USE OF BIOGAS IN FUEL CELLS

ABSTRACT

Energy demand rises worldwide, due to the growth in global population, and the fast
development of transportation. Historically, gasoline and diesel have been used as vehicle
fuels for a long time. But the decline of oil supply and unstable oil price drive people to
find alternative energy for vehicle fuel. Alternative energy solutions may shift energy
consumption to less carbon, less pollution and provide more energy diversity. The waste
which was produced from the agriculture is used to generate BIOGAS which is been used
as a cooking gas. Biogas is a fuel which is produced from the breakdown of organic matter.
It is estimated that the domestic biomass consumption or fuel consumption is as high as
94% with very little use of modern use of energy. The biogas has many applications like
corrosion preventive, cleaning up oil spills, producing hydrogen for fuel cell. Fuel cell is
the advanced technology being the likely prospect in time to come. Fuel cells generate
electricity by an electrochemical reaction in which oxygen and a hydrogen-rich fuel to
combine water. This allows fuel cell to be highly energy efficient and even higher efficiency
can be gained with cogeneration. A typical fuel cell produces voltage from 0.6 – 0.8 V at
full rated load. Fuel cell can be developed for portable electronic devices.

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1. INTRODUCTION

1.1 Biogas

Biogas 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. Biogas
is a renewable energy source. Biogas can be produced by anaerobic digestion with
methanogen or anaerobic organisms, which digest material inside a closed system, or
fermentation of biodegradable materials. This closed system is called an anaerobic digester,
bio digester or a bioreactor. Biogas is primarily methane (CH4) and carbon dioxide (CO2)
and may have small amounts of hydrogen sulphide (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 as natural gas is
compressed to CNG, and used to power motor vehicles. Biogas can be cleaned and
upgraded to natural gas standards, when it becomes bio-methane. Biogas is considered to
be a renewable resource because its production-and use cycle is continuous, and it generates
no net carbon dioxide. As the organic material grows, it is converted and used. It then
regrows in a continually repeating cycle. From a carbon perspective, as much carbon
dioxide is absorbed from the atmosphere in the growth of the primary bio-resource as is
released, when the material is ultimately converted to energy.

1.1.1 Production of Biogas

Biogas is produced by fermentation of biomass (biodegradable waste) in digester by

bacteria. Anaerobic digestion is breakdown of biomass into simpler compounds by bacteria
in the absence of air. It is a biological process taking place in the absence of oxygen and
where wet biodegradable substance is present in high concentration. Anaerobic digestion
happens in three main stages namely

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1) Hydrolysis –breaking of organic complex (proteins, carbohydrates and fats) into
monomers (amino acids, sugars and fatty acids).
2) Acidogenesis –conversion of monomers and products of hydrolysis into organic acids
(butyric acid and propionic acid), carbon dioxide and hydrogen.
3) Acetogenesis –this stage involves production of acetic acid which is used for forming
methane. Bacteria convert products of Acidogenesis (butyric acid, propionic acid, carbon
dioxide and hydrogen) to Acetic acid.
4) Methanogenesis –process of forming methane from products of Acetogenesis (acetic
acid, carbon dioxide and hydrogen).

Biomass is biodegradable material obtained from the environment. Biomass consists of

agricultural wastes (crop residue), animal dung, industrial waste, municipal waste,
household wastes, etc. the wastes have to be biodegradable. Biogas and biomass have been
used as a fuel for cooking in rural India since long time. Due to increase in use of fossil
fuels biogas usage has decreased. The cost of oil and demand for fuel has also increased
rapidly. This problem can be addressed by encouraging production and use of biogas at
different scales.

Fig 1: Process flow Diagram

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1.1.2 Composition of Biogas

Methane (CH4): 50-75%

Carbon dioxide (CO2): 25-50%

Nitrogen (N2): 0-10%

Hydrogen (H2): 0-1%

Hydrogen Sulphide (H2S): 0-3%

Oxygen (O2): 0-0.5%

1.2 Fuel Cells

A fuel cell is a device that generates electricity by a chemical reaction. Every fuel cell has
two electrodes, one positive and one negative, called respectively, the anode and cathode.
The reactions that produce electricity takes place at the electrodes. Every fuel cell also has
an electrolyte, which carries electrically charged particles from one electrode to the other,
and a catalyst, which speeds the reactions at the electrodes. Hydrogen is the basic fuel, but
fuel cells also require oxygen. One great appeal of fuel cells is that they generate electricity
with very little pollution–much of the hydrogen and oxygen used in generating electricity
ultimately combine to form a harmless by-product, namely water. One detail of
terminology: a single fuel cell generates a tiny amount of direct current (DC) electricity. In
practice, many fuel cells are usually assembled into a stack. Cell or stack, the principles are
the same.

Fig 2: Energy Conversion Process Flow diagram in Fuel Cell

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1.2.1 Working of Fuel Cells

The purpose of a fuel cell is to produce an electrical current that can be directed outside the
cell to do work, such as powering an electric motor or illuminating a light bulb or a city.
Because of the way electricity behaves, this current returns to the fuel cell, completing an
electrical circuit. (To learn more about electricity and electric power, visit "Throw The
Switch" on the Smithsonian website Powering a Generation of Change.) The chemical
reactions that produce this current are the key to how a fuel cell works. There are several
kinds of fuel cells, and each operates a bit differently. But in general terms, hydrogen atoms
enter a fuel cell at the anode where a chemical reaction strips them of their electrons. The
hydrogen atoms are now "ionized," and carry a positive electrical charge. The negatively
charged electrons provide the current through wires to do work. If alternating current (AC)
is needed, the DC output of the fuel cell must be routed through a conversion device called
an inverter.

Oxygen enters the fuel cell at the cathode and, in some cell types it combines with electrons
returning from the electrical circuit and hydrogen ions that have travelled through the
electrolyte from the anode. In other cell types the oxygen picks up electrons and then travels
through the electrolyte to the anode, where it combines with hydrogen ions. The electrolyte
plays a key role. It must permit only the appropriate ions to pass between the anode and
cathode. If free electrons or other substances could travel through the electrolyte, they
would disrupt the chemical reaction. www.studymafia.org Whether they combine at anode
or cathode, together hydrogen and oxygen form water, which drains from the cell. As long
as a fuel cell is supplied with hydrogen and oxygen, it will generate electricity. Even better,
since fuel cells create electricity chemically, rather than by combustion, they are not subject
to the thermodynamic laws that limit a conventional power plant (see "Carnot Limit" in the
glossary). Therefore, fuel cells are more efficient in extracting energy from a fuel. Waste
heat from some cells can also be harnessed, boosting system efficiency still further.

1.2.2 Components of Fuel Cells

The fuel cell has three major components namely, anode, cathode, electrolyte, catalyst. An
anode is an electrode through which conventional current flows in to a polarized electrical

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device. A common mnemonic is ACID for "anode current into device”. The direction of
(positive) electric current is opposite to the direction of electron flow: (negatively charged)
electrons flow out the anode to the outside circuit. Cathode polarity with respect to the
anode can be positive or negative; it depends on how the device operates. Although
positively charged cations always move towards the cathode (hence their name) and
negatively charged anions move away from it, cathode polarity depends on the device type,
and can even vary according to the operating mode. These positive ions pas through the
perforated cathode and constitute positive ions.

Fig 3: Schematic Diagram of Fuel Cell

1.2.3 Types of Fuel Cells

 Polymer electrolyte membrane fuel cells (PEMFC).

 Direct methanol fuel cells (DFC).

 Alkaline fuel cells (AFC).

 Phosphoric acid fuel cells (PAFC).

 Molten carbonate fuel cells (MCFC).

 Solid oxide fuel cells (SOFC).

 Reversible fuel cells.

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2. LITERATURE SURVEY

Due to the increasing amount of renewable energy in the power network different energy
conversion and storage technologies are needed to balance the fluctuations in the grid. One
attractive storage medium is fuel derived from biomass. Whereas in commercial biogas
power plants biogas is burned off with low efficient combustion engines, solid oxide fuel
cells (SOFC's) could be a more efficient alternative. Furthermore, most biogases are
unattractive for combustion engines due to their low heating values. With SOFC's, which
can be operated at temperatures between 700°C and 1000°C, it is possible to convert
hydrogen or carbon containing fuels, as for example biogas, directly into electricity and the
side product heat in a highly efficient way

2.1 Economic benefits of biogas powered fuel cells

Fuel cells are a good technical fit in biogas applications. Apart from the technical and
environmental benefits, a strong economic case can be made for biogas-powered fuel cells.

The capital and operating costs for a biogas-powered fuel cell exceed those for one powered
by natural gas due to the additional biogas treatment equipment. However, these increased
costs are offset over the lifecycle of the plant since the raw biogas is essentially free. In a
market of volatile natural gas prices, using biogas as a fuel becomes an attractive
alternative.

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2.2 Working of a Solid Oxide Fuel Cell

Fig 4: Schematic diagram of Solid Oxide Fuel Cell

Schematic of Working Principle of SOFC Hydrogen fuel is fed into the anode of the fuel
cell and oxygen from the air, enters the cell through the cathode. By burning fuel containing
hydrogen on one side of the electrolyte, the concentration of oxygen is greatly reduced. The
electrode on this surface will allow oxygen ions to leave the electrolyte and react with the
fuel which is oxidized, thereby releasing electrons (e ─ ). On the other side of the plate,
which is exposed to air, an oxygen concentration gradient is created across the electrolyte,
which attracts oxygen ions from the air side, or cathode, to the fuel side, or anode. If there
is an electrical connection between the electrodes, electrons flow from anode to cathode
where a continuous supply of oxygen ions (O 2─ ) for the electrolyte is maintained and
oxygen ions from cathode to anode, maintaining overall neutral charge thus generating
useful electrical power from the combustion of the fuel. The only byproduct of this process
is a pure water molecule (H 2 O) and heat, as shown in Fig 4. The reactions taking place at
the two electrodes are given as follows.

Anode Reaction: 2H2 + 2O2-  2H2O + 4e-

Cathode Reaction: O2 + 4e-  2O2-

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Overall Reaction: 2H2 + O2  2H2O

2.3 Advantages of using Biogas for Fuel Cells

 Available in large amount. As biogas is generated from renewable biomass and

livestock waste. Cost of production of these resources is very low or almost free.
 The fuel cost generated from biogas for fuel cells would be low in turn reducing the
cost of power generated using fuel cells.
 Higher electrical efficiency of fuel cells in comparison to internal combustion
engine would result in higher power generation with the same input of fuel.
 Biogas contains CO2, which reduces its calorific value; in turn lowering the amount
of power generated using internal combustion engines. Removal of CO2 for power
generation using fuel cells is not required. In fact, the presence of CO2 is beneficial
for the operation of the fuel cell i.e. SOFC’s
 Carbon dioxide generated from use of biogas in fuel cell will be in part counter
balanced by the biomass used for biogas generation.
 Small scale generation is possible.
 No moving parts in fuel cells result in silent operation.
 Scalable.
 Simpler purification system.
 Hybridization with other technologies such as solar and wind power and heat pumps
have great market potential.
 Remote power generation is possible.
 Few commercially available technologies for using biogas using fuel cells.

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3. USE OF BIOGAS IN FUEL CELLS

3.1 Generation of Hydrogen from Biogas

3.1.1 Steam Reforming (SR)

On industrial scale for the last 10 decades, H2 is mainly produced by processes of steam
reforming of methane (SMR). The H2 produced by SMR is mainly used for utilization in
refineries and fertilizer plants. It is used in hydro treating, (hydrocracking, hydrogenation,
hydrodesulphurization, hydrodemetallization and hydrodenitrogenation) in the refineries
for producing clean fuels like gasoline, diesel and many other products. In fertilizer plants
it is used for the manufacture of ammonia, methanol and many other derived chemicals like
urea, nitric acid and ammonium nitrate. Most industrial steam reformers use Ni catalysts
on a ceramic support, operating in the temperatures ranging from 700-1000 oC in the
pressure range of 15-30 atm.

The main disadvantage of steam reforming (SR) is the endothermic nature of the reaction;
i.e. it consumes a large amount of heat to shift the equilibrium towards the right to yield H2
and CO. Further harsh conditions required during SR result in formation of carbon on
catalyst surface and sintering of the active metals.

Reaction: CH4 + H2O CO + 3H2, ΔH = 206.2 kJ/mol

3.1.2 Partial Oxidation Reforming (POR)

POR is an alternative method to produce H2 with reduced energy costs, since the reaction
is moderately exothermic, contrary to SR which is highly endothermic. In this type of
reaction, methane is partially oxidized to CO and H2 (synthesis gas), at atmospheric
pressure, requiring temperatures between 700 and 900 oC to ensure complete conversion
(H2/CO ratio close to 2) and to reduce soot formation. However, a slight decrease in CO
selectivity cause the methane to react with oxygen to form CO2 (Eq. 8), leading to complete
combustion (strong exothermic reaction), which results in high reaction temperature
increase, which can form hot-spots in the reactor bed and form coke on the catalyst surface.

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Reaction: CH4 + ½ O2 CO + 2H2, ΔH = 36 kJ/mol

3.1.3 Autothermal Reforming (ATR)

A combination of steam reforming and partial oxidation is defined autothermal reforming

(ATR), in which the endothermic and exothermic reactions are coupled. In fact, by this
combination, exothermic heat from the partial oxidation can directly supply the energy
required for the endothermic steam reforming reaction.

In this system the partial oxidation reaction of methane occurs simultaneously with SR,
which makes the process self-sustaining, significantly reducing energy costs. Thus, for SR
methane to be advantageous over others, it is necessary that it takes place under autothermal
conditions, performed adiabatically together with partial oxidation reaction, in order to
produce synthesis gas with a H2/CO ratio between 2.0 and 3.5, using H2O/CH4 ratios
between 1.0 and 2.5, O2/CH4 between 0.25 and 0.55. It should be noted that the selectivity
of products in the oxidation zone is highly dependent on temperature, that is, partial
oxidation reactions are favoured by increased temperature, and total oxidation (Eq. 8)
favoured by decreased temperature.
Reaction: CH4 + x1/2 O2 + yCO2 + (1 -x - y) H2O  (y + 1) CO + (3 - x - y) H2

3.1.4 Dry Reforming (DR)

Along with the above-mentioned processes H2 can be produced by reacting the fuel i.e.
hydrocarbon with CO2 as the source of oxygen, producing H2 and CO. As a result of large
negative enthalpy of CO2, the process is highly endothermic process in comparison to other
process like SR. The process is generally referred as dry reforming (DR) due to absence of
steam reactant, although it can be generated as a by-product or intermediate. Dry reforming
of CH4 (DRM) has been widely investigated to produce H2 and CO.

The highly endothermic nature of the process mandates the use of an external heat source
similar to SMR. The process is slow, requiring long residence time and hence slower

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transient responses. Likewise, the process is prone to carbon deposition by CO
disproportionation (also called the Boudouard reaction) and CH4 decomposition reactions.

Reaction: CH4 + CO2  2CO + 2H2, ΔH = 247 kJ/mol

4. ADVANCEMENTS IN USE OF BIOGAS IN FUEL CELLS

4.1 Internal Reforming

With high grade heat generation in the MCFC and SOFC type it is possible to have internal
reforming of methane gas at the anode. The fuel cell reaction products in the MCFC appear
at 650oC and a nickel catalyst is required to promote reforming at this temperature. In the
SOFC the reaction products appear at a temperature of 1000oC which is sufficient to
perform the reforming process without the requirement for a precious metal catalyst. This
reduces the sensitivity of this type of fuel cell to sulphur.

Fig 5: Process of internal reforming in a solid oxide fuel cell

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The above figure demonstrates the process of internal reforming in a solid oxide fuel cell.
Note the work and heat output equations, where the remaining heat after reforming is
shown.
Internal reforming can be considered to occur in two ways:
 Indirect internal reforming
 Direct internal reforming
In the former, the reforming reaction occurs at the anode, upstream and separate to the fuel
cell reaction. Since the section of the anode where reforming occurs is adjacent to the
section where the fuel cell reaction occurs, the heat of the fuel cell reaction supplies the
reforming reaction by internal heat transfer with minimal losses.
In the latter, the reforming reaction occurs in the anode fuel channels alongside the fuel cell
reaction. In theory, the removal of hydrogen by the fuel cell reaction helps shift the
reforming reaction to the right, but in practice indirect internal reforming predominates as
all the methane is converted to hydrogen close to the inlet of the fuel cell.

A disadvantage of the internal reforming process is the formation of CO, which acts as a
poison to the fuel cell when in the range of 50 ppm. Additionally, the variability of biogas
composition and the poisoning of the catalysts of the fuel cell by carbon deposition (coke)
by CO disproportionation and the presence of sulphur traces, represent the main problems
commonly faced.

4.2 Current Research

4.2.1 Autothermal and Steam Reforming

Hydrogen production via SR of biogas is (SRB) is considered as a feasible alternative to

SMR with similar efficiency. An economics analysis showed that H2 can be produced at
the rate of 0.27US$/kWh with a payback period of 8 years with an ecological efficiency of
94.95%, even without considering the cycle of CO2.

One of the main challenges in developing catalysts for H2 production form biogas is
preventing

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carbon deposition on the active phase in order to increase its useful life. In addition, it
includes
improving the resistance of the catalyst to sulphur poisoning and developing high surface
area
catalyst to promote activity.

Presence of H2S in biogas affects the activity and stability of the catalyst. Sulphur from
H2S reacts with active metal sites limiting the access of the reactants to the active sites and
reducing activity of the catalyst. Further, formation of the stable metal-adsorbate bonds can
lead to non-selective side reactions.

4.2.2 Dry and Oxy-Dry Reforming

Apart from SRB and ATRB reforming, several investigations involving dry reforming and
oxy dry reforming of biogas (DRB and ODRB) have been reported. The major advantage
of this process is utilization of two greenhouse gases. Although the process uses CO2 for
reaction, the endothermic nature of the reaction requires external burning of fuel to provide
heat, which in turn generates CO2 emissions. Reducing the energy requirement of the
process, by driving the endothermic reforming reaction with partial combustion of CH4,
CO, H2 and C, has been researched. Due to the lack of steam-carbon reaction during the
DR process, formation of coke
occurs over catalyst active sites and support, which is responsible for clogging the reactor
and
destroying it. Development of carbon tolerant and thermally stable catalysts has directed
the
research in H2 production via DR. Noble metals like Pt, Rh and Ru are very well suited for
DR
reaction. But the availability and cost of these materials make them expensive and
undesirable for industrial scale or even small-scale applications. Depending on the cost and
availability of the materials, use of Ni based catalyst is best suited. The higher temperature
requirement of the DR reaction and the high carbon content in its reactants makes these
materials prone to deactivation by sintering and carbon deposition respectively.

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5. CONCLUSION

By 2050 renewable energy resources are projected to contribute to 50% of the world energy
demand. In order to keep with the global trend, India will also have to adapt to the changing
circumstances and will have to adopt new and renewable energy resources. Looking at the
forecast, biogas has potential to become an integral part of the renewable energies circle.
India being an agricultural country, a tremendous amount of agricultural and livestock
waste is available. Likewise, the rise in population has resulted in growth in food and
agriculture processing industry, bringing about large amount of waste being produced
which remain unprocessed, and causing environmental concerns as well as spreading
diseases. It is an important and valuable resource for India. It has diverse applications and
has great potential for generating environment friendly and suitable bio-fuels using surplus
biomass, livestock waste along with industrial and domestic waste water. It possesses
potential to address the pressing economic issues like depletion of fossil fuels, management
of renewable energy resource, emission of GHG and replacement of chemical fertilizers
which have arrived over the past few years.

Hydrogen energy in addition to solar, hydro and biomass would be one of the key
renewable energy sources essential for India to maintain its high GDP. The technology is
new, and considerable work in the field is required for the adoption in India. The utilization
of biogas for H2 generation would have a prominent impact on the successful
implementation of H2 energy technology for India. It will help minimize the environmental
effects along with increasing the affordability for wide scale application.

6. BIBLIOGRAPHY

[1] Gaurav Nahar, Dhananjay Mote and Valerie Dupont, “Hydrogen production from
reforming of biogas: review of technological advances and an Indian perspective”,
http://eprints.whiterose.ac.uk/114497/

[2] V. Scholz and J. Ellner, “Use of Biogas in Fuel Cells - Current R&D”, Journal of
Sustainable Energy & Environment Special Issue (2011) 11-15

15
[3] A. Galvagno, V. Chiodo, F. Urbani and F. Freni, “Biogas as hydrogen source for fuel
cell applications”, international journal of hydrogen energy 38 (2013) 3913 – 3920

[4] R. Senthil Kumar, S. Joyal and Isac M.Kuzhali, “Implementation of Biogas Powered
Fuel Cell”, IEEE International Conference on Power, Control, Signals and Instrumentation
Engineering (ICPCSI-2017)

[5] Helton Jose Alves, Cicero Bley Junior, Rafael Rick Niklevicz, Elisandro Pires Frigo,
Michelle Sato Frigo, Carlos Henrique Coimbra-Araujo, “Overview of hydrogen production
technologies from biogas and the applications in fuel cells”, Internal Journal Of Hydrogen
energy 38 (2013) 5215 – 5225

[6] Dicks, Andrew L, “Hydrogen generation from natural gas for the fuel cell systems of
tomorrow”, Journal of Power Sources 61 (1996) 113- 124, Elsevier 1996,

[7] Gardener,F J, “Thermodynamic processes in solid oxide and other fuel cells”, Proc Instn
Mech Engrs Vol211 Part A 1997

[8] Reforming of Biogas Feed for Fuel Cells,

http://www.esru.strath.ac.uk/EandE/Web_sites/9900/bio_fuel_cells/groupproject/library/r
eformers/text.htm

[9] Yilmaz IT, Gumus M, “Investigation of the effect of biogas on combustion and
emissions of TBC diesel engine”, Fuel.2017;188:69-78.

[11] Kohn MP, Lee J, Basinger ML, Castaldi M, “Performance of an Internal Combustion
Engine Operating on Landfill Gas and the Effect of Syngas Addition”, Ind Eng Chem
Res.2011;50:3570-9.

[12] Sharma CK, “Biogas – A Boon for India”, Biofuels. 2010;11:1-3.

16
[13] Lal K, Mani U, Pandey R, Singh N, Singh AK, Patel DK, et al, “Multiple approaches
to
evaluate the toxicity of the biomass fuel cow dung (kanda) smoke”, Ecotoxicol Environ
Safety.2011;74:2126-32.43

[14] Sen A, Mandal TK, Sharma SK, Saxena M, Gupta NC, Gautam R, et al, “Chemical
propertiesof emission from biomass fuels used in the rural sector of the western region of
India”, Atmos Environ.2014;99:411-24.

[15] Rao PV, Baral SS, Dey R, Mutnuri S, “Biogas generation potential by anaerobic
digestion for sustainable energy development in India”, Renew Sustainable Energy
Rev.2010;14:208694.

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