very reliable and furnish high quality power, HFC's are perfect backup systems for
data centers, hospitals, prisons, etc. where power outages are intolerable.

Hydrogen is also ideal for commercial fleets because they use centralized fueling stations. These
include buses, port and local delivery trucks, forklifts and airport ground service vehicles. Performance
is the same or better and refueling is fast.
A few companies make hydrogen-powered cars. Currently, these are very expensive and have limited
availability due to the high cost of HFC's and the lack of an adequate hydrogen infrastructure. Both
problems can be solved.
Recently, ACAL Energy announced it had successfully removed 80% of the Pt from its HFC's,
reducing their cost 30%. A prototype was operated continuously for 9,000 hours.
I believe that the high cost projections for building hydrogen fueling stations stem from assuming that
they would have to replace existing gas stations one-for-one. There are 170,000 gas stations in the
US. Nissan and Tesla are each building just 100 fast charging stations to cover 98% of the US and
parts of Canada. Hydrogen stations in California cost about $1 million each, so an adequate national
network could be built for $100 million. The key is affordable, adequate capacity home refueling.
Long-Term Roles for Hydrogen

Eliminating fossil fuels for electricity generation and transportation is possible. Although some
companies are using hydrogen for space heating, converting all homes seems unlikely because of the
availability of free fuels, e.g. scrap wood.
For centralized renewable electricity generation, hydrogen's most likely role is energy storage to
balance the variability in wind and solar sources.
Centralized hydrogen production and distribution through repurposed natural gas pipelines is more
probable where natural gas is scarce, like Europe. Germany has successfully coated existing natural
gas pipelines and used them for hydrogen.
Replacing diesel in long-haul trucks is more likely for large companies having depots scattered
throughout the area where hydrogen stations can be located. The cost can be mitigated by the
maintenance savings derived from eliminating the engine, transmission, cooling and emission
More rapid adoption might be achieved by combining HFC's with Li-ion batteries. The batteries
provide propulsion and are charged by the HFC's and regenerative braking. Refueling with hydrogen
takes a few minutes vs. 45 minutes plus to charge the batteries using a fast charger. Hybrid cars
could eliminate the need for home hydrogen refueling as the batteries could be charged by electricity.
Vision Motors uses this technology in its Tyrano trucks.
Hydrogen-powered trains and ships have been demonstrated and may be long-term candidates.
Many countries are actively pursuing hydrogen as a replacement for fossil fuels in electricity
generation, grid management, transportation and heating. Those with low fossil fuel reserves and
high fuel costs are more likely to embrace hydrogen for strategic and environmental reasons.

Considerable progress has been made in hydrogen generation from renewables, solid storage and
leak detection equipment. Future challenges include:
1. Continuing to improve hydrogen economics by reducing the cost of hydrogen generation, fuel 2. Greatly increasing the availability of solid storage systems; 3. Developing robust, inexpensive sensitive, selective, long-lived hydrogen sensors with short 4. Building hydrogen fueling networks; and, 5. Eliminating the need for subsidies.
This last item is very important to the future of hydrogen because cash-strapped entities lose patience.
The Czech Republic, Greece and Italy have all cut subsidies. Uncertainties exist in Australia and
India. In some US states, all-electric car owners are being assessed a fee for road use since they pay
no gas taxes. Similar measures would likely be enacted for hydrogen car owners.

Source: http://leonardo-energy.dev.o-a.be/sites/leonardo-energy/files/documents-and-links/Article_Global_Potential_Hydrogen.pdf


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THURSDAY SPEAKERS Michael Gurevitz Symposium on “toxins and ion channels” Thursday 27 July “Mechanisms and specificity in the interaction of scorpion toxins with voltage-gated sodium channels” Michael Gurevitz was born in 1946 in Germany and received his BS, MSc and PhD degrees at the Hebrew University of Jerusalem. He spent six years (1981-1986)

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