TECHNICAL REPORT

ON
BIOGAS, HYDROGEN AND HYTHANE
FUELS

Submitted to

Prof. Kumar G N
Mechanical department
NITK

MANOJ 13ME237
KARTHIK KUMAR K 13ME238
KOUSHIK 13ME239
KISHAN R - 13ME240
MANISH K-13ME241

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Acknowledgement
As a part of completion of Mechanical lab course, writing a technical report on biogas,
hythane and hydrogen fuel was indeed knowledge gaining experience. This report gave an
insight of current scenario of the usage of fuels both in India and Internationally.
Composition of fuels, Production, Utilisation of fuels leads to deeper understanding of their
applications and research in the areas.
We would like to express our heartfelt gratitude to Prof. Kumar G N, Mechanical engineering
department, National Institute of Technology, Karnataka NITK, for providing an
opportunity to conduct a technical survey of fuels and construct a technical report of our
understanding about the fuels.

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INDEX
1) Biogas 4

2) Hydrogen ...10

3) Hythane. 18

4) References. 23

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BIOGAS
Biogas typically refers to a mixture of different gases produced by the breakdown of organic
matter in the absence of oxygen. Biogas can be produced from raw materials such as
agricultural waste, manure, municipal waste, plant material, sewage, green waste or food
waste. It is a renewable energy source and in many cases exerts a very small carbon footprint.
Biogas can be produced by anaerobic digestion with anaerobic bacteria, which digest material
inside a closed system, or fermentation of biodegradable materials.
Biogas is primarily methane (CH4) and carbon dioxide (CO2) and may have small amounts of
hydrogen sulfide (H2S), moisture and siloxanes. The gases methane, hydrogen, and carbon
monoxide (CO) can be combusted or oxidized with oxygen. This energy release allows
biogas to be used as a fuel; it can be used for any heating purpose, such as cooking. It can
also be used in a gas engine to convert the energy in the gas into electricity and heat.
Biogas can be compressed, the same way natural gas is compressed to CNG, and used to
power motor vehicles. In the UK, for example, biogas is estimated to have the potential to
replace around 17% of vehicle fuel. It qualifies for renewable energy subsidies in some parts
of the world. Biogas can be cleaned and upgraded to natural gas standards, when it becomes
bio methane.

PROPERTIES
The composition of biogas varies depending upon the origin of the anaerobic digestion
process. Landfill gas typically has methane concentrations around 50%. Advanced waste
treatment technologies can produce biogas with 55%75% methane, which for reactors with
free liquids can be increased to 80%-90% methane using in-situ gas purification techniques.
As produced, biogas contains water vapor. The fractional volume of water vapor is a function
of biogas temperature; correction of measured gas volume for water vapor content and
thermal expansion is easily done via simple mathematics which yields the standardized
volume of dry biogas.
In some cases, biogas contains siloxanes. They are formed from the anaerobic decomposition
of materials commonly found in soaps and detergents. During combustion of biogas
containing siloxanes, silicon is released and can combine with free oxygen or other elements
in the combustion gas. Deposits are formed containing mostly silica (SiO
2) or silicates (SixOy) and can contain calcium, sulphur, zinc, phosphorus. Such white
mineral deposits accumulate to a surface thickness of several millimetres and must be
removed by chemical or mechanical means.
Practical and cost-effective technologies to remove siloxanes and other biogas contaminants
are available.

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For 1000 kg (wet weight) of input to a typical bio-digester, total solids may be 30% of the
wet weight while volatile suspended solids may be 90% of the total solids. Protein would be
20% of the volatile solids, carbohydrates would be 70% of the volatile solids, and finally fats
would be 10% of the volatile solids.

PRODUCTION
International Scenario
With the many benefits of biogas, it is starting to become a popular source of energy and is
starting to be used in the United States more. In 2003, the United States consumed 147
trillion BTU of energy from "landfill gas", about 0.6% of the total U.S. natural gas
consumption. Methane biogas derived from cow manure is being tested in the U.S. According
to a 2008 study, collected by the Science and Children magazine, methane biogas from cow
manure would be sufficient to produce 100 billion kilowatt hours enough to power millions
of homes across America.
Initiated by the events of the gas crisis in Europe during December 2008, it was decided to
launch the EU project "SEBE" (Sustainable and Innovative European Biogas Environment)
which is financed under the CENTRAL programme. The goal is to address the energy
dependence of Europe by establishing an online platform to combine knowledge and launch
pilot projects aimed at raising awareness among the public and developing new biogas
technologies.
In February 2009, the European Biogas Association (EBA) was founded in Brussels as a
non-profit organisation to promote the deployment of sustainable biogas production and use
in Europe. EBA's strategy defines three priorities: establish biogas as an important part of
Europes energy mix, promote source separation of household waste to increase the gas
potential, and support the production of bio-methane gas vehicle fuel. In July 2013, it had 60
members from 24 countries across Europe
Germany is Europe's biggest biogas producer and the market leader in biogas technology. In
2010 there were 5,905 biogas plants operating throughout the country; Lower Saxony,
Bavaria and the eastern federal states are the main regions. Most of these plants are employed
as power plants. Usually the biogas plants are directly connected with a CHP which produces
electric power by burning the bio methane. Biogas in Germany is primarily extracted by the
co-fermentation of energy crops (called NawaRo, an abbreviation of nachwachsende
Rohstoffe, which is German for renewable resources) mixed with manure. The main crop
used is corn. Organic waste and industrial and agricultural residues such as waste from the
food industry are also used for biogas generation.

India Scenario

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Biogas in India has been traditionally based on dairy manure as feed stock and these "gobar"
gas plants have been in operation for a long period of time, especially in rural India. In the
last 2-3 decades, research organisations with a focus on rural energy security have enhanced
the design of the systems resulting in newer efficient low cost designs such as the
Deenabandhu model.
The Deenabandhu Model is a new biogas-production model popular in India. (Deenabandhu
means "friend of the helpless.") The unit usually has a capacity of 2 to 3 cubic metres. It is
constructed using bricks or by a ferrocement mixture. In India, the brick model costs slightly
more than the ferrocement model; however, India's Ministry of New and Renewable Energy
offers some subsidy per model constructed.
In India, Nepal, Pakistan and Bangladesh biogas produced from the anaerobic digestion of
manure in small-scale digestion facilities is called gobar gas; it is estimated that such
facilities exist in over 2 million households in India, 50,000 in Bangladesh and thousands in
Pakistan, particularly North Punjab, due to the thriving population of livestock. The digester
is an airtight circular pit made of concrete with a pipe connection. The manure is directed to
the pit, usually straight from the cattle shed. The pit is filled with a required quantity of
wastewater. The gas pipe is connected to the kitchen fireplace through control valves. The
combustion of this biogas has very little odour or smoke. Owing to simplicity in
implementation and use of cheap raw materials in villages, it is one of the most
environmentally sound energy sources for rural needs. One type of these systems is the
Sintex Digester. Some designs use vermiculture to further enhance the slurry produced by the
biogas plant for use as compost.
To create awareness and associate the people interested in biogas, the Indian Biogas
Association was formed. It aspires to be a unique blend of nationwide operators,
manufacturers and planners of biogas plants, and representatives from science and research.
The association was founded in 2010 and is now ready to start mushrooming. Its motto is
"propagating Biogas in a sustainable way".
Some Gas Production Figures
If the daily amount of available dung (fresh weight) is known, gas production per day in
warm tropical countries will approximately correspond to the following values:

1 kg cattle dung 40 litres biogas

1 kg buffalo dung 30 litres biogas

If the live weight of all animals whose dung is put into the biogas plant is known, the daily
gas production will correspond approximately to the following values:

cattle, buffalo and chicken: 1,5 litres biogas per day per 1 kg live weight.

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pigs, humans: 30 litres biogas per day per 1 kg weight

STORAGE
There are two basic reasons for storing biogas or bio methane: storage for later on-site usage
and storage before and/or after transportation to off-site distribution points or systems. The
least expensive and easiest to use storage systems for on-farm applications are low-pressure
systems; these systems are commonly used for on-site, intermediate storage of biogas. The
energy, safety, and scrubbing requirements of medium- and high-pressure storage systems
make them costly and high-maintenance options for on-farm use. Such extra costs can be best
justified for biome thane, which has a higher heat content and is therefore a more valuable
fuel than biogas.

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Low-Pressure Storage of Biogas

Floating gas holders on the digester form a low-pressure storage option for biogas systems.
These systems typically operate at pressures up to 10-inch water column (less than 2 psi).
Floating gas holders can be made of steel, fibreglass, or a flexible fabric. A separate tank may
be used with a floating gas holder for the storage of the digestate and also storage of the raw
biogas.
Medium-Pressure Storage of Cleaned Biogas
Biogas can also be stored at medium pressure between 2 and 200 psi, although this is rarely,
if ever done, in the USA. To prevent corrosion of the tank components and to ensure safe
operation, the biogas must first be cleaned by removing H2S. Next, the cleaned biogas must
be slightly compressed prior to storage in tanks. Typical propane gas tanks are rated to 250
psi. Compressing biogas to this pressure range uses about 5 kWh per 1,000 ft3. Assuming the
biogas is 60% methane and a heat rate of 13,600 Btu/kWh, the energy needed for
compression is approximately 10% of the energy content of the stored biogas.

UTILISATION
Biogas can be used for electricity production on sewage works, in a CHP gas engine, where
the waste heat from the engine is conveniently used for heating the digester; cooking; space
heating; water heating; and process heating. If compressed, it can replace compressed natural
gas for use in vehicles, where it can fuel an internal combustion engine or fuel cells and is a
much more effective displacer of carbon dioxide than the normal use in on-site CHP plants.
Biogas upgrading

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Raw biogas produced from digestion is roughly 60% methane and 29% CO2 with trace
elements of H2S it is not of high enough quality to be used as fuel gas for machinery. The
corrosive nature of H2S alone is enough to destroy the internals of a plant.
Methane in biogas can be concentrated via a biogas up-grader to the same standards as fossil
natural gas, which itself has had to go through a cleaning process, and becomes bio-methane.
If the local gas network allows, the producer of the biogas may use their distribution
networks. Gas must be very clean to reach pipeline quality and must be of the correct
composition for the distribution network to accept. Carbon dioxide, water, hydrogen sulfide,
and particulates must be removed if present.
There are four main methods of upgrading: water washing, pressure swing adsorption, selexol
adsorption, and amine gas treating. In addition to these, the use of membrane separation
technology for biogas upgrading is increasing, and there are already several plants operating
in Europe and USA.
The most prevalent method is water washing where high pressure gas flows into a column
where the carbon dioxide and other trace elements are scrubbed by cascading water running
counter-flow to the gas. This arrangement could deliver 98% methane with manufacturers
guaranteeing maximum 2% methane loss in the system. It takes roughly between 3% and 6%
of the total energy output in gas to run a biogas upgrading system.

Biogas gas-grid injection

Gas-grid injection is the injection of biogas into the methane grid (natural gas grid).
Injections includes biogas until the breakthrough of micro combined heat and power twothirds of all the energy produced by biogas power plants was lost (the heat), using the grid to
transport the gas to customers, the electricity and the heat can be used for on-site generation
resulting in a reduction of losses in the transportation of energy. Typical energy losses in
natural gas transmission systems range from 1% to 2%. The current energy losses on a large
electrical system range from 5% to 8%.

Biogas in transport
If concentrated and compressed, it can be used in vehicle transportation. Compressed biogas
is becoming widely used in Sweden, Switzerland, and Germany. A biogas-powered train,
named Biogastget Amanda (The Biogas Train Amanda), has been in service in Sweden since
2005. Biogas powers automobiles. In 1974, a British documentary film titled Sweet as a Nut
detailed the biogas production process from pig manure and showed how it fueled a customadapted combustion engine. In 2007, an estimated 12,000 vehicles were being fueled with
upgraded biogas worldwide, mostly in Europe.

Electricity Production
Whereas using the gas for direct combustion in household stoves or gas lamps is common,
producing electricity from biogas is still relatively rare in most developing countries. In
Germany and other industrialised countries, power generation is the main purpose of biogas
plants; conversion of biogas to electricity has become a standard technology.

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This document will discuss the potentials, obstacles and necessary framework conditions for
the utilisation of biogas for small and medium scale electricity generation in developing
countries. This paper will not address the biogas production process in general but focus
uniquely on electricity generation.
The findings presented here are based mainly on available experience from GTZ-related pilot
biogas power plants in different countries. They focus on more or less well-documented
existing country cases even though little extensive documentation of practical long term
operating experience is available. Besides the cases described here, we know of further
examples from other GTZ projects (e.g. Bolivia, Tunisia and the Ivory Coast). However,
there is not yet sufficient information concerning these to merit inclusion in this assessment.

HYDROGEN
FUEL PROPERTIES
On reacting with oxygen, hydrogen releases
energy explosively in combustion engines or quietly in fuel cells to produce water as its only
by-product.

Energy Content
Hydrogen has the highest energy content per unit mass of any fuel. For example, on a weight
basis, hydrogen has nearly three times the energy content of gasoline (140.4 MJ/kg versus
48.6 MJ/kg). However, on a volume basis the situation is reversed: 8,491 MJ/m3 for liquid
hydrogen versus 31,150 MJ/m3 for gasoline. The low volumetric density of hydrogen results
in storage problem, especially for automotive applications. The energy density of hydrogen
is
also affected by the physical nature of the fuel, whether the fuel is stored as a liquid or as
a gas; and if a gas, at what pressure. Energy-related properties of hydrogen are compared
with other fuels in Tables 1.3 through 1.5.
One of the important and attractive features of hydrogen is its electrochemical property,
which can be utilized in a fuel cell? At present, H2/O2 fuel cells are available operating at
an efficiency of 5060% with a lifetime of up to 3000 h. The current output range from 440
to 1720 A/m2 of the electrode surface, which can give a power output ranging from 50 to
2500 W.

Wide Range of Flammability

In ambient air, hydrogen is fl ammable in 475% concentrations (which is much broader than
gasoline range, 17.6%) and is explosive in 1559% concentration range [9,13]. However,
for
internal combustion engines, it is more meaningful to define fl ammability range in terms of
equivalence ratio (), defined as the mass ratio of actual fuel/air ratio to the stoichiometric
fuel/air ratio. Then, the fl ammability range for hydrogen is 0.1 < < 7.1, and that for
gasoline is 0.7 < < 4, which indicates that H2 internal combustion engine is amenable to

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stable operation even under highly dilute conditions. In fact, the wider range gives additional
control over the engine operation for emissions and fuel metering [25]. The engine
operation at hydrogen-lean mixture (i.e., hydrogen amount less than the theoretical or
stoichiometric amount needed for combustion with a given amount of air) allows an ease
of start. Also, due to the complete combustion, the fuel economy is good. In addition, the
final combustion temperature is generally lower with hydrogen fuel than with gasoline,
reducing the amount of pollutants, such as nitrogen oxides, emitted in the exhaust.

Low Ignition Energy

The amount of energy needed to ignite hydrogen is 0.02 mJ, which is about 10-fold less
than that required for gasoline (0.24 mJ). The low ignition energy enables hydrogen
engines to ensure prompt ignition even for lean mixtures. Unfortunately, the low ignition
energy means that hot gases and hot spots on the cylinder can serve as sources of ignition,
creating problems of premature ignition and fl ash back. Prevention of hot spots is one of
the challenges associated with running an engine on hydrogen, which is further exacerbated
due to the wide fl ammability range.

Small Quenching Distance

Hydrogen has a smaller (0.64 mm) quenching distance than that for gasoline (~2 mm).
Consequently, hydrogen flames travel closer to the cylinder wall than other fuels before
extinguishing. Thus, it is more difficult to quench a hydrogen flame than a gasoline flame.
The smaller quenching distance can also increase the tendency for backfire since the flame
from a hydrogenair mixture can more readily pass a nearly closed intake valve, than a
hydrocarbonair flame.

Auto ignition Temperature

The auto ignition temperature is the minimum temperature required to initiate self sustained
combustion in a combustible fuel mixture in the absence of an external ignition.
For hydrogen, the auto ignition temperature is relatively high585oC. This makes it difficult
to ignite a hydrogenair mixture on the basis of heat alone without some additional ignition
source. The auto ignition temperatures of various fuels are shown in Table 1.3. This
temperature has important implications when a hydrogenair mixture is compressed. In
fact, the auto ignition temperature is an important factor in determining what maximum
compression ratio an engine can use, since the temperature rise during compression is
related to the compression ratio. The temperature should not exceed the auto ignition
temperature
of hydrogen to avoid premature ignition. Thus, the absolute final temperature
limits the compression ratio. The high auto ignition temperature of hydrogen facilitates
higher compression ratios than those in hydrocarbon engines. The higher compression
ratio is important, since it is related to the thermal efficiency of the system. However, the
drawback of a high auto ignition temperature is that hydrogen is difficult to ignite in a
compression ignition or diesel engine because the temperatures needed for these types of
ignitions are relatively high.

High Flame Speed

At stoichiometric ratio, hydrogen flame speed (3.46 m/s) is nearly an order of magnitude
higher (faster) than that of gasoline (0.42 m/s). Hence, due to the high flame speed,
hydrogen engines can more closely approach the thermodynamic engine cycle. However,
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at leaner mixtures, the flame velocity decreases significantly.

Hydrogen Embrittlement
Constant exposure to hydrogen causes hydrogen embrittlement in many materials, which
can lead to leakage or catastrophic failures in both metal and non-metallic components.
Factors known to influence the rate and severity of hydrogen embrittlement include
hydrogen concentration, purity, pressure, temperature, type of impurity, stress level,
stress rate, metal composition, metal tensile strength, grain size, microstructure, and heat
treatment history. Additionally, moisture content in the hydrogen gas may lead to metal
embrittlement through the acceleration of the formation of fatigue cracks. Chapters 10 and
16 discuss various embrittlement aspects in detail.

PRODUCTION
Indian scenario
Steam Methane Reforming of Natural Gas
Steam methane reforming (SMR) is the most common and least expensive method of
producing hydrogen (almost 48% of the worlds hydrogen is produced from SMR). There are
two basic steps in steam methane reforming. The first one involves the mixing of methane
with steam to produce a gaseous mixture that is mostly hydrogen with about 12% CO and
10% CO2. This process occurs at about 800o C. The next step is called water gas shift
reaction which involves combining the carbon monoxide with water to produce hydrogen gas
and carbon dioxide. The shift conversion may be conducted in either one or two stages
operating at three temperature levels. High temperature (350C) shift utilizes an iron-based
catalyst, whereas medium and low (205C) temperature shifts use a copper based catalyst.
Assuming a 76% SMR efficiency coupled with CO shift, the hydrogen yield from methane
on a volume is 2.4:1. This process results in mostly CO2 and H2 as gas outputs with smaller
amounts of carbon monoxide, methane, water and other gases. CO is removed by absorption
or membrane separation. Hydrogen is separated from carbon dioxide and other gases using
Pressure Swing Absorption (PSA), which results in pure (>99.9%) hydrogen.

Coal Gasification
The first step in hydrogen production from coal is to basify it by combining it with steam and
oxygen to produce a raw gas mixture. After the ash is removed, the raw gas is de-sulfurized
to produce synthetic gas (often called syn gas) which contains mostly hydrogen, carbon
monoxide and carbon dioxide. Carbon monoxide is converted to carbon dioxide and
hydrogen using water gas shift reaction and hydrogen is separated from the carbon dioxide
using PSA (Pressure Swing Absorption) or other separation techniques. The drawback in the
cost of hydrogen produced by coal gasification is the cost of CO2 abatement. Hydrogen
production from gasification releases about 38 kg of carbon per GJ of hydrogen.

Electrolysis of Water
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A small amount (4%) of the worlds hydrogen is produced by electrolysis of water.

Electrolysis process uses electricity to split water into hydrogen and oxygen atoms. In these
process two electrodes, one positive and another negative, are submerged in pure water that
has been made more conductive by the addition of an electrolyte. When direct current (DC) is
applied, hydrogen bubbles up at negatively charged electrodes and oxygen at positively
charged electrode. Alkaline water electrolysis is the most common technology used in larger
production capacity units (0.2 kg/day). Electrolysis is an energy intensive process. The power
consumption at 100% efficiency is about 40 kWh/kg hydrogen; however, in practice it is
closer to 50 kWh/kg. Since electrolysis units operate at relatively low pressures (10
atmospheres), higher compression is needed to distribute the hydrogen by pipelines or tube
trailers compared to other hydrogen production technologies. This process offers the potential
to produce hydrogen with almost no pollution or greenhouse gas production. The
environmental effects of renewable electrolysis depend on the technique that is used to
produce electricity. Nuclear energy can also produce carbon free electricity that can be used
to split water into hydrogen and oxygen.

International Scenario
Photo electrochemical Water Splitting
Nonporous
black
silicon
electrochemical water splitting.

photocathode

for

H2 production

by

photo

Nanostructure Si eliminates several critical problems with Si photocathode and dramatically

improves a photo electrochemical (PEC) reaction important to water-splitting. The
nanostructure black Si photocathode's improve the H2 production by providing (1) near-ideal
anti-reflection that enables the absorption of most incident light and its conversion to
photogene rated electrons and (2) extremely high surface area in direct contact
with water that reduces the over potential needed for the PEC hydrogen half-reaction.
Application of these advances would significantly improve the solar H2 conversion efficiency
of an ideal tandem PEC system. Finally, the nanostructure Si surface facilitates bubble
evolution and therefore reduces the need for surfactants in the electrolyte.

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Fermentation:
Hydrogen production from cellulose in a two-stage process combining fermentation and
electrohydrogenesis.
A two-stage dark-fermentation and electrohydrogenesis process can be used to convert the
recalcitrant lignocellulosic materials into hydrogen gas at high yields and rates. Fermentation
using Clostridium thermocellum produced 1.67 mol H2/mol-glucose at a rate of 0.25 L H2/L-d
with a corn Stover lignocelluloses feed, and 1.64 mol H2/mol-glucose and 1.65 L H2/L-d with
a cellobiose feed. The lignocelluose and cellobiose fermentation effluent consisted primarily
of: acetic, lactic, succinic, and formic acids and ethanol. An additional 800 290 mL H2/gCOD was produced from a synthetic effluent with a wastewater inoculum (fermentation
effluent inoculum; FEI) by electrohydrogensis using microbial electrolysis cells (MECs).
Hydrogen yields were increased to 980 110 mL H2/g-COD with the synthetic effluent by
combining in the inoculum samples from multiple microbial fuel cells (MFCs) each preacclimated to a single substrate (single substrate inocula; SSI). Hydrogen yields and
production rates with SSI and the actual fermentation effluents were 980 110 mL/g-COD
and 1.11 0.13 L/L-d (synthetic); 900 140 mL/g-COD and 0.96 0.16 L/L-d (cellobiose);
and 750 180 mL/g-COD and 1.00 0.19 L/L-d (lignocellulose). A maximum hydrogen
production rate of 1.11 0.13 L H2/L reactor/d was produced with synthetic effluent. Energy
efficiencies based on electricity needed for the MEC using SSI were 270 20% for the
synthetic effluent, 230 50% for lignocellulose effluent and 220 30% for the cellobiose

effluent. COD removals were 90% for the synthetic effluents, and 7085% based on VFA
removal (65% COD removal) with the cellobiose and lignocellulose effluent. The overall
hydrogen yield was 9.95 mol-H2/mol-glucose for the cellobiose.

Solar Thermal Water Splitting

The High-Flux Solar Furnace reactor is used to concentrate solar energy and generate
temperatures between 1,000 and 2,000 degrees Celsius. Ultra-high temperatures are required
for thermo chemical reaction cycles to produce hydrogen. Such high-temperature, high-flux,
solar-driven thermo chemical processes offer a novel approach for the environmentally
benign production of hydrogen. Very high reaction rates at these elevated temperatures give
rise to very fast reaction rates, which significantly enhance production rates and more than
compensate for the intermittent nature of the solar resource

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STORAGE
Compressed Gas Storage
Compressed gas storage of hydrogen is the simplest storage solution. The equipments
required are a compressor and a pressure vessel. The main problem with compressed gas
storage is the low storage density which depends on the storage pressure. High storage
pressure results in higher capital and operating costs. At low production rates, the capital cost
of the pressure vessel dominates while at higher volumes the critical factor is the electricity
cost for compression. As storage time increases, the capital cost of the pressure vessel begins
to dictate the cost. One option is to increase the operating pressure of the system (smaller,
lower cost tank; higher compressor capital and compression running costs): for short times,
there is a balance between these costs, at longer times the capital cost reduction is the
dominant factor resulting in an optimum at maximum operating pressure.

Liquid Hydrogen Storage

Liquefaction is done by cooling a gas to form a liquid. A combination of compressors, heat
exchangers, expansion engines, and throttle valves are used in liquefaction processes to
achieve the desired cooling. The simplest liquefaction process is the linde cycle or Joule
Thompson expansion cycle. In this process, the gas is compressed at ambient pressure, and
then cooled in a heat exchanger, before passing through a throttle valve where it undergoes an
isenthalpic Joule-Thompson expansion, producing some liquid. This liquid is removed and
the cool gas is returned to the compressor via the heat exchanger. An alternative to this
process is to pass the high-pressure gas through an expansion engine which consists of an
isothermal compressor, followed by an isentropic expansion to cool the gas and produce a
liquid. It is used as a theoretical basis for the amount of energy required for liquefaction and
also to compare liquefaction processes. In practice, an expansion engine can be used only to
cool the gas stream, not to condense it because excessive liquid formation in the expansion
engine would damage the turbine blades.

Metal Hydride Storage

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Metal hydrides store hydrogen by chemically bonding it to metal or metalloid elements and
alloys. Hydrides are unique because they can absorb hydrogen at or below atmospheric
pressure and then release at significantly higher pressures when heatedthe higher the
temperature, the higher the pressure. There is a wide operating range of temperatures and
pressures for hydrides depending on the alloy chosen. Each alloy has different performance
characteristics, such as cycle life and heat of reaction. When the partial pressure of hydrogen
is increased, it dissolves in the metal or alloy and then begins to bond to the metal. During the
bonding period the equilibrium or plateau pressure remains constant from the time that 10%
of hydrogen has been stored until about 90% of the storage capacity is reached. After the 90%
point, higher pressures are required to reach 100% of the hydride storage capacity. Heat
released during hydride formation must be continuously removed to prevent the hydride from
heating up. If the temperature is allowed to increase the equilibrium pressure will increase
until no more bonding occurs. If hydrogen is being recovered from another gas, some
hydrogen can be allowed to escape or blow off; taking away any contaminants that did not
bond to the hydride. To recover the hydrogen from the metal hydride, heat must be added to
break the bonds between the hydrogen and the metal. Again, the higher the temperature, the
higher the release pressure. Initially the pressure of the gas is high as any free hydrogen is
released, and then the pressure plateaus as the hydride bonds are broken. When only about
10% of the hydrogen remains the equilibrium pressure drops off. This last bit of hydrogen
dissolved in the metal matrix is difficult to remove, and represents strongly bonded hydrogen
that cannot be recovered in the normal charge/discharge cycle. Metal hydride storage is
perceived to have no economy of scale (high capital cost of storage alloy). So it does not
compete with other options at high production rates or long storage times, but may be ideal at
low flow rates and short storage times. Since it is considered as the safest storage option, this
makes it a leading candidate for on-vehicle storage, subject to achieving satisfactory energy
densities.

Underground Storage
Depending on the geology of an area, underground storage of hydrogen gas may be possible.
Underground storage of natural gas is common and underground storage of helium, which
diffuses faster than hydrogen, has been practiced successfully in Texas. For underground
storage of hydrogen, a large cavern or area of porous rock with an impermeable cap rock
above it is needed to contain the gas. A porous layer of rock saturated with water is an
example of a good cap rock layer. Other options include abandoned natural gas wells;
solution mined salt caverns, and manmade caverns. Underground storage is the cheapest
method at all production rates and storage times (due to low capital cost of the cavern):
biggest cost item is electricity cost for compression; relatively insensitive to changes in
production rate and storage time; additional transport cost to consumer may be high, but
underground storage may have applications for seasonal storage or security of supply.

UTILIZATION
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Using hydrogen in Internal Combustion Engines

Conventional combustion engines require modification to burn hydrogen. The proven
commercially available technology to use natural gas in combustion engines is similar to the
one needed to use hydrogen. Hydrogen combustion releases no carbon monoxide,
hydrocarbons, particulate pollution, or carbon dioxide but there is emission of nitrogen oxides
which are very low. Use of hydrogen in an internal combustion engines has several potential
advantages, like increased efficiency (25%-30%), a wide range of ignition limits, and high
flame and diffusion speeds.

Using hydrogen in fuel cells

Hydrogen and oxygen merge in a fuel cell, forming water and releasing electricity. Because
fuel cells require no lubricating oil, and no combustion to generate high temperatures that
lead to the formation of nitrogen oxides, fuel cell-powered electric vehicles offer the cleanest
way of using hydrogen (they are zero-emission vehicles). Fuel cells are two to three times as
energy efficient as combustion engines. An internal combustion engine loses more than 80%
of energy it generates, either as waste heat or friction. When a hydrogen fuel cell is used, the
energy loss is 40 to 60%, so the percent of energy that is delivered as movement is much
greater. However, various technological hurdles must be overcome before fuel cells can 10
compete effectively, in terms of overall performance and cost, with internal combustion
engines in automotive applications. Fuel cell demonstration projects now under way around
the world will likely yield improved solutions to these technical challenges.

Hydrogen Electric Hybrid vehicles

By combining onboard engines or fuel cells that generate power with electrical systems that
store power, electric hybrids may offer greater market potential than vehicles powered solely
by single systems. Demonstrations of hybrid technology, involving hydrogen, indicate that
these vehicles may be lighter, smaller, more versatile, and offer better performance than
vehicles running solely on hydrogen engines, fuel cells, or batteries. There are two primary
types of hydrogen hybrid electric vehicles that are proposed parallel and series. In parallel
hybrid vehicle, both electric motor and the ICE are coupled through the transmission to the
wheels. In series, the ICE is not connected to the wheels and the power to the wheels comes
from the electric motor. The overall efficiencies for these vehicles are estimated at 39% for
ICE series version and 35% for the fuel cell series version. Efficiency of series hybrid ICE
vehicles ranges between 38 and 39%, for parallel hybrid ICE vehicles it is 25%.

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HYTHANE
Hydrogen and methane are the two main gaseous energy carriers and also are widely used in
the chemical industry. Each has independently attracted broad commercial interest and is
highly valued. Hydrogen is regarded as the cleanest fuel. The hydrogen-based economy is
described as a developing trend of future society with zero carbon emissions (Turner, 2004),
as it is clean and sustainable compared with the current fossil fuel-based economy. However,
the development of a hydrogen-based society has been restricted mainly by its cost-intensive
processes and operations. Methane is being commonly used, not only in the chemical
industry but also in transport as compressed natural gas (CNG), which has been regarded as
the clean energy carrier in comparison to gasoline or diesel.
A mixture of hydrogen and methane is called hythane, which was trademarked by Eden
(2010), HCNG or methagen (Ljunggren and Zacchi, 2010). Typically, the suggested hydrogen
content in hythane is 1025% by volume (Fulton et al., 2010). By combining the advantages
of hydrogen and methane, hythane is considered one of the important fuels involved in
achieving the transition of technical models from a fossil fuel-based society to a terminal
Hydrogen based society. Hythane has been used commercially as vehicle fuel in the USA and
India (Das et al., 2000; Eden, 2010) and has also received much attention from many
individual companies such as Volvo, Fiat, Air products and others.

PROPERTIES
When used in an internal combustion engine, even the addition of small amount of hydrogen
to natural gas (5-30% by volume) leads to many advantages, because of some particular
physical and chemical properties .They developed a new HCNG premixed system which was
used to blend desired amount of hydrogen into CNG. According to Daltons partial pressure
law, hydrogen fraction was decided by the partial pressure of these two fuels in HCNG tank.
The influence of gas composition on engine behaviour can be adequately characterized by
Wobbe index. If the Wobbe index remains constant, change in the gas composition will not
lead to a noticeable change in the air-fuel ratio and combustion rate. The overall comparison
of properties of Hydrogen, CNG, 5% HCNG blend is given in tabs. 1 and 2 show the
characteristic values of the HCNG fuels with different hydrogen fractions. Also, these
confirm that the properties of HCNG lie in between those of hydrogen and CNG. There are a
number of unique features associated with HCNG that make it remarkably well suited in
principle to engine applications. Addition of hydrogen increases the H/C ratio of the fuel. A
higher H/C ratio results in less CO2 per unit of energy produced and thereby reduces
greenhouse gas emissions. When excess air ratio is much higher than the stoichiometric
condition, the combustion of natural gas is not as stable as HCNG. The problem encountered
using natural gas is that the engine will experience incomplete combustion (misfire) before
sufficient NOx reductions are achieved. Adding hydrogen to the fuel extends the amount of
charge dilution that can be achieved while still maintaining efficient combustion .Hydrogen
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also has a very low energy density per unit volume and as a result, volumetric heating value
of the HCNG mixture decreases.

PRODUCTION
INDIAN SCENARIO
H-CNG requires blending of hydrogen and natural gas. While CNG is available in the city,
hydrogen has to be produced. The cost of hydrogen production is high. There are various
processes by which hydrogen can be produced. At the Dwarka station, hydrogen for H-CNG
fuel is being produced through electrolysis. Electrolysis is the decomposition of water into
hydrogen and oxygen. The hydrogen produced is blended with CNG to fuel vehicles. In
addition to the electrolyser, the station has a compressor along with a buffer storage facility.
The station which will enable the IOC to continue its R&D for use of hydrogen as a transport
fuel has capacity to fuel nearly fifteen three-wheelers. Initially, CNG vehicles will be targeted
which will run on a mixture of hydrogen fuel with little modification.
Hythane meets from Euro I to Euro V emission standards. Says John Nadeau, business
development manager, Hythane company, Regarding the engine modifications, the
electronics in the engine will have to be re-tuned to take advantage of the lower emissions of
hythane. This is only a software modification, and does not require any change in hardware to
an existing natural gas engine.

INTERNATIONAL SCENARIO
Through the pyrolysis process, developed by Eden with the University of Queensland and
which Eden now owns 100%, and which is being commercialised in Colorado, USA at
Hythane Companys facility, methane (natural gas) is broken down into its constituents of
hydrogen gas and carbon, without the production of carbon dioxide. The carbon is produced
as a solid as either carbon nano fibres or carbon nano-tubes that each are many times
stronger, in certain applications, than steel, whilst each also has a great a capacity to conduct
both electricity and heat.
Low-cost hydrogen production without the production of carbon dioxide as a by-product that
could help facilitate the more rapid spread of both hydrogen as a vehicle fuel and also Edens

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Hythane technology as an ultra-clean, highly efficient premium blend of hydrogen and

natural gas that it is marketing in India and USA.
Additionally, the only other major by-product from Edens pyrolysis process is hydrogen, the
real cost of which will be dependent upon the value of the carbon produced. The quantity of
hydrogen produced will be 33.33% (by weight) of the quantity of carbon produced. This
hydrogen can be either captured and fed into the various hydrogen/Hythane applications
that Eden has been developing around the world, with the intention of accelerating the
commercial rollout of these downstream hydrogen applications based on the prospect of
relatively low cost hydrogen, or else it can be used to help fuel the pyrolysis reactor.
There are various methods of hydrogen production; however, some of them are not especially
relevant in the UK context e.g., geothermal energy. Therefore, this analysis will be restricted
to the production sources, shown in Fig. 1. Renewable electricity, biomass energy crops, such
as short rotation coppice SRC, and miscanthus were identified the major potential renewable
hydrogen energy sources for UK 1,3. The hydrogen production technologies, currently at
research and demonstration stage e.g., photosynthesis, fermentation, photochemi-cal, and
thermochemical processes could be important in future. The cost of different renewable
hydrogen fuel options, including distribution and 5% profit margin, by the year 2020 is
shown in Fig. 2. The cost of supplying renewable hydrogen from wind or biomass resources
are likely to lie above the current pump price of untaxed petrol and diesel, though some costs
are very close to this level. It is also expected that, based on mature technologies, the
production costs of hydrogen from biomass will be lower than hydrogen from wind
electricity. The production costs of hydrogen from biomass may be close to those of hydrogen
produced from the steam reforming of natural gas. However, GHG and other emissions are
likely to be higher for hydrogen produced from biomass than that produced from wind
energy.

STORAGE
Carbons with slitlike pores can serve as effective host materials for storage of hythane fuel, a
bridge between the petrol combustion and hydrogen fuel cells. We have used grand canonical
Monte Carlo simulation for the modeling of the hydrogen and methane mixture storage at 293
K and pressure of methane and hydrogen mixture up to 2 MPa. We have found that these
pores serve as efficient vessels for the storage of hythane fuel near ambient temperatures and
low pressures. We find that, for carbons having optimized slitlike pores of size H 7 (pore
width that can accommodate one adsorbed methane layer), and bulk hydrogen mole fraction
0.9, the volumetric stored energy exceeds the 2010 target of 5.4 MJ dm-3 established by the
U.S. FreedomCAR Partnership. At the same condition, the content of hydrogen in slitlike
carbon pores is 7% by energy. Thus, we have obtained the composition corresponding to
hythane fuel in carbon nanospaces with greatly enhanced volumetric energy in comparison to
the traditional compression method.
Storage vessels with pressure capabilities ranging from 3,600 to 10,000 psi, (25 to 69 MPa)
are available in both cylindrical and spherical configurations. All tanks are manufactured to
ASME pressure vessel standards and are approved for Hythane use.

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UTILISATION
INTERNATIONAL SCENARIO
Results of a test project for the US electricity market show that a 400kW Cummins diesel
generator can run on a mixture of Eden Energys Hythane (a hydrogen-CNG mix) and diesel
fuel to reduce the cost of electricity production from 10.97 to 6.5 Rupees per kilowatt hour
(US$0.26 to $0.15 per kWh). The savings result from a 78% reduction of diesel in the fuel
mix.
In tests performed at Edens Hythane Company test facility in Colorado, US, a dual-fuel kit
was developed to enable the generator to run on a combination of petroleum diesel and either
natural gas or Hythane. The natural gas and diesel mixture also showed a significant cost
decrease (US$0.26 to $0.21 per kWh). Savings were calculated using recent prices for natural
gas and petroleum diesel in India.
Products like compressors, dispensers in bunks, Optiblend, hythane reformers are the devices
which could be used from hytane. Every project based on hythane is unique.

INDIAN SCENARIO
It is advantageous for India to use the existing CNG infrastructure for investigating the
feasibility of using HCNG as an automotive and gain experience in handling the new fuel.
Furthermore, no major engine modifications are required. Government of India has taken
decision to treat up to 20% HCNG blend on par with CNG. Government has also constituted
a committee to frame regulations for HCNG blends above 20% hydrogen. ISO standards for
HCNG and hydrogen kit component testing are being framed in ISO.
A number of research and development programs have been initiated on the use of H2-CNG
blends with the Ministry of New of Renewable Energy (MNRE), Automotive Research
Association of India (ARAI) and automobile manufacturers R&D centre of Indian oil
corporation has taken major steps towards using HCNG as a fuel in automotive engines.
Numerous experiments were conducted in three - wheelers with different HCNG blends and
18% HCNG blend is selected for further optimization. Field trials are in progress to study the
long term effect of HCNG fuel. Vehicle optimization for suitable HCNG blends in LCV and
buses are in progress. Further experimental optimization is in progress at ARAI to convert the
developed CNG injection engine to run on HCNG blends and to achieve Euro-IV norms.
EFFECTS OF HCNG ON DIESEL ENGINE EMISSIONS
Considering emissions, when HCNG fuel is compared with gasoline and diesel it appears to
be a very appealing alternative fuel. When compared with diesel, it nearly eliminates the
particulate matter which is often of great concern. Methane has a relatively stable chemical
structure, therefore making it difficult to reduce emissions by after treatment. For this reason,
the engine fueled with HCNG has a large advantage regarding the hydrocarbon emissions
21 | P a g e

than that of CNG fueling. Probably the largest advantage to running the engine on lean burn
is that it has the ability to greatly reduce the NOx emissions. The reduction in NOx emissions
are due to the increased airflow which causes the engine to run at a lower temperature,
therefore reducing the NOx emissions. Emissions can also be improved with the addition of
hydrogen. Compared to pure natural gas, HCNG reduces the HC emissions, which is in part
due to the increased combustion stability that comes with the addition of hydrogen. However,
due to the increased temperature and combustion duration that accompanies the hydrogen
addition, an increase in NOx emissions is observed [6]. A report which has an experimental
investigation and reinforced with Figure1, Figure 2 an Figure 3; mentioned that, when excess
air ratio changed from 1.2 to 2.0, NOx emission could research to an extremely low level.
When excess air ratio was about 1.8, maximum cylinder pressure and maximum heat release
have got more significance rise due to hydrogen addition compared to excess air ratio was
1.2. It has been suggested that, when adding more than 20% volume into CNG, lean mixture
combustion and ignition timing optimization could significantly decrease NOx emission and
maintain relatively higher thermal efficiency under certain fixed engine conditions[8]. Figure
1 and 2 shows the gas consumption and green house gases emissions for different contents of
hydrogen in HCGN and local emissions of different volumes of hydrogen in HCNG,
respectively.

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