ECONOMIC ROOTS IN PRODUCTION

OF HYDROGEN GAS IN PAKISTAN

Currently, hydrogen is primarily used in the chemical industry as a reactant, but it

is being proposed as future fuel. H 2 has great potential as an environmentally clean
energy fuel and as a way to reduce reliance on imported energy sources. A
combination of the need to cut carbon dioxide emissions, the prospect of
increasingly expensive oil and the estimated growth in the world's vehicle fleet
indicates that only H2 can plug the gap. There are many processes for H 2
production. The key issue to make H2 an attractive alternative fuel is to optimize its
production from renewable raw materials instead of the more common energy
intensive processes such as natural gas reforming or electrolysis of water. With
such vision, this paper reviews developments in microbial processes for H 2
production followed by a road map to H2 economy in Pakistan. The H2 economy
potentially offers the possibility to deliver a range of benefits for the country;
however, significant challenges exist and these are unlikely to be overcome
without serious efforts.

At the start of the 21st century, we face significant energy challenges. The concept
of sustainable development is evolved for a livable future where human needs are
met while keeping the balance with nature. Driving the global energy system into a
sustainable path is progressively becoming a major concern and policy objective.

At the present, world’s energy requirement is by large being fulfilled by fossil

fuels which serve as a primary energy source. Fossil fuel has delivered energy and
convenience, in our homes, for transport and industry. However, the overwhelming
scientific evidence is that the unfettered use of fossil fuels is causing the world’s
climate to change, with potential disastrous effect on our planet. The dramatic
increase in the price of petroleum are also forcing for the search for new energy
sources and alternative ways. World is in search of convenient, clean, safe,
efficient and versatile energy source as well as energy carrier that can be delivered
to the end user.

Electricity is one of the energy carriers which are being used worldwide.
Electricity is a convenient form of energy, which can be produced from various
sources and transported over large distances. Hydrogen is another clean energy
source as well as energy carrier. H 2 economy has often been proposed by
researchers as another clean, efficient and versatile renewable energy sources as
well as energy carrier, but the transformation from the present fossil fuel economy
to a H2 economy will need the solution of numerous complex scientific and
technological issues. The provision of cost competitive hydrogen in sufficient
quantity and quality is the groundwork of a hydrogen energy economy. Presently
H2 is not an alternative fuel but only an energy carrier produced from H 2-rich
compounds. H2 holds the promise as a dream fuel of the future with many social,
economic and environmental benefits to its credit. It has the long potential to
reduce the dependence on foreign oil and lower the carbon and its compounds from
the transportation sector as shown in Table 1.

Table 1: Comparison of energy and emissions of combustible

Fuels
Fuel Type Energy per unit Energy per Kg of carbon
mass volume release per kg
(MJ/kg) (MJ/l) of fuel used
(approx.)
H2 gas 120 2 0
H2 liquid 120 8.5 0
Coal 15-19 ---- 0.5
(anthracite)
Coal 27-30 ---- 0.7
(sub- bituminous)
Natural gas 33-50 9 0.46
Petrol 40-43 31.5 0.86
Diesel 42.8 35 0.9
Bio-Diesel 37 33 0.5
Ethanol 21 23 0.5
Charcoal 30 ---- 0.5
Agricultural 10-17 ---- 0.5
Residue
Wood 15 ---- 0.5
Oil 42-45 38 0.84
H2 has some unique characteristics which make it suitable for H 2 economy,
namely:

 H2 is one of the most plentiful elements on Earth and in the Cosmos

Combustion of molecular H2 with oxygen produces heat.
 H2 has the highest energy content per unit weight of any known fuel
(142 KJ /g or 61,000 Btu/lb).
 H2 can be produced from and converted into electricity at a relatively
high efficiency. The only byproduct is water, while burning of fossil
fuels generates CO2 and a variety of pollutants. H2 may be completely
renewable fuel.
 It can be stored as liquid, gas. It can be transported over large distances
using pipelines, tankers, or rail trucks.
 It can be converted into other forms of energy in more ways and more
efficiently than any other fuel, i.e., in addition to flame combustion
(like any other fuel) H2 may be converted through catalytic
combustion, electrochemical conversion, and hydrating.

Some vehicle manufacturers have already demonstrated that H2 can be used

directly in an internal combustion engine, and fuel cell-powered prototype cars
have also been constructed. H2 can be transported for domestic/industrial
consumption through conventional means.

Production of H2 from petroleum product or natural gas does not offer any
advantage over the direct use of such fuels while production from coal by
gasification techniques with capture and elimination of CO 2 could be an interim
solution. The key issue to make H 2 an attractive alternative fuel particularly for the
transportation sector is to optimize the production process from renewable raw
materials instead of the more common energy intensive processes. Water splitting
by artificial photosynthesis, photo-biological methods based on algae, and high
temperatures obtained by nuclear or concentrated solar power plants are promising
approaches. The H2 economy is an inevitable energy system of the future where the
renewable sources will be used to generate H 2 and electricity as energy carriers,
which are capable of satisfying all the energy needs of human civilization.
However nearly all H2 produced today for the industrial sector, is largely by
thermal processes with natural gas as the H2 feedstock. Thus the development of
alternative and renewable pathways for producing H 2 fuels is of utmost
importance. The purpose of this paper is to provide a brief summary of significant
current and developing biological H2 production technologies. A vision for H2
economy in Pakistan is also discussed.

Industrial Applications of Hydrogen

Approximately 49% of hydrogen produced is used for the manufacture of
ammonia, 37% for petroleum refining, 8% for methanol production and about 6%
for miscellaneous smaller-volume uses. It is also used in the petrochemical
manufacturing, glass purification, semiconductor industry and for the
hydrogenation of unsaturated fats in vegetable oil. In metallurgical processes,
hydrogen mixed with N2, is used for heat treating applications to remove O2 as O2
scavenger. The future widespread use of hydrogen is likely to be in the
transportation sector, where it will help reduce pollution.

Vehicles can be powered with hydrogen fuel cells, which are three times more
efficient than a gasoline-powered engine.

Current Hydrogen Production

Worldwide, H2 is being considered as a fuel for the future. It is an environmentally
benign replacement for gasoline, diesel, heating oil, natural gas, and other fuels in
both the transportation and non-transportation sectors.

Although abundant on earth as an element, H2 combines readily with other

elements and is almost always found as part of some other substances, such as
water, biomass and hydrocarbons like petroleum and natural Gas. Currently 500
billion cubic meters H2 are produced annually worldwide. Presently, 40 % H 2 is
produced from natural gas, 30 % from heavy oils and naphtha, 18 % from coal,
and 4 % from electrolysis and about 1 % is produced from biomass. Currently, the
most developed and most used technology is the reforming of natural gas/
hydrocarbon fuels. Each method of H2 production requires a source of energy, i.e.,
thermal or electrolytic. The merits and demerits of the biomass processes are
discussed in Table 2.

Table 2: Advantages and disadvantages of different H2

production processes from biomass
 Process Advantages Disadvantages
Thermochemical Maximum conversion can  The significant gas
gasification be achieved conditioning is required
 Removal of tar
 Produces carbonaceous Chances of catalyst
Pyrolysis material along with bio- deactivation
oil,
 Chemicals and minerals
Solar gasification Good H2 yield Required effective collector
plates
Supercritical Can process sewage sludge, Selection of supercritical
conversion which is difficult to gasify medium

Production from coal

Hydrogen can be produced from coal through a variety of gasification processes
(e.g. fixed bed, fluidised bed or entrained flow). In practice, high-temperature
entrained flow processes are favoured to maximise carbon conversion to gas, thus
avoiding the formation of significant amounts of char, tars and phenols, in which
carbon is converted to carbon monoxide and hydrogen.

C(s) + H2O + heat CO + H2

Since this reaction is endothermic, additional heat is required, as with methane

reforming. The CO is further converted to CO2 and H2 through the water-gas shift
reaction.

Hydrogen production from coal is commercially mature, but it is more complex

than the production of hydrogen from natural gas. The cost of the resulting
hydrogen is also higher. But since coal is plentiful in many parts of the world and
will probably be used as an energy source regardless, it is worthwhile to explore
the development of clean technologies for its use.
Capture and storage of CO2

Carbon dioxide is a major exhaust in all production of hydrogen from fossil fuels.
The amount of CO2 will vary with respect to the hydrogen content of the feedstock.
To obtain a sustainable (zero emission) production of hydrogen, the CO 2 should be
captured and stored. This process is known as de-carbonization. There are three
different options to capture CO2 in a combustion process:

 POST-COMBUSTION:
The CO2 can be removed from the exhaust gas of
the combustion process in a conventional steam turbine or CCGT (combined cycle
gas turbine) power plant. This can be done via the “amine” process, for example.
The exhaust gas will contain large amounts of nitrogen and some amounts of
nitrogen oxides in addition to water vapors, CO2 and CO.

 PRE-COMBUSTION:
CO2 is captured when producing hydrogen through
any of the processes discussed above.

 OXY-FUEL-COMBUSTION:
The fossil fuel is converted to heat in a
combustion process in a conventional steam turbine or CCGT power plant. This is
done with pure oxygen as an oxidizer. Mostly CO2 and water vapors are produced
in the exhaust or flue gases, and CO 2 can be easily separated by condensing the
water vapors.

In post-combustion and oxyfuel-combustion systems, electricity is produced in

near-conventional steam and CCGT power plants. The electricity produced could
then be used for water electrolysis.

If the capture and storage of CO 2 is applied to an energy conversion process of

relatively low efficiency, and the electricity is used to electrolyze water, then the
overall efficiency of fuel to hydrogen would not exceed 30%.

The captured CO2 can be stored in geological formations like oil and gas fields, as
well as in aquifers, but the feasibility and proof of permanent CO 2 storage are
critical to the success of de-carbonization. The choice of the transportation system
for the CO2 (pipeline, ship or combined) will largely depend on the site chosen for
the production plant and the site chosen for storage.
Steam Reforming 
Steam reforming is a catalytic process that produces hydrogen from hydro carbons
involving a reaction between natural gas or other light hydrocarbons and steam.
The process is 70%–90% energy efficient but is energy-intensive because it is done
under high-temperature conditions (700°–1100°C). 

Steam reforming is currently the least expensive method of producing hydrogen. It

accounts for about 95% of the hydrogen produced in the United States and about
half of the world’s hydrogen supply. The hydrogen produced today through steam
reforming is not used as a fuel, but in the manufacturing of fertilizers, chemicals,
and electronics and in petroleum refining. 

The large-scale generation of hydrogen is done in steam reformers with production

capacities of usually 100,000 cubic meters of hydrogen per hour at facilities such
as the one shown in the photo.

Natural gas contains methane (CH4) that can be used to produce hydrogen with
thermal processes, such as steam-methane reformation and partial oxidation.

Steam-Methane Reforming
Most hydrogen produced today in the United States is made via steam-methane
reforming, a mature production process in which high-temperature steam (700°C -
1,000°C) is used to produce hydrogen from a methane source, such as natural gas.
In steam-methane reforming, methane reacts with steam under 3–25 bar pressure
(1 bar = 14.5 psi) in the presence of a catalyst to produce hydrogen, carbon
monoxide, and a relatively small amount of carbon dioxide. Steam reforming is
endothermic—that is, heat must be supplied to the process for the reaction to
proceed.

Subsequently, in what is called the "water-gas shift reaction," the carbon monoxide
and steam are reacted using a catalyst to produce carbon dioxide and more
hydrogen. In a final process step called "pressure-swing adsorption," carbon
dioxide and other impurities are removed from the gas stream, leaving essentially
pure hydrogen. Steam reforming can also be used to produce hydrogen from other
fuels, such as ethanol, propane, or even gasoline.

Steam-Methane Reforming Reaction

CH4 + H2O (+heat) → CO + 3H2

Water-Gas Shift Reaction

CO + H2O → CO2 + H2 (+small amount of heat)

Partial Oxidation
In partial oxidation, the methane and other hydrocarbons in natural gas react with a
limited amount of oxygen (typically from air) that is not enough to completely
oxidize the hydrocarbons to carbon dioxide and water. With less than the
stoichiometric amount of oxygen available, the reaction products contain primarily
hydrogen and carbon monoxide (and nitrogen, if the reaction is carried out with air
rather than pure oxygen), and a relatively small amount of carbon dioxide and
other compounds. Subsequently, in a water-gas shift reaction, the carbon monoxide
reacts with water to form carbon dioxide and more hydrogen.
Partial oxidation is an exothermic process—it gives off heat. The process is,
typically, much faster than steam reforming and requires a smaller reactor vessel.
As can be seen in chemical reactions of partial oxidation, this process initially
produces less hydrogen per unit of the input fuel than is obtained by steam
reforming of the same fuel.
Partial Oxidation of Methane Reaction

CH4 + ½O2 → CO + 2H2 (+heat)

Water-Gas Shift Reaction

CO + H2O → CO2 + H2 (+small amount of heat)

HYDROGEN FROM SPLITTING OF WATER

Hydrogen can be produced from the splitting of water through various processes.
Here we will discuss different processes like water electrolysis, photo-electrolysis,
photo-biological production and high-temperature water decomposition.

Water electrolysis
Water electrolysis is the process whereby water is split into hydrogen and oxygen
through the application of electrical energy, as in equation (3.1). The total energy
that is needed for water electrolysis is increasing slightly with temperature, while
the required electrical energy decreases.
A high-temperature electrolysis process might, therefore. be preferable when high-
temperature heat is available as waste heat from other processes. This is especially
important globally, as most of the electricity produced is based on fossil energy
sources with relatively low efficiencies. Where the possibilities to considerably
reduce the production cost are evident.

H2O + electricity H2 + 1/2O2

Alkaline electrolysis
Alkaline electrolysers use an aqueous KOH solution (caustic) as an electrolyte that
usually circulates through the electrolytic cells. Alkaline electrolysers are suited for
stationary applications and are available at operating pressures up to 25 bars.

Alkaline electrolysis is a mature technology, with a significant operating record in

industrial applications that allows remote operation.

The following reactions take place inside the alkaline electrolysis cell:

ELECTROLYTE: 4H2O 4H+ + 4OH–

CATHODE: 4 H+ + 4e– 2H2
–
ANODE: 4OH O2 + 2H2O + 4e–
SUM: 2H2O O2 + 2H2

Commercial electrolysers usually consist of a number of electrolytic cells arranged

in a cell stack.
The major R&D challenge for the future is to design and manufacture electrolyser
equipment at lower costs with higher energy efficiency and larger turn-down
ratios.

Process diagram of alkaline electrolysis

Polymer electrolyte membrane (PEM) electrolysis

PEM electrolysers require no liquid electrolyte, which simplifies the design

significantly. The electrolyte is an acidic polymer membrane. PEM electrolysers
can potentially be designed for operating pressures up to several hundred bars, and
are suited for both stationary and mobile applications. The main drawback of this
technology is the limited lifetime of the membranes. The major advantages of PEM
over alkaline electrolysers are the higher turndown ratios, the increased safety due
to the absence of KOH electrolytes, a more compact design due to higher densities,
and higher operating pressures.

ANODE: H2O 1/2O2 + 2 H+ + 2e–

CATHODE: 2H+ + 2e– H2

With relatively high cost, low capacity, poor efficiency and short lifetimes, the
PEM electrolysers currently available are not as mature as alkaline electrolysers. It
is expected that the performance of PEM electrolysers can be improved
significantly by additional work in materials development and cell stack design.
High-temperature electrolysis
High-temperature electrolysis is based on technology from high-temperature fuel
cells. The electrical energy needed to split water at 1000 °C is considerably less
than electrolysis at 100 °C. This means that a high-temperature electrolyser can
operate at significantly higher overall process efficiencies than regular low-
temperature electrolysers.

A typical technology is the solid oxide electrolyser cell (SOEC). This electrolyser
is based on the solid oxide fuel cell (SOFC), which normally operates at 700 to
1000 °C. At these temperatures, the electrode reactions are more reversible, and the
fuel cell reaction can more easily be reversed to an electrolysis reaction. Attempts
are currently underway to develop systems in which some of the electricity
consumed by the electrolyser can be replaced with the heat available from
geothermal, solar or natural gas sources, thus reducing the consumption of
electricity significantly.

Similar to the main challenges for SOFCs, the main R&D needs for SOECs relate
to materials development and thermo-mechanical stress within the functional
ceramic materials.

Photo-electrolysis (photolysis)
Photovoltaic (PV) systems coupled to electrolysers are commercially available.
The systems offer some flexibility, as the output can be electricity from
photovoltaic cells or hydrogen from the electrolyser. Direct photo-electrolysis
represents an advanced alternative to a PV-electrolysis system by combining both
processes in a single apparatus. Such systems offer great potential for cost
reduction of electrolytic hydrogen, compared with conventional two-step
technologies.

Fundamental and applied R&D efforts in relation to materials science and systems
engineering for photo-electrochemical cells (PEC) are currently being undertaken
worldwide, with at least 13 OECD countries maintaining PEC-related R&D
projects and/or entire programs. The IEA-HIA coordinates and manages a
significant part of these R&D efforts in a collaborative, task-shared Annex.
Four major PEC concept areas are being studied, comprising two-photon tandem
systems, monolithic multi-junction systems, dual-bed redox systems, and one-pot
two-step systems. While the first two concepts employ thin-film-on-glass devices
immersed in water, the latter two concepts are based on the application of
photosensitive powder catalysts suspended in water. Various laboratory-scale PEC
devices have been developed over the past couple of years, thus far demonstrating
solar to hydrogen conversion efficiencies of up to 16%.

The key challenges to advance PEC cell innovation toward the market concern
progress in materials science and engineering. It is very important to develop
photo-electrode materials and their processing technologies with high-efficiency
(performance) and corrosion-resistance (longevity) characteristics, paving the path
toward smart system integration and engineering. Since no “ideal” photo-electrode
material commercially exists for water splitting, tailored materials have to be
engineered.

Combinatorial chemistry approaches offer fast-tracking experimental options for

the necessary materials screening, while modeling capabilities of photo-oxidation
based on quantum transition theory need to be developed. Most important, there is
a need for fundamental research on semiconductor doping for band-gap shifting
and surface chemistry modification, including studies of the associated effects on
both surface and bulk semi-conducting properties. Corrosion and photo corrosion
resistance present further significant R&D challenges to be addressed, with most of
the promising materials options at hand. Current-matching between anode and
cathode, in addition to ohmic resistance minimization, requires considerable
systems design as well as sophisticated engineering solutions. Optimization of
fluid dynamics (with its effects on mass and energy transfer) and gas collection and
handling (with its effects on operational safety) will demand major conceptual and
application-specific R&D attention.

Centralized hydrogen production

Large-scale, industrial hydrogen production from all fossil energy sources can be
considered a commercial technology for industrial purposes, though not yet for
utilities. Hydrogen production at a large scale has the potential for relatively low
unit costs, although the hydrogen production cost from natural gas in medium sized
plants may be reduced towards the cost of large-scale production. An important
challenge is to decarbonize the hydrogen production process. CO2 capture and
storage options are not fully technically and commercially proven. They require
R&D on absorption or separation processes and process line-up, as well as
acceptance for CO2 storage. It is also important to increase plant efficiency, reduce
capital costs and enhance reliability and operating flexibility.

Further R&D is particularly needed on hydrogen purification (to produce H2

suitable for fuel cells) and on gas separation (to separate hydrogen or CO 2 from gas
mixtures). This involves the development of catalysts, adsorption materials and gas
separation membranes for the production and purification of hydrogen.

Hydrogen and power can be co-produced in integrated gasification combined cycle

(IGCC) plants. The IGCC plant is the most advanced and efficient solution in
which the carbon in the fuel is removed and the hydrogen is produced in a pre
combustion process.

However, successful centralized hydrogen production requires large market

demand, as well as the construction of a new hydrogen transmission and
distribution infrastructure and pipeline for CO2 storage.

In the future, centralized hydrogen production from high-temperature processes

based on renewable energy and waste heat can also be an option to enhance
sustainability and remove the need for capture and storage of CO2.

Distributed hydrogen production

Distributed hydrogen production can be based on both water electrolysis and the
natural gas processes discussed above. The benefit would be a reduced need for the
transportation of hydrogen fuel, and hence less need for the construction of a new
hydrogen infrastructure. Distributed production would also utilize existing
infrastructure, such as natural gas or water and electric power. However, the
production costs are higher for the smaller-capacity production facilities, and the
efficiencies of production will probably be lower than those of centralized plants.

In addition, carbon capture and sequestration would be more difficult and costly in
small fossil-fuelled plants. Also, it is unlikely that CO 2 from fossil fuels will be
captured and stored when hydrogen is produced from distributed reformers.

Small-scale reformers will enable the use of existing natural gas pipelines for the
production of hydrogen at the site of the consumer. Such reformers therefore
represent an important technology for the transition to a larger hydrogen supply.
The availability of commercial reformers is limited and most reformers are
currently in an R&D stage. Further development and R&D is essential to meet
customer requirements. Some of these gaps are challenging and require more effort
by the technology developers and suppliers. The technology achievements in the
last three years have been remarkable and the technology gaps have been reduced
significantly. Compactness (i.e. footprint and height) is an especially important
market requirement. Suppliers have significantly reduced the footprint and height.

The optimum system for the future would be an underground system that requires a
space of 10 x 3 x 3 meters for a capacity of 500 – 700 Nm3/hour. The target is
within reach with some additional R&D effort. However, the space required by
hydrogen production is a disadvantage for the technology when compared with
conventional trucked-in systems for gasoline/diesel or hydrogen.
Minimizing footprint and visibility has been an important R&D priority. Also,
codes and standards for hydrogen production and storage will need to be revised to
permit the use of enclosed or underground spaces, at least in some countries.

Biological H2 production processes

Producing H2 using conventional methods defeats the purpose of using H 2 as a
clean alternative fuel. The production of H 2 from non-fossil fuel sources has
become central for better transition to H2 economy. Certain microorganisms can
produce enzymes that can produce H2 provides an attractive option to produce
hydrogen through microbial process. A large number of microbial species,
including significantly different taxonomic and physiological types, can produce
H2.

Diversity in microbial physiology and metabolism means that there are a variety of
different ways in which microorganisms can produce H2, each one with seeming
advantages, as well as problematic issues. From an engineering perspective, they
all potentially offer the advantages of lower cost catalysts (microbial cells) and less
energy intensive reactor operation (mesophilic) than the present industrial process
for making hydrogen (steam reformation of methane).

The H2 metabolism of green algae was first discovered in the early 1940s by Hans
Gaffron. He observed that green algae (under anaerobic conditions) can either use
H2 as an electron donor in the CO2-fixation process or evolve H2 in both dark and
the light. Although the physiological significance of H 2 metabolism in algae is still
a matter of basic research, the process of photo-hydrogen production by green
algae is of interest because it generates H2 gas from the most plentiful resources,
light and water.

All microbial conversions can be carried out at ambient conditions, however lower
rate of H2 production and low yield are chief drawbacks. All processes are
controlled by the hydrogen-producing enzymes, such as hydrogenase and
nitrogenase. Hydrogenases exist in most of the photosynthetic microorganisms and
they can be classified into two categories:
(i) Uptake hydrogenases and
(ii) Reversible hydrogenases.
Uptake hydrogenases, such as NiFe hydrogenases and NiFeSe hydrogenases, act
as important catalysts for hydrogen consumption.
Reversible hydrogenases, as indicated by its name, have the ability to produce H 2
as well as consume hydrogen depending on the reaction condition. The major
components of nitrogenase are MoFe protein and Fe protein. Nitrogenase has the
ability to use magnesium adenosine triphosphate (MgATP) and electrons to
reduce a variety of substrates (including protons). This chemical reaction yields
hydrogen production by a nitrogenase-based system where ADP and Pi refer to
adenosine diphosphate and inorganic phosphate, respectively

2e- + 2H+ + 4ATP H2 + 4ADP + 4Pi

The processes of biological H2 production can be broadly classified into following

distinct approaches for
include:

1) Direct bio-photolysis
2) Indirect bio-photolysis
3) Photofermentation
4) Dark fermentation
5) Microbial fuel cell (MFC) (bioelectrohydrogenesis )

Direct Biophotolysis
The process of photosynthetic H2-production with electrons derived from H2O
entails H2Ooxidation and a light-dependent transfer of electrons to the [Fe]
hydrogenase, leading to the synthesis of molecular H2. The concerted action of the
two photosystems of plant-type photosynthesis to split water with absorbed
photons and generate reduced ferredoxin to drive the reduction of protons to
hydrogen, is carried out by some green algae and some cyanobacteria as shown in
(Fig. 1). The two photosynthetic systems responsible for photosynthesis process
are:
(i) photo system I (PSI) which produces reductant for CO2
(ii) photo system II (PSII) which splits water to evolve O2.
The two photons obtained from the splitting of water can either reduce CO 2 by PSI
or form H2 in the presence of hydrogenase. In plants, due to the lack of
hydrogenase, only CO2 reduction takes place. On the contrary, green algae and
cyanobacteria (blue-green algae) contain hydrogenase and thus have the ability to
produce H2. In these organisms, electrons are generated when PSII absorbs light
energy, which is then transferred to ferredoxin. A reversible hydrogenase accepts
electrons directly from the reduced ferredoxin to generate H 2 in the presence of
hydrogenase.

Figure-1. Direct Biophotolysis (green algae – cyanobacteria)

Since hydrogenase is sensitive to oxygen, it is necessary to maintain the oxygen

content at a low level (under 0.1 %) so that the hydrogen production can be
sustained. This process results in the simultaneous production of O2 and H2 with a
H2:O2 = 2:1 ratio. This mechanism holds the promise of generating hydrogen
continuously and efficiently through the solar conversion ability of the
photosynthetic apparatus. In the absence of provision for the active removal of
oxygen, this mechanism can operate only transiently, as molecular oxygen is a
powerful inhibitor of the enzymatic reaction and a positive suppressor of [Fe]
hydrogenase gene expression. At present, this direct mechanism has limitations as
a tool of further research and for practical application, mainly due to the great
sensitivity of the [Fe]- hydrogenase to O2, which is evolved upon illumination by
the water-oxidizing reactions of PSII. Nevertheless, such H 2 co-production can be
prolonged under conditions designed to actively remove O2 from the reaction
mixture.
Even though photosynthetic hydrogen production is a theoretically perfect process
with transforming solar energy into hydrogen by photosynthetic bacteria, applying
it to practice is difficult due to the low utilization efficiency of light and difficulties
in designing the reactors for hydrogen production .

Photofermentation

Photofermentation also requires input of light energy for hydrogen production

from various substrates, in particular organic acids, by photosynthetic bacteria
(Fig .2). Photosynthetic bacteria have long been studied for their capacity to
produce hydrogen through the action of their nitrogenase system. Fermentative
hydrogen production has the advantages of rapid hydrogen production rate and
simple operation. Photosynthetic bacteria have long been studied for their capacity
to produce significant amounts of hydrogen due to their high substrate conversion
efficiencies and ability to degrade a wide range of substrates.

The photosynthetic bacteria have been shown to produce hydrogen from various
organic acids and food processing and agricultural wastes. Although pure
substrates have usually been used in model studies, some success in using
industrial wastewater as substrate has been shown. In general, rates of hydrogen
production by photo heterotrophic bacteria are higher when the cells are
immobilized in or on a solid matrix, than when the cell is free-living.

However, pre-treatment may be needed prior to photosynthetic bio hydrogen gas

production due to either the toxic nature of the effluent, or its color/ opaqueness.
 Figure-2. Photofermentation (Photosynthetic bacteria)

Dark fermentation
In dark fermentation, H2 production is inherently more stable since it takes place in
the absence of oxygen. The oxidation of the substrate by bacteria generates
electrons which need to be disposed off in order to maintain the electrical
neutrality. Under the aerobic conditions O2 serves as the electron acceptor while
under the anaerobic or anoxic conditions other compounds, such as protons, act as
the electron acceptor and are reduced to molecular H2.

Hydrogen can be produced by anaerobic bacteria, grown in the dark on

carbohydrate-rich substrates.

While direct and indirect photolysis systems produce pure H 2, dark-fermentation

processes produce a mixed biogas containing primarily H 2 and carbon dioxide
(CO2), but which may also contain lesser amounts of methane (CH4), CO, and/or
hydrogen sulfide (H2S). The gas composition presents technical challenges with
respect to using the biogas in fuel cells. In order for hydrogen production by dark
fermentation to be economically feasible and sustainable, a two-step/hybrid
biological hydrogen production process would be necessary.
Higher overall substrate conversion efficiency is possible by combining the
anaerobic and photosynthetic steps, as shown in Fig. 3. The photosynthetic
microbes can degrade the soluble metabolites from the fermentative step using
sunlight to overcome the energy barrier.

Dark fermentation reactions can be operated at mesophilic (25 –40°C),

thermophilic (40–65°C), extreme thermophilic (65–80°C), or hyperthermophilic
(80°C) temperatures. Biohydrogen production by dark fermentation is highly
dependent on the process conditions such as temperature, pH, mineral medium
formulation, type of organic acids produced, hydraulic residence time (HRT), type
of substrate and concentration, hydrogen partial pressure, and reactor
configuration.
Since organic substrates are the ultimate source of hydrogen in photofermentations
or indirect biophotolysis processes, it can be argued that it should be simpler and
more efficient to extract the hydrogen from such substrates using a dark
fermentation process.

Figure 3. Dark fermentation (Clostridia, Enterobacteracae)

Microbial fuel cell (MFC)
It is based on the concept and practice of a microbial fuel cell (MFC). Fact the idea
is to add a little electrical potential to that generated by a microbial fuel cell, thus
reaching a sufficient force to reduce protons to hydrogen, in a process that can be
called bioelectrohydrogenesis. A MEC consists of four parts: first, the anodic
chamber with the anode; second, the cathodic chamber with cathode; third, an
external electrical power source; and fourth, an electronic separator as shown in
Fig. 4.Thus the cell could be called a microbial electrohydrogenesis cell (MEC).

Acetate is typically used as the electron donor and it is oxidized according to the
following reaction:

Acetate - + 4H2O 2HCO3- + 9H+ + 9e-

The pH at the anode surface has a strong tendency to decrease, as one proton is
produced per electro transferred. At the cathode the hydrogen evolution reaction
takes place, in which protons and electrons are combined to form hydrogen:

2H2 + 2e H2

The reaction can be catalyzed by microorganisms or by a chemical catalyst like

platinum or nickel. When microorganisms are used as catalyst these reactions are
essentially anaerobic respirations where the external electron acceptor is an
electrode instead of the more usual oxidized compound (nitrate, TMAO, fumurate,
etc.). Thus bioelectrohydrogenesis utilizes electrochemically active micro
organisms which, with a small to moderate voltage input, convert dissolved
organic matter into hydrogen inside an electrochemical cell/microbial fuel cell via
coupled anode-cathode reactions. Expressed per amount of organic matter, the
MEC can achieve much higher hydrogen yields (80–100%) compared to
fermentative hydrogen production (<33%). This is because the MEC uses
electricity to overcome the energetic barrier for acetate oxidation.
 Figure-4. Layout of the microbial electrolysis cell.
Microorganisms present on the anode catalyze the oxidation of
substrate to bicarbonate, protons and electrons. The production of
hydrogen on the cathode may be catalyzed by a chemical catalyst or
by microorganisms (biocathode)

The performance of a MEC is determined on the one hand by the physiology of the
microorganisms, and on the other hand by the physical chemical transport
processes involved. There remains a great challenge to reduce the overpotential at
both the bioanode and biocathode. A typical application of a MEC would be
wastewater treatment, in which the organic compounds in the wastewater serve as
electron donors for the bioanode. MEC could also produce hydrogen from
agroindustrial residues containing biopolymers like cellulose and starch.

Indirect Biophotolysis
Indirect biophotolysis processes involve separation of the H2 and O2 evolution
reactions into separate stages (Fig. 5), coupled through CO 2 fixation/evolution.
Indirect biophotolysis, consists of two stages in series: photosynthesis for
carbohydrate accumulation, and dark fermentation of the carbon reserve for
hydrogen production. In this way, the oxygen and hydrogen evolutions are
temporally and/or spatially separated. This separation not only avoids the
incompatibility of oxygen and hydrogen evolution (e.g., enzyme deactivation and
the explosive property of the gas mixture), but also makes hydrogen purification
relatively easy because CO2 can be conveniently removed from the H2/CO2
mixture.
 Figure 5. Indirect biophotolysis

One elaboration of this concept involved four distinct

steps:
1. Production in open ponds at 10% solar efficiency of a biomass high in
storage carbohydrates.
2. Concentration of the biomass from the ponds in a settling pond.
3. Anaerobic dark fermentation to yield 4H2 /glucose stored in the algal
cells, plus 2 acetates.
4. A photobioreactor in which the algal cells would convert the two
acetates to 8 mol of H2.
After this last step the algal biomass would be returned to the ponds, to repeat the
cycle. Support systems included the anaerobic digestion (methane fermentation) of
any wasted biomass (assumed at 10% for each cycle), an inoculum production
system to provide make-up biomass and a gas handling and separation system (to
recycle the CO2 from the H2 back to the ponds). Genetic modifcation of strains to
eliminate uptake hydrogenases and increase levels of bidirectional hydrogenase
activity may yield signi6cant increases in H2 production.
Two-stage System
Photosynthetic O2 formation and H2 evolution occur simultaneously in green algae
as electrons and protons released from photosynthetic H2O oxidation are used in
the hydrogenase catalysed H2 evolution. In this one-stage process, H2 evolution is
transient and cannot be sustained due to strong deactivation of hydrogenase
activity by O2 (at as low as 2% partial pressure) evolved from photosynthesis. This
mutually exclusive nature of the O2 and H2 photoproduction reactions has halted
the development of H2 production process by green algae under ambient
conditions.

To overcome this problem, a two-stage protocol has been developed to evolve H2

from green algae, in which photosynthetic O2 evolution and carbon accumulation
(stage 1) is temporally separated from the consumption of cellular metabolites and
concomitant H2 production (stage 2). H2 evolution strongly depended upon the
duration of anaerobic incubation, deprivation of sulphur (S) from the medium and
the medium pH.

It has been reported that inhibition of the hydrogenase by oxygen can be partially
overcome by cultivation of algae under sulfur deprivation for 2–3 days to provide
anaerobic conditions under the light. Melis and Ghirardi devised a mechanism to
partially inactivate PSII activity to a point where all the O 2 evolved by
photosynthesis is immediately taken up by the respiratory activity of the culture.
This mechanism is based on a two-step process. The steps, growth mode and H 2
production mode, are initiated by cycling between sulfur-containing and sulfur-free
culture medium. This results in a temporal separation of net O 2- and H2- evolution
activities in the green alga Chlamydomonas reinhardtii. This discovery eliminates
the need for a purge gas, but introduces the need for careful sulfate controls in the
aqueous medium.

The absence of sulfur nutrients from the growth medium of algae acts as a
metabolic switch, one that selectively and reversibly inhibits photosynthetic O 2
production. Thus, in the presence of S, green algae do normal photosynthesis
(H2O-oxidation, O2-evolution and biomass accumulation). In 2002, NREL
researchers developed a system using two continuous-flow reactors for producing
H2 continuously for periods of up to several weeks [46]. The continuous H 2
production process involves using two continuously-stirred tanks. Fig.6 shows the
tank configuration. In Reactor 1, cells are cultured in media containing minimal
levels of sulfur. PS-II is slowed and oxygen production remains lower than oxygen
consumption for cellular respiration, but by bubbling the solutions with carbon
dioxide and a small amount of oxygen, the cells are able to remain in Reactor 1
indefinitely, obtaining some energy from photosynthesis and some energy through
respiration of acetate in solution.

Cells from Reactor 1 are transferred to Reactor 2, which is maintained under

anaerobic conditions. Cells entering Reactor 2 already have suppressed PS-II
systems, so they will not cause Reactor 2 to go aerobic. Any residual oxygen is
quickly consumed by the algae in Reactor 2. Finding themselves under anaerobic
conditions, the cells will start producing hydrogenase and subsequently, H 2. The
transition step that consumes the oxygen in solution in the batch system is avoided
by having Reactor 2 already anaerobic. At the same time, some cells are
continuously removed from Reactor 2. The effect is that the cells are removed
from Reactor 2 before they completely stop producing H2. Successful operation has
been shown with a dilution rate of 0.5/day, which is equivalent to an average
residence time of 2 days for the cells. Because Reactor 2 is a continuously-stirred
reactor (like Reactor 1), the average residence time is 2 days, but some individual
cells removed from the reactor may have been there longer or shorter times. With
an average residence time of 2 days, one would expect a H 2 production rate lower
than the initial production rate of the batch system, but higher than the production
rate at the end of a batch production cycle.

Figure 6. Continuous H2 Production

The merits and demerits of each biological process are discussed in Table 3.
 Table 3. Comparison of important biological H2 production processes

Process Advantages Disadvantages Maximum

reported
rate
(mmol
H2 /L h)
Direct  Can produce H2  Requires high 0.07
Biophotolysis directly from intensity of light
water and sunlight  Simultaneous
 Solar conversion production of O2 and
energy increased H2. O2 can be
by ten folds as dangerous for the
compared to trees, system
crops  Hydrogenase (green
algae) is highly
sensitive to even
moderately low
concentrations of O2
 Lower photochemical
efficiency
Indirect  Cyanobacteria can  Uptake hydrogenase 0.36
Biophotolysis produce H2 from enzymes are to be
water removed to stop
 Has the ability to degradation of H2
fix N2 from  About 30% O2
atmosphere present in gas mixture
Photofermentation  A wide spectral  Production rate of H2 0.16
light energy can be is slow
used by these  O2 has an inhibitory
bacteria effect on nitrogenase
 Can use different  Light conversion
organic wastes efficiency is very low,
 High substrate only 1–5%
conversion  Pre-treatment may be
efficiencies needed due to either
 Degrade a wide the toxic nature of the
range of substrate (effluent), or
substrates. its color/opaqueness.
 Large reactor surface
 areas requirement
 Expensive equipment
Dark  Simpler, less  O2 is a strong 75.60
Fermentation expensive, and inhibitor of
produce hydrogen hydrogenase
at much higher  Relatively lower
rate achievable yields of
 It can produce H2 H2
all day long  As yields increase H2 64.50
without light fermentation becomes
A variety of thermodynamically
carbon sources can unfavorable
be used as  Product gas mixture
substrates contains CO2 which
 It produces has to be separated
valuable
metabolites such
as butyric, lactic
and acetic acids as
by products
 It is anaerobic
process, so there is
no O2 limitation
problem
 Microbial Energy available in  Metabolic pathways ----
fuel cell waste streams can be involved are not clear
(MFC) directly recovered as  MEC studies have
electricity (MFC) or been carried out only
hydrogen (MEC). with mixed cultures,
promising future often using those
approach to already enriched and
hydrogen generation active in microbial
from wastewater, fuel cells (MFC).
especially for  Power densities at the
effluents with low electrode surface are
organic content low, which translates
into low volumetric
hydrogen production.
 Higher yields require
increased Voltage,
adversely affecting
energy efficiency.

Barriers for bio-hydrogen production

The diffuse nature of solar energy and the consequent low energy density places
severe economic restrictions on potential light-driven processes for biological
conversion of solar energy to hydrogen.

Major challenges need to be overcome for the smooth transition from the fossil
fuel based economy to the H2 energy based economy and may be outlined as
follows:
 The yield of H2 from any of the processes defined above is low for
commercial application.
 The pathways of H2 production have not been identified and the reaction
remains energetically unfavorable.
 There is no clear contender for a robust, industrially capable
microorganism that can be metabolically engineered to produce more
than 4 mol H2/mol of glucose.
Several engineering issues need to be addressed which include the appropriate
bioreactor design for H2 production, difficult to sustain steady continuous H 2
production rate in the long term, scale-up, preventing interspecies H 2 transfer in
non sterile conditions and separation/purification of H 2. Sensitivity of hydrogenase
to O2 and H2 partial pressure severely disrupts the efficiency of the processes and
adds to the problems of lower yields. Insufficient knowledge on the metabolism of
H2 producing bacteria and the levels of H 2 concentration tolerance of these
bacteria. Other barriers to microbial based, large-scale production of H2 include:

 Inherent properties of the microbes that preclude continuity and efficiency of

H2 production
 Underlying limitations of photosynthetic efficiency
 Limitations of the hydrogenase catalytic function.

Immobilization
One of the largest challenges of optimizing molecular H 2 production by
Chlamydomonas reinhardtii cells is the transfer of the cells from sulfur deficient
conditions to sulfur rich conditions (for regenerative purposes) and then back to
sulfur deficient conditions (for further H2 production). Recent research in
immobilization has provided a new technique to eliminate this challenge.

Prior to the development of immobilizations, cells were suspended in aqueous

media with either sulfur rich or deficient conditions present. This posed a problem
for scientists because the cells had to be filtered out of the media to be transferred
to the next media in the cycle of molecular H 2 production. The filtration process
was very time consuming and so was not feasible on an industrial scale. Another
dilemma that plagued the free suspension in liquid media technique was the
inability to make the media with cells very concentrated. This restricted the amount
of light that could interact with the cells decreasing the overall yield of molecular
H2. To avoid difficulties with media transition or cellular concentration
immobilization techniques were developed.
 Table 4. Scientific and technical barriers for bio-hydrogen production

Type Of Barrier Barrier Putative

Solution

 Isolate more
novel microbes
and
combinational
Bacteria do not produce screen for H2
Organism more than 4 production rates
mol H2/mol glucose yields, and
naturally durability.
 Genetic
manipulation of
Basic established
Science bacteria.
 Greater
understanding of
the enzyme
 Hydrogenase over regulation and
Enzyme expression.
expression not stable
(hydrogenase)  O2 sensitivity  Mutagenic
 H2 feedback inhibition studies.
 Low H2 partial
pressure
fermentation.
 Renewable
biomass as
 High cost of suitable feedstock.
Feedstock feedstock (glucose)  Co-digestion/use
 Low yield using of microbial
renewable biomass consortia which
Fermentative can increase the
yield
Development of
Lack of industrial- industrially viable
Strain strain(s)/consortia
suitable strain
  Commercially feasible Hybrid system (photo
+ dark fermentation)
product yield
 Link fermentation
to a second process
that makes both
economically
possible
 Application and
 Incomplete substrate utilization of
fermentation tools
Process utilization such as continuous
 Sustainable process culture.
 Sterilization  Development of low
cost stream
sterilization
technology/process
that can bypass
sterilization
 Lack of Incorporation of
process engineering
kinetics/appropriate
concepts to develop a
Reactor reactor design for H2 suitable reactor for
production the defined
 Light intensity in case strain/process, flat
of photo bioreactor panel or hollow tube
reactor can be
employed
Engineering Reverse electron
Thermodynamic barrier
transport to drive H2
Thermodynamic NAD(P)H → H2 (+4.62 production past barrier
kJ/mol)
H2 H2 purification/separate Selection absorption of
CO2 /H2S
on Storage Basic studies on H2
storage

Maximum possible yield of H2 by green algae

Even though the catalytic activity of the various enzymes differs enormously, there
is no evidence for the quantity of hydrogen-producing enzyme being the limiting
factor. Indeed, in many microbial systems, potential catalytic activity far surpasses
the amount of hydrogen produced, suggesting that other metabolic factors are
limiting.
The use of light attenuation devices that transfer sunlight into the depths of a dense
algal culture is an approach to overcoming the light saturation effect in light
driven. The simplest approach is to arrange photobioreactors in vertical arrays to
reduce direct sunlight. Of course, this arrangement also proportionally increases
the area of required photobioreactors, which is the limiting economic factor in any
photobiological fuel production process.
Another alternative is the use of optical fiber photobioreactors, in which light
energy is collected by large concentrating mirrors and piped into small
photobioreactors with optical fibers. Application of the two-stage photosynthesis
and H2 production protocol to a green alga mass culture could provide a
commercially viable method of renewable H2 generation. Calculations were based
on the integrated luminosity of the sun during a cloudless spring day. In mid
latitudes at springtime, this would entail delivery of approximately 50 mol photons
photosynthetic apparatus. It is generally accepted that electron transport by the two
photosystems and via the hydrogenase pathway for the production of 1 mol H 2
requires the absorption and utilization of a minimum of 5 mol photons in the
photosynthetic apparatus. On the basis of these “optimal” assumptions, it can be
calculated that green algae could produce a maximum 10 mol (20 g) H 2 per m2
culture area per day. If yields of such magnitude could be approached in mass
culture, this would constitute a viable and profitable method of renewable H 2
production.

Optical properties of light absorption by green algae

Light absorption by the photosynthetic apparatus is essential for the generation of
H2 gas. However the optical properties of light absorption by green algae impose a
limitation in terms of solar conversion efficiency in the algae chloroplast. This is
because wild type green algae are equipped with a large size light harvesting
chlorophyll antenna to absorb as much sunlight as they can. Under direct and
bright sunlight, they could waste up to 60% of the absorbed irradiance.

This evolutionary trait may be good for survival of the organism in the wild, where
light is often limiting, but it is not good for the photosynthetic productivity of a
green algal mass culture. This optical property of the cells could further lower the
productivity of a commercial H2 production farm.
The analysis up to this point has shown that H2 production can be limited by the
photons available or the capacity of algae to process the photons into H 2. Another
observation is that the number of photons absorbed is much higher than the algae’s
ability to process the photons. By reducing the number of excess photons absorbed
and let them reach deeper into the liquid, it may be possible to produce more H2.

By reducing the size of the algae’s light collecting antennae, but not affecting the
organism’s ability to process the photons to produce H2, one gets deeper light
penetration for the same cell concentration, which means more photons are
available at the lower depths for H2 production.

While regular green algae absorb most of the light falling on them, algae
engineered to have less chlorophyll let some light left through. In University of
California, Berkeley, Melis and his colleagues are designing algae that have less
chlorophyll so that they absorb less sunlight. When grown in large, open
bioreactors in dense cultures, the chlorophyll-deficient algae will let sunlight
penetrate to the deeper algae layers and thereby utilize sunlight more efficiently.

The critical enzymatic component of this photosynthetic reaction is the reversible

hydrogenase enzyme, which reduces protons with high potential energy electrons
to form H2. During normal photosynthesis, algae focus on using the sun’s energy to
convert carbon dioxide and water into glucose, releasing oxygen in the process.
Only about 3 to 5 percent of photosynthesis leads to H2. Because hydrogenase is
sensitive to oxygen, this H2 production must be carried out in an anaerobic
environment.

Photosynthetic H2 production by green algae involves water splitting to produce H2

and oxygen. Unfortunately, H2 production by this process is quite ineffective since
it simultaneously produces oxygen, which inhibits the hydrogenase enzyme. Thus,
during light reaction, H2 evolution ceases due to an accumulation of oxygen.
Therefore the prerequisite for photo hydrogen production by green algae is that
they have to adapt to an anaerobic condition.

By exposing the cells to specific conditions scientists are able to modify

photosynthesis so that oxygen will not act as the final electron carrier of the
electron transport chain; rather H2 will allow the cells to release molecular H 2 as
opposed to molecular oxygen. Melis estimates that, if the entire capacity of the
photosynthesis of the algae could be directed toward H 2 production, 80 kilograms
of H2 could be produced commercially per acre per day. The yield of H2 production
currently achieved in the laboratory corresponds to only 15 to 20% of the measured
capacity of the photosynthetic apparatus for electron transport.

In a laboratory, Melis worked with low-density cultures and have thin bottles so
that light penetrates from all sides. Because of this, the cells use all the light falling
on them. But in a commercial bioreactor, where dense algae cultures would be
spread out in open ponds under the sun, the top layers of algae absorb all the
sunlight but can only use a fraction of it.

Hydrogen Fuel Cell Technology

Fuel cells operate using hydrogen, the most abundant element in the universe.
Hydrogen combines readily with other elements and forms compounds. On Earth,
hydrogen is chiefly combined with oxygen in the form of water. One method of
hydrogen production is via electrolysis – passing electricity through water between
two electrodes. This process that can be made extremely clean and emissions-free
by using electricity generated by renewable resources, such as solar or wind
power. 

Hydrogen is a clean, sustainable, safe and efficient energy vector that, in the future,
will complement electricity when it comes to ensuring the supply of energy to the
population, while also increasing the penetration of renewable sources. This new
situation is leading various Public Agencies, institutions and companies around the
world to position themselves by preparing strategies and action plans focused on a
future that contemplates the use of hydrogen and fuel cells. In this respect,
hydrogen and fuel cells are considered crucial to the introduction of renewable
sources into the energy mix, as their use as an energy storage system eliminates the
intermittent nature itself of these resources.

Many aspects of the Fuel Cell Technology make it a viable energy source for any
developing economy, among others namely:

 Energy required to make Hydrogen is lesser than many alternative fuels. 

 Safety of Hydrogen as compared to other fuels is higher for use in
transportation. 
 Convenient storage of Hydrogen being highly compressible, as it is the
lightest element. 
 Envioronmentally friendly both in terms of reduction of noise and Green
House Gases. 
  Provides energy security since it is found in abundance world over. 
 Higher efficiency of Energy conversion. 

Global positioning, as regards the development of hydrogen and fuel cell

technologies, as well as the approach taken to implement a Hydrogen Economy, is
determined on the basis of three cornerstones: US-Canada, Japan and the European
Union. Pakistan has yet to see any development in this field.

According to the Freedonia Group and Pike Research, it is projected that global
revenues in hydrogen and fuel cells combined will be between $3.2 billion and
$9.2 billion in 2015 and between $7.7 billion and $38.4 billion in 2020,
respectively. The global hydrogen and fuel cell market could be worth over $180
billion in 2050. Revenues in the fuel cell sector are projected to grow at a rate of
26% over the next decade. In comparison, other renewable energy sectors are
expected to grow at slower rates, such as solar (12%), biofuels (10%) and wind
(6%). Additionally, in 2009 the global fuel cell market grew 41%, compared to
2008, and the industry shipped roughly 24,000 fuel cell systems. 

Along with increasing financial market knowledge, global statistics on

employment are also more readily available for the hydrogen and fuel cell industry.
It is estimated that there are currently 13,272 jobs around the world directly related
to hydrogen and fuel cells with another 25,764 indirectly related, bringing the total
to nearly 40,000 jobs worldwide . By 2019, there may be as many as 700,000 jobs
worldwide employed by the hydrogen and fuel cell industry. 

This calls for a concerted effort by the government to invest and secure Pakistan's
energy market with this technology. The discussants are welcomed to build on the
impact this technology may have on the future energy mix and on utilizing this
technology in different areas. 

Further research and development aimed at increasing rates of synthesis and final
yields of H2 are essential. Optimization of bioreactor designs, rapid removal and
puri6cation of gases, and genetic modification of enzyme pathways that compete
with hydrogen producing enzyme systems offer exciting prospects for bio
hydrogen systems. Increase in the rate of H 2 would reduce bioreactor size
dramatically to overcome the engineering challenges of scale up, and create new
opportunities for practical applications.
Fuel sells if it is cheap, clean, and carbon-free. That may become a maxim of this
millennium and an argument in favor of fuel cells. These devices may be used to
produce electricity in homes and cars using oxygen from air and hydrogen from
natural gas. Their chief waste product is harmless water vapor.
At ORNL, Tim Armstrong of the Metals and Ceramics (M&C) Division is leading
the effort to develop solid-oxide fuel cells and components using advanced
materials. This type of fuel cell is flexible in the fuels it can use; for example, it
can use natural gas in a process to convert chemical energy to electrical energy.
How is the system made and how does it work?
Hydrogen from natural gas is passed over an anode (negative electrode) made of
nickel and yttria-stabilized zirconia (YSZ). The hydrogen atoms break apart into
positively charged ions and electrons. The electrons travel through an external
circuit to a cathode (positive electrode) made of the rare-earth oxide lanthanum
strontium manganate (LaSrMnO3).

Oxygen from the air or carbon monoxide is collected at the cathode where the gas
accepts electrons to form negatively charged oxygen ions, which are passed
through a YSZ electrolyte separating the anode and cathode. The electrolyte is
heated to 600 to 1000°C by an electric heater to start the electrochemical reaction.
On arrival at the anode, each oxygen ion is discharged by reacting with two
hydrogen ions to form water. The heat from the electrochemical reaction maintains
the cell temperature, allowing the electric heater to be turned off.

Iron aluminide alloys developed in the M&C Division by C. T. Liu, Claudette

McKamey, and Vinod Sikka are candidates for solid-oxide fuel cell containment
vessels. ORNL Fossil Fuel Energy Program Manager Rod Judkins and Sikka
worked with Siemens Westinghouse to confirm the efficacy of iron aluminide in
the fuel cell application. Compared with the stainless steels currently used for
containment, the iron aluminide alloys are stronger and more resistant to the
simultaneous oxidizing and reducing conditions to which containment vessels are
exposed. Thus, iron aluminide containments are expected to be more reliable and
to last much longer. Mike Santella of the M&C Division is working with industrial
partners to develop the technology for fabricating iron aluminide containment
vessels.

"This solid-oxide fuel cell can also provide high-quality waste heat that can be
used to warm the home or provide refrigeration and air conditioning," Armstrong
says. "Its only emissions are steam, trace amounts of nitrogen oxides and sulfur
oxides, and a small amount of carbon dioxide."
For powering many homes at once while eliminating carbon dioxide emissions, the
M&C group has designed a power plant using a solid-oxide fuel cell and gas
turbine and incorporating ORNL's novel activated-carbon and membrane-
separation technologies and heat-exchange technologies, such as the carbon foam
that rapidly transports heat. The most efficient gas turbines available today produce
electricity using 60% of the energy in the fuel gas. Siemens-Westinghouse has
designed a solid-oxide fuel cell that is 60% efficient and a hybrid fuel cell–
microturbine plant in which waste heat from the fuel cell is used to drive the
microturbine. This combined-cycle power plant is 70% efficient.
"Based on the results of our computer model, the ORNL design for a similar
combined-cycle power plant is 80% efficient," Armstrong says. "The reason is that
we combine our efficient heat-exchange technologies with membrane technologies
for separating hydrogen and carbon monoxide from natural gas for use in the fuel
cell." In addition, the power plant allows carbon sequestration because ORNL's
carbon fiber composite molecular sieve technology (see Capturing Carbon the
ORNL Way article) can capture the carbon dioxide leaving the fuel cell as a waste
product. This gas can then be collected and used for enhanced oil recovery or
sequestered in geological formations.

Cars powered by electricity from hydrogen fuel cells are being designed because
they will eliminate discharges of carbon dioxide, nitrogen oxides, and particulate
emissions. Such a "zero emissions" vehicle is a goal of the Partnership for a New
Generation of Vehicles, which involves the automobile industry and the
Department of Energy.

A proton exchange membrane (PEM) fuel cell is the technology of choice in the
automobile industry for future electric cars because of its low-temperature
operation and rapid startup. PEM fuel cells have been plagued with problems, but
recent developments at ORNL may make this technology more feasible and
affordable.

The problem with using today's PEM fuel cells to power cars is that their bipolar
plates (positive and negative electrodes), which are made of machined graphite, are
too heavy, too brittle, and too costly for use in automobiles. ORNL's solution is to
make bipolar plates from a carbon-fiber composite, which is lighter, tougher, and
cheaper than machined graphite.

Ted Besmann, James Klett, Tim Burchell, and John J. Henry, Jr., all of the M&C
Division, have developed a method for making composite plates that includes
chemical vapor infiltration. Basically, carbon fibers are molded to make an
electrode, and methane is flowed over the plate at high temperatures to deposit
carbon that seals its surface pores. Because a fuel cell is a stack of bipolar plates
with electrolytes between, the porous plate surfaces must be sealed to prevent
leakage of hydrogen and oxygen from one cell to another—a showstopper for fuel
cells.

ORNL researchers have shown that carbon-fiber composite plates not only can be
made to perform as well as graphite plates but also are half as heavy, may cost one-
fifth as much, are more conductive and corrosion resistant, and are easier to
manufacture.
Thanks to ORNL's progress in this area, the fuel-cell car may be just around the
bend.

A new method for the sustained production of hydrogen has been discovered by
researchers in ORNL's Chemical Technology Division (CTD). The discovery
could lead to the development of palm-sized fuel cells that cost only a few cents
apiece. The fuel cells could be used to power compact environmental sensors for
the military, as well as cell phones, cameras, and portable audio and video
equipment.

Soldiers could easily carry these fuel cells on the battlefield and recharge them by
adding iron powder and vinegar and then shaking them. These cells could serve as
micro power sources for sensors that can detect the presence of hazardous gases
and emissions from nearby chemical and biological warfare weapons.

In the summer of 1998, CTD's Jonathan Woodward and researchers John Getty and
Mark Orr tried a new way to make hydrogen from sugar, which involved the
deposition of the metal platinum on a glucose-digesting enzyme. The experiment
worked.

"After several different experiments," Woodward says, "we then observed that
mixing iron powder with water also produced hydrogen at ambient temperatures,
but the production was not sustained. Then we discovered that if we add gluconic
acid as well as iron powder to the water, we obtained sustained hydrogen
production under certain conditions."

Gluconic acid is an organic acid consisting of carbon, hydrogen, and oxygen

(C6H11O7) that is produced from glucose sugar, an abundant and renewable
carbon source. Woodward noted that the sustained hydrogen-production reaction
works well under three conditions: a temperature of 80°C, neutral pH, and the
absence of oxygen.

Although the mechanism of the reaction is not fully understood, Woodward says
that iron may be serving as the active catalyst for the production of hydrogen gas
from water under anaerobic conditions. During the reaction, the metal iron (Fe) is
converted to an iron-oxide compound called magnetite (Fe3O4). The magnetite
would then be reduced back to iron in the oxygen-free atmosphere containing
gluconic acid. Thus, the iron catalyst would be regenerated from the magnetite,
enabling the continuing production of hydrogen.
"We found that after 100 hours of the experiment, we lost little metal and got more
hydrogen than we expected," Woodward says. "We generated more hydrogen than
the typical metal displacement reaction where iron is normally consumed. We
believe that some of the hydrogen is produced by the reaction of the iron metal
with the organic acid, but more experiments must be done to prove that.

"Hydrogen produced this way could be used as a power source for fuel cells that
power sensors and cameras requiring very low current in the micro- to milli
ampere range. Larger-scale applications may also be possible."

New formula for fast, abundant hydrogen production may

help power fuel cells
Scientists in Lyon, a French city famed for its cuisine, have discovered a quick-
cook recipe for copious volumes of hydrogen (H2).

The breakthrough suggests a better way of producing the hydrogen that propels

rockets and energizes battery-like fuel cells. In a few decades, it could even help
the world meet key energy needs—without carbon emissions contributing to the
greenhouse effect and climate change.

It also has profound implications for the abundance and distribution of life, helping
to explain the astonishingly widespread microbial communities that dine on
hydrogen deep beneath the continents and seafloor.

Describing how to greatly speed up nature's process for producing hydrogen will
be a highlight among many presentations by Deep Carbon Observatory (DCO)
experts at the American Geophysical Union's annual Fall Meeting in San Francisco
Dec. 9 to 13.

The DCO is a global, 10-year international science collaboration unraveling the

mysteries of Earth's inner workings—deep life, energy, chemistry, and fluid
movements.

Muriel Andreani, Isabelle Daniel, and Marion Pollet-Villard of University Claude

Bernard Lyon 1 discovered the quick recipe for producing hydrogen:
In a microscopic high-pressure cooker called a diamond anvil cell (within a tiny
space about as wide as a pencil lead), combine ingredients: aluminum oxide, water,
and the mineral olivine. Set at 200 to 300 degrees Celsius and 2 kilobars pressure
—comparable to conditions found at twice the depth of the deepest ocean.

Dr. Daniel, a DCO leader, explains that scientists have long known nature's way of
producing hydrogen. When water meets the ubiquitous mineral olivine under
pressure, the rock reacts with oxygen (O) atoms from the H2O, transforming
olivine into another mineral, serpentine—characterized by a scaly, green-brown
surface appearance like snake skin. Olivine is a common yellow to yellow-green
mineral made of magnesium, iron, silicon, and oxygen.

The process also leaves hydrogen (H2) molecules divorced from their marriage
with oxygen atoms in water.

The novelty in the discovery, is how aluminum profoundly accelerates and impacts
the process.
Finding the reaction completed in the diamond-enclosed micro space overnight,
instead of over months as expected, left the scientists amazed. The experiments
produced H2 some 7 to 50 times faster than the natural "serpentinization" of
olivine.

Over decades, many teams looking to achieve this same quick hydrogen result
focused mainly on the role of iron within the olivine, Dr. Andreani says.
Introducing aluminum into the hot, high-pressure mix produced the eureka
moment.

Dr. Daniel notes that aluminum is Earth's 5th most abundant element and usually is
present, therefore, in the natural serpentinization process. The experiment
introduced a quantity of aluminum unrealistic in nature.
Jesse Ausubel, of The Rockefeller University and a founder of the DCO program,
says current methods for commercial hydrogen production for fuel cells or to
power rockets "usually involve the conversion of methane (CH 4), a process that
produces the greenhouse gas carbon dioxide (CO2) as a byproduct. Alternatively,
we can split water molecules at temperatures of 850 degrees Celsius or more—and
thus need lots of energy and extra careful engineering."

"Aluminum's ability to catalyze hydrogen production at a much lower temperature

could make an enormous difference. The cost and risk of the process would drop a
lot."

"Scaling this up to meet global energy needs in a carbon-free way would probably
require 50 years," he adds. "But a growing market for hydrogen in fuel cells could
help pull the process into the market."

"We still need to solve problems for a hydrogen economy, such as storing the
hydrogen efficiently as a gas in compact containers, or optimizing methods to turn
it into a metal, as pioneered by Russell Hemley of the Carnegie Institution's
Geophysical Laboratory, another co-founder of the DCO."

Deep energy, Dr. Hemley notes, is typically thought of in terms of geothermal

energy available from heat deep within Earth, as well as subterranean fluids that
can be burned for energy, such as methane and petroleum. What may strike some
as new is that there is also chemical energy in the form of hydrogen produced by
serpentinization.

At the time of the AGU Fall Meetings, Dr. Andreani will be taking a lead role with
Javier Escartin of the Centre National de la Recherche Scientifique in a 40-member
international scientific exploration of fault lines along the Mid-Atlantic Ridge. It is
a place where the African and American continents continue to separate at an
annual rate of about 20 mm (1.5 inches) and rock is forced up from the mantle only
4 to 6 km (2.5 to 3.7 miles) below the thin ocean floor crust. The study will
advance several DCO goals, including the mapping of world regions where deep
life-supporting H2 is released through serpentinization.

Aboard the French vessel Pourquoi Pas?, using a deep sea robot from the French
Research Institute for Exploitation of the Sea (IFREMER), and a deep-sea vehicle
from Germany's Leibniz Institute of Marine Sciences (GEOMAR), the team
includes researchers from France, Germany, USA, Wales, Spain, Norway and
Greece.
Notes Dr. Daniel, until now it has been a scientific mystery how the rock + water +
pressure formula produces enough hydrogen to support the chemical-loving
microbial and other forms of life abounding in the hostile environments of the
deep.

With the results of the experiment in France, "for the first time we understand why
and how we have H2 produced at such a fast rate. When you take into account
aluminum, you are able to explain the amount of life flourishing on hydrogen,"
says Dr. Daniel.

Indeed, DCO scientists hypothesize that hydrogen was what fed the earliest life on
primordial planet Earth—first life's first food.

And, she adds: "We believe the serpentinization process may be underway on
many planetary bodies—notably Mars. The reaction may take one day or one
million years but it will occur whenever and wherever there is some water present
to react with olivine—one of the most abundant minerals in the solar system."

Enigmatic evidence of a deep subterranean microbe network

Meanwhile, the genetic makeup of Earth's deep microbial life is being revealed
through DCO research underway by Matt Schrenk of Michigan State University,
head of DCO's "Rock-Hosted Communities" initiative, Tom McCollom of the
University of Colorado, Boulder, Steve D'Hondt of the University of Rhode Island,
and many other associates.

At AGU, they will report the results of deep sampling from opposite sides of the
world, revealing enigmatic evidence of a deep subterranean microbe network.
Using DNA, researchers are finding hydrogen-metabolizing microbes in rock
fractures deep beneath the North American and European continents that are highly
similar to samples a Princeton University group obtained from deep rock fractures
4 to 5 km (2.5 to 3 miles) down a Johannesburg-area mine shaft. These DNA
sequences are also highly similar to those of microbes in the rocky seabeds off the
North American northwest and northeastern Japanese coasts.

"Two years ago we had a scant idea about what microbes are present in subsurface
rocks or what they eat," says Dr. Schrenk. "Since then a number of studies have
vastly expanded that database. We're getting this emerging picture not only of what
sort of organisms are found in these systems but some consistency between sites
globally—we're seeing the same types of organisms everywhere we look."

"It is easy to understand how birds or fish might be similar oceans apart, but it
challenges the imagination to think of nearly identical microbes 16,000 km apart
from each other in the cracks of hard rock at extreme depths, pressures, and
temperatures" he says.

"In some deep places, such as deep-sea hydrothermal vents, the environment is
highly dynamic and promotes prolific biological communities," says Dr.
McCollom. "In others, such as the deep fractures, the systems are isolated with a
low diversity of microbes capable of surviving such harsh conditions."

"The collection and coupling of microbiological and geochemical data made

possible through the Deep Carbon Observatory is helping us understand and
describe these phenomena."

How water behaves deep within earth's mantle

Among other major presentations, DCO investigators will introduce a new model
that offers new insights into water / rock interactions at extreme pressures 150 km
(93 miles) or more below the surface, well into Earth's upper mantle. To now, most
models have been limited to 15 km, one-tenth the depth.

"The DCO gives a happy twist to the phrase 'We are in deep water'," says
researcher Dimitri Sverjensky of Johns Hopkins University, Baltimore MD.
Dr. Sverjensky's work, accepted for publication by the Elsevier
journal Geochimica et Cosmochimica Acta, is expected to revolutionize
understanding of deep Earth water chemistry and its impacts on subsurface
processes as diverse as diamond formation, hydrogen accumulation, the transport
of diverse carbon-, nitrogen- and sulfur-fed species in the mantle, serpentinization,
mantle degassing, and the origin of Earth's atmosphere.

In deep Earth, despite extreme high temperatures and pressures, water is a fluid
that circulates and reacts chemically with the rocks through which it passes,
changing the minerals in them and undergoing alteration itself—a key agent for
transporting carbon and other chemical elements. Understanding what water is like
and how it behaves in Earth's deep interior is fundamental to understanding the
deep carbon cycle, deep life, and deep energy.

This water-rock interaction produces valuable ore deposits, creates the chemicals
on which deep life and deep energy depend, influences the generation of magma
that erupts from volcanoes—even the occurrence of earthquakes. Humanity gets
glimpses of this water in hot springs.

Says Dr. Sverjensky: "The new model may enable us to predict water-rock
interaction well into Earth upper mantle and help visualize where on Earth H2
production might be underway."

The DCO is now in the 5th year of a decade-long adventure to probe Earth's
deepest geo-secrets: How much carbon is stored inside Earth? What are the
reservoirs of that carbon? How does carbon move among reservoirs? How much
carbon released from Earth's deep interior is primordial and how much is recycled
from the surface? Are there deep abiotic sources of hydrocarbons? What is the
nature and extent of deep microbial life? And did deep Earth chemistry play a role
in life's origins?

The $500 million global collaboration is led by Dr. Robert Hazen, Senior Staff
Scientist at the Geophysical Laboratory, Carnegie Institution of Washington.
Says Dr. Hazen: "Bringing together experts in microbes, volcanoes, the micro-
structure of rocks and minerals, fluid movements, and more is novel. Typically
these experts don't connect with each other. Integrating such diversity in a single
scientific endeavor is producing insights unavailable until the DCO."

Ninety percent or more of Earth's carbon is thought to be locked away or in motion

deep underground, he notes, a hidden dimension of the planet as poorly understood
as it is profoundly important to life on the surface.

New Method for Producing Clean Hydrogen

While hydrogen is ubiquitous in the environment, producing and collecting
molecular hydrogen for transportation and industrial uses is expensive and
complicated. Just as importantly, a byproduct of most current methods of
producing hydrogen is carbon monoxide, which is toxic to humans and animals.
The Duke engineers, using a new catalytic approach, have shown in the laboratory
that they can reduce carbon monoxide levels to nearly zero in the presence of
hydrogen and the harmless byproducts of carbon dioxide and water. They also
demonstrated that they could produce hydrogen by reforming fuel at much lower
temperatures than conventional methods, which makes it a more practical option.
Catalysts are agents added to promote chemical reactions. In this case, the catalysts
were nanoparticles combinations of gold and iron oxide (rust), but not in the
traditional sense. Current methods depend on gold nanoparticles ability to drive the
process as the sole catalyst, while the Duke researchers made both the iron oxide
and the gold the focus of the catalytic process.

"Our ultimate goal is to be able to produce hydrogen for use in fuel cells," said
Titilayo "Titi" Shodiya, a graduate student working in the laboratory of senior
researcher Nico Hotz, assistant professor of mechanical engineering and materials
science at Duke's Pratt School of Engineering. "Everyone is interested in
sustainable and non-polluting ways of producing useful energy without fossil
fuels," said Shodiya, the paper's first author.

Fuel cells produce electricity through chemical reactions, most commonly

involving hydrogen. Also, many industrial processes require hydrogen as a
chemical reagent and vehicles are beginning to use hydrogen as a primary fuel
source.

"We were able through our system to consistently produce hydrogen with less than
0.002 percent (20 parts per million) of carbon monoxide," Shodiya said.
The Duke researchers achieved these levels by switching the recipe for the
nanoparticles used as catalysts for the reactions to oxidize carbon monoxide in
hydrogen-rich gases. Traditional methods of cleaning hydrogen, which are not
nearly as efficient as this new approach, also involve gold-iron oxide nanoparticles
as the catalyst, the researchers said.

"It had been assumed that the iron oxide nanoparticles were only 'scaffolds'
holding the gold nanoparticles together, and that the gold was responsible for the
chemical reactions," Sodiya said. "However, we found that increasing the surface
area of the iron oxide dramatically increased the catalytic activity of the gold."

One of the newest approaches to producing renewable energy is the use of

biomass-derived alcohol-based sources, such as methanol. When methanol is
treated with steam, or reformed, it creates a hydrogen-rich mixture that can be used
in fuel cells.
"The main problem with this approach is that it also produces carbon monoxide,
which is not only toxic to life, but also quickly damages the catalyst on fuel cell
membranes that are crucial to the functioning of a fuel cell," Hotz said. "It doesn't
take much carbon monoxide to ruin these membranes."
The researchers ran the reaction for more than 200 hours and found no reduction in
the ability of the catalyst to reduce the amount of carbon monoxide in the hydrogen
gas.

"The mechanism for this is not exactly understood yet. However, while current
thinking is that the size of the gold particles is key, we believe the emphasis of
further research should focus on iron oxide's role in the process," Shodiya said.

The Duke team's research was supported by the California Energy Commission
and the Oak Ridge Associated Universities. Duke postdoctoral associates Oliver
Schmidt and Wen Peng were also part of the research team.

As part of an international collaboration, scientists in the University of Aberdeen

have worked out a method for completely converting ethanol into hydrogen and
carbon dioxide. Ethanol iself is produced by fermenting crops, and is thus carbon
neutral--any carbon biproducts from using it are simply part of the normal
environmental carbon cycle, unlike the greenhouse-gas effect of using fossil fuels.
The new process is a catalytic one, involving small nanoparticles of metal
embedded onto larger nanoparticles of cerium oxide (itself used already in catalytic
converters for cars.) The catalysis converts ethanol into H2 gas and CO2, and
amazingly also converts the noxious carbon monoxide bi-product of the process
into harmless CO2 at the same time. According to the team "at present the
generation of hydrogen needed to power a mid size fuel cell can be achieved using
1 Kg of this catalyst."
But why's hydrogen so important? Hydrogen has a bad press--the Hindenburg
Zeppelin disaster is a particularly strong image.

But an electricity-generating proton-exchange membrane fuel cell, powered by

hydrogen and oxygen gas, has one of the simplest, safest waste products you can
imagine: water. And that's a powerful argument for using such technology to
power our vehicles and even gadgets and homes in the future.
Despite the evident dangers of hauling compressed H2 gas around in a car, safe
hydrogen gas tanks are already in existence. And there's significant progress
towards producing nanotechnology H2 tanks for the future that are safer yet.
Switching to hydrogen-powered vehicles would reduce the need for fossil fuel,
immediately protecting the environment.

But 90% of the world's current hydrogen production is as a bi-product of fossil-

fuel, meaning that although hydrogen fuel itself is less polluting; its source is still
an environmentally damaging one. And that's where the new process' strength lies:
it's both carbon neutral and reduces the need for fossil fuel.

H2 Economy
A typical energy chain for sustainable H 2 comprises the harvesting of sunlight into
H2 as energy carrier, the storage and distribution of this energy carrier to the end
device where it is converted to power. The key market for fuel cells has always
assumed to be the automotive industry. The great expectation that hydrogen fuel
cell powered vehicles will displace gasoline and diesel powered vehicles has not
materialized for a variety of reasons, but primarily because fuel cell technology has
not yet matured and the infrastructure required for hydrogen storage,
transportation, and refueling has been slow to develop. Consumer energy
applications will require delivery systems that can supply H 2 as readily as gasoline
and natural gas are supplied today. Higher pressure gaseous storage and non
conventional storage technologies will be used to meet the requirements of
transportation applications (storage at 350–700 bar compared to the 200 bar
storage pressure commonly used in normal merchant gas systems).

Gas purity requirements are important for the H2 energy market. They very much
depend on the energy conversion device used, as well as on the storage technology.
Combustion systems are much less sensitive to impurity levels; however, fuel cells
are very sensitive to CO and sulfur poisoning.

The U.S. Department of Energy has developed a multiyear plan with aggressive
milestones and targets for the development of H 2 infrastructure, fuel cells, and
storage technologies. The targeted H2 cost is $2–4 kg-1 (energy equivalent of 1
gallon of gasoline) delivered.

A rollout of such a sustainable H2 chain in developed countries could go either

gradually via a H2 economy based on fossil fuels or discontinuously in the case of
inventions of disruptive technologies. For developing countries the situation may
be different. Introduction of such H2 chains for their fast-growing primary energy
demands might enable them to skip the stage of conventional, fossil fuel-based
technologies and markets and leapfrog directly to a sustainable H2 economy.

The salient features of a H2 economy will be as follows:

 A H2-based energy system will increase the opportunity to use renewable

energy in the transport sector.
 This will increase the diversity of energy sources and reduce overall
greenhouse gas emissions.
 H2 in the transport sector can reduce local pollution, which is a high priority
in many large cities.

The robustness and flexibility of the energy system will be increased by the
introduction of H2 as a strong new energy carrier that can interconnect different
parts of the energy system. The targets for reducing vehicle noise may be met by
replacing conventional engines with H2- powered fuel cells. Fuel cells for battery
replacement and backup power systems are niche markets in which price and
efficiency are relatively unimportant. Sales in this market will drive the technology
forward towards the point at which fuel cells will become economic for the
introduction into the energy sector. H2 electrolysers/fuel cells connected directly to
wind turbines are a convenient way to balance out local fluctuations in the
availability of wind power. The development of fuel cells and a H 2 economy will
provide new market opportunities and new jobs. Present knowledge indicates that
H2 as an energy carrier will involve little environmental risk. All renewable
hydrogen production technologies face the common challenge of integration with
hydrogen purification and storage.

Present energy scenario of Pakistan

Pakistan is basically an energy deficient country. Pakistan’s per capita energy
consumption, 3894kWh as against the world average of 17620kWh, gives it a
ranking of 100 amongst the nations of the world. The demand for primary energy
in Pakistan has increased considerably over the last few decades and the country is
facing serious energy shortage problems. The energy supply is not increasing by
any means to cope with the rising energy demands. As a result the gap between the
energy demand and supply is growing every year. The country is meeting about
86% of oil demand from imports by spending around US$6.65 billion per annum.
Pakistan’s future energy system looks rather uncertain. In recent years, the
combination of rising oil consumption and flat oil production in Pakistan has led to
rising oil imports from Middle East exporters. The balance recoverable reserves of
crude oil in the country as on January 1st 2010 have been estimated at 303.63
million barrels.

Natural gas accounts for the largest share of Pakistan’s energy use, amounting to
nearly 43.7 percent of total energy consumption. As on January 1, 2010, the
balance recoverable natural gas reserves have been estimated at 28.33 trillion cubic
feet. The average production of natural gas during July- March 2009-10 was
4,048.76 million cubic feet per day (mmcfd). As the demand of natural gas exceeds
the supply, country is already facing shortage of natural gas and during the peak
demand most of the gas fired generating units are shutdown while duel fuel units
are fired by oil. Pakistan is presently facing shortage of around 300-350 MMCDF
of natural gas which is likely to go up because of rising needs and slowing down of
supplies at home. According to The Energy Security Action Plan of the Planning
Commission, Pakistan will be facing a shortfall in gas supplies rising from 1.4
Billion Cubic Feet (BCF) per day in 2012 to 2.7 BCF in 2015 and escalating to
10.3 BCF per day by the year 2025. It is therefore a matter of economic security to
develop alternative H2 resources to avoid mid century energy crises in the country.

Natural gas is used in general industry to prepare consumer items, produce cement,
fertilizer and generate electricity. At present, the power sector is the largest user of
gas accounting for 33.5 percent share followed by the industrial sector (23.8
percent), household (18.1 percent), fertilizer (15.6 percent), transport (5.4 percent)
and cement (0.9 percent) [75]. Natural gas is used in the transport sector in the
form of CNG. There are about 3,116 established CNG stations in the country and
approximately 2 million vehicles are using CNG. Pakistan has become the largest
CNG consuming country among Natural Gas Vehicle (NGV) countries. According
to Petroleum Policy 1997; the use of CNG in vehicles was encouraged by
Government to reduce pressure on petroleum imports, to curb pollution and to
improve the environment [75].

Transport sector is one of the major consumers of commercial energy in Pakistan.

It accounted for about 28% of the total final commercial energy consumed (33.95
MTOE) and 55.8% of the total petroleum products consumed (15 MTOE) in the
country.
H2 Production in Pakistan
In Pakistan H2 is largely produced in the fertilizer industry from natural gas, which
is used for the production of anhydrous ammonia. All urea plants in the country are
based on natural gas as feedstock. On an average, the fertilizer sector consumes
15.6 per cent of natural gas produced in country. The government provides an
indirect subsidy to fertilizer manufacturers by selling feedstock gas at rates ranging
up to $1.0 against commercial rates of $4.0 per MMBTU. The return on paid-up
capital in the fertilizer industry is about 80-100 per cent per annum. The current
energy scenario in the country, already discussed above, identifies the transport
sector and fertilizer sector as key sectors where the H 2 gas can be immediately
employed as substitute to fossil fuel. Mirza has presented complete road map to H 2
economy in Pakistan. They have concluded that the H 2 economy potentially offers
the possibility to deliver a range of benefits for the country including reducing
dependence on oil imports, environmental sustainability and economic
competitiveness. In medium term advent of H2 will bring about technological
developments in many fields, including power generation, agriculture, the
automotive industry, and other as yet unforeseen applications. It will increase
employment, stimulate the economy, and will have a positive impact on the
environment in which atmospheric pollution is all but alleviated and the so-called
greenhouse effect is mitigated.

To ensure a sustainable energy future for Pakistan, it is necessary that the energy
sector be accorded a high priority. In Pakistan efforts to reduce reliance on fossil
fuels through increasing the share of renewable energy in the energy supply
systems have met with little success so far. Mirza and Sahir and Qureshi have
discussed the barriers to development of renewable energy. Mirza, has broadly
classified these barriers as policy and regulatory barriers, institutional barriers,
fiscal and financial barriers, market-related barriers, technological barriers and
information and social barriers. They have also suggested better coordination
among various stakeholders and indigenization of renewable energy technologies
to overcome these barriers. Sahir, and Qureshi has suggested an integrated energy
planning approach, consistency in government policies and rational policy
instruments to deal with the techno-economic and socio-political barriers are the
prerequisites for long-term sustainable development of the renewable energy
technologies.
There is little doubt that power production by renewable energies, energy storage
by H2, and electric power transportation and distribution by smart electric grids
will play an essential role in phasing out fossil fuels.

Conclusions
Concerns about global warming and environmental pollution due to the use of
fossil fuels, combined with projections of potential fossil fuel shortfall toward the
middle of the 21st century, make it imperative to develop alternative energy
sources that would clean, renewable, and environmentally friendly. It is important
to note that hydrogen can be produced from a wide variety of feed stocks available
almost anywhere. There are many processes under development which will have a
minimal environmental impact.

Development of these technologies may decrease the world’s dependence on fuels

that come primarily from unstable regions. The ‘‘in house’’ hydrogen production
may increase both national energy and economic security. The ability of hydrogen
to be produced from a wide variety of feedstocks and using a wide variety of
processes makes it so that every region of the world may be able to produce much
of their own energy. It is clear that as the technologies develop and mature,
hydrogen may prove to be the most ubiquitous fuel available.

The vision for a H2 future is one based on clean sustainable renewable energy
supply of global proportions that plays a key role in all sectors of the economy.

Microbial Processes provides an attractive option to produce H 2 at ambient

conditions. A large number of microbial species, including significantly different
taxonomic and physiological types, can produce H2, Diversity in microbial
physiology and metabolism means that there are a variety of different ways in
which microorganisms can produce H2, each one with seeming advantages, as well
as problematic issues. Lower rate of H2 production and low yield are chief
drawbacks. From an engineering perspective, they all potentially offer the
advantages of lower cost catalysts (microbial cells) and less energy intensive
reactor operation (mesophilic) than the present industrial process for making
hydrogen.
The recently developed single-organism, two-stage photosynthesis and H 2
production protocol with green algae is of interest because significant amounts of
H2 gas can be generated essentially from sunlight and water.
Further, this method does not entail the generation of any undesirable, harmful, or
polluting byproducts and it may even offer the advantage of value-added products
as a result of the mass cultivation of green algae.
However, several biological and engineering challenges must be overcome before
this promising technology becomes a practical reality. Foremost, the cellular
metabolism and basic biochemistry that support this process must be well
understood and much fundamental research on the mechanism of H 2 production by
S- deprivation remains to be done.

For Pakistan the indigenous H2 production may increase both national energy and
economic security. The ability of H2 to be produced from a wide variety of
feedstocks and using a wide variety of processes makes it so Pakistan may be able
to produce much of her own energy. Fertilizer sector is key area where the H 2 gas
can be immediately employed as substitute to natural gas.

The advent of H2 will bring about technological developments in many fields,

including power generation, agriculture, the automotive industry, and other as yet
unforeseen applications. It will increase employment, stimulate the economy of all
nations on earth, and will have a positive impact on the environment in which
atmospheric pollution is all but alleviated and the socalled greenhouse effect is
mitigated.

Non-incorporation of renewable energy issues in the regulatory policy and lack of

awareness among regulators restrict technology penetration. There is a lack of
financial resources and proper lending facilities, particularly for small-scale
projects in country. In addition, the absence of a central body for overall
coordination of energy sector activities results in duplication of R&D activities.
Unfortunately private sector especially transports and fertilizer sector has made no
contributions to promote research activities to produce H 2 from renewable
resources.