CHAPTER ONE

INTRODUCTION

1.1 Background of study

In the last decade, there has been an increasing focus on waste management. Growing
Population and economic development have led to a continuous increase in waste
generation, which has resulted in development of new technologies for waste
management. In order to minimize the environmental impact from waste, the Waste
Framework Directive (2008/98/EC) has established a waste management hierarchy. This
hierarchy defines the priority order for waste management, and ensures a continuous
effort to carry out waste management with best practice. New laws are frequently being
established in order to improve the framework (Brendeløkken, 2016).
Biogas production is a treatment technology that generates renewable energy, and
recycles organic waste into a digested biomass, which can be used as fertilizer and soil
amendment. Carbon footprints from food waste can be reduced by both the recovery of
green energy, and the use of biofertilizers instead of chemical fertilizers. Biogas is a
renewable energy source, which is considered carbon-neutral since the organic waste
has photosynthesized carbon dioxide. Production of biogas from organic waste has
shown to be more environmentally friendly compared to other waste handling options
such as landfilling, incineration and composting. Biogas production can therefore be
considered a favorable treatment for organic waste (Brendeløkken, 2016). It is evident
that by anaerobic digestion, biogas can be generated from different materials such as
animal dung, sewage, industrial effluents, municipal waste, kitchen waste and any
matter that once lived.(Eze & Agbo, 2016).
Biogas is a fuel gas consisting of a mixture of methane (CH 4), carbon dioxide (CO2) and
traces of other gases, produced through microbial processes under anaerobic conditions
from bio-degradable materials. It’s a renewable high quality fuel that burns without
leaving soot’s or particulate matter (Ossai, 2012). In fact, the contribution of a methane
molecule (CH4) to the greenhouse effect is 21 times greater than that of a carbondioxide

1
molecule. Therefore burning methane, even though producing CO2, reduces its impact
on the environment. Bioreactors can be used to treat municipal waste and generate
electricity. One of the options to utilize biogas is to produce electricity using a gas
engine or gas turbine (Cassada and Safley, 2017, cited in Alfa, 2013).
Commercial biogas production has increased for at least two reasons. Firstly, biogas can
be used as fuel or energy production. Secondly, it contributes to a lower greenhouse gas
(GHG) concentration when it is collected in a closed process. Methane is considered a
strong greenhouse gas, and by capturing it in a biogas production plant it is not emitted
to the atmosphere (Brendeløkken, 2016).

1.2 THE BENEFITS OF BIOGAS TECHNOLOGY

I.2.1 Agriculture
Anaerobic digestion of livestock manure and organic food residuals provides security to
the agricultural/food sector. Several benefits include:
1. Financial diversification and risk mitigation through energy sales.
2. Implementing strong nutrient management practices.
3. Supporting local processing of agricultural production.
4. Reduce commercial fertilizer requirement and costs.
I.2.2 Economic
The green economy benefits of biogas are considerable and include:
1. local job creation in technical, manufacturing and construction/trades.

2. economic development generating billions of dollars of investment in rural

communities.

3. creation of useful by-products from wastes, acting as a significant economic

multiplier.

1.2.3 Energy

1. As a source of renewable energy, biogas has unique characteristics and offers

many energy end uses. Biogas generate reliable, flexible power 24/7

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 2. manage intermittent renewable power supply through means of storage and
flexible power

3. improve/support local infrastructure and power quality

4. upgrade to renewable natural gas (RNG) for injection into the natural gas grid,
delivering ‘green’ renewable energy through existing infrastructure

5. can :

6. be compressed for use as transportation fuel, or direct replacement of fossil-

sourced natural gas in household heating, or industrial, commercial and
institutional processes

1.2.4 Environmental

The environmental benefits of biogas are numerous.

1. control weed seed germination, reducing herbicide use

2. remove odour-causing compounds

3. capture and use of methane, a greenhouse gas 21 times worse than CO2

4. convert high energy waste streams into fuel, diverting them from landfill.

I.3 The impact on the greenhouse effect

Biogas produced on a sustainable basis can significantly reduce greenhouse gas (GHG)
emissions. About half of the worldwide 30 million ton of methane emissions per year
generated from the different animal waste management systems like solid storage,
anaerobic lagoon, liquid/slurry storage, pasture etc. could be avoided through anaerobic
treatment. It is estimated that through anaerobic treatment of animal waste and energy
use of the methane produced, about 13.24 million tons of CH4 emission can be avoided
worldwide per year (Cassada and Safley, 2017, cited in Abafor, 2017).

3
1.4 Statement of the Research Problem
Energy is an important instrument in speeding up economic growth, mitigating poverty
and creating employment opportunities. Energy consumption in Nigeria has been
increasing on a relatively high rate. The inadequate energy service provision has
negatively affected living standards of the population and worsen income and energy
poverty in an economy where the majority of the people live on less than $2 a day (Alfa,
2013). It is highly appropriate to researched on the use of biogas produced from food
and other biodegradable wastes as alternative fuel source for both domestic and
industrial uses (Ossai, 2012).
The abundant hydrocarbon natural resource (crude oil and natural gas) represented
almost 80% of the population source of independent energy supply. Given that over
70% of the country estimated 150 million people are involved in agricultural activities,
and producing diverse varieties of plants and animal wastes. Transforming these wastes
into biogas energy for variety of domestic and industrial purpose represents a long-term
sustainable approach to energy self-sufficiency and economic development (Ossai,
2012).
Poorly managed forests have to shoulder immense burden to meet the increasing
demand for energy caused by both the rising population and the lack of development
alternative energy resources. Wood fuel has been and still is the major source of fuel
daily used by rural mass in Nigeria. This total dependence on wood fuel as the source of
energy for cooking has resulted in deterioration of the quality and quantity of forests and
has posed a serious threat in maintaining ecological balance, thereby manifesting
various problems like deforestation, flood, Global warming, soil erosion , landslides,
climate change etc. Thus, an alternative energy source that would be affordable and
environmentally friendly becomes necessary if the green forest must be preserved.
Furthermore, there exist abundant evidence that climate change is a severe threat to
socio-economic development and can substantially affect a nation’s GDP, as it affects
water, forest, sanitation, food security, industrial development, housing, energy, health
and the very air we breathe. Thus, development of biogas technology is a suitable

4
alternative energy source that would be affordable and environmentally friendly that
would help preserve the green forest thus achieving the 7th mandate of the Millennium
Development Goal on environmental sustainability (Ossai, 2012).

1.5 Justification of Study

The lack of commercial production and utilization of biogas has been of major concern
in Nigeria due to the high potential demand for sustainable renewable energy. Biogas
has become a major source of renewable energy in developed countries like United
States, Germany, Switzerland, United Kingdom etc. where the technology had been
adopted for commercialization. However, in third world nations such as Nigeria, Ghana,
Kenya, etc. major breakthrough is yet to be recorded in terms of commercialization
despite their huge biogas potential, thus their dependence on other sources of fuel is
deplorable. Majority of Nigerians rely on the use of kerosene and fire wood for
cooking. The rampant use of firewood for domestic heating in Nigeria invariably
necessitates the destruction of forests and this is harmful to our environment. The use of
kerosene also contributes to the amount of greenhouse gas emission in our environment
and this can drastically affect the ozone layer, thus aiding global warming (Osunde,
2017).

Kerosene and other oil based sources of fuel are scarce and costly to be easily available
for small marginal and medium farmers residing in rural areas. Furthermore, frequent
alarming hike in prices of imported oil and chemical fertilizer have serious economic
threat to the rural poor. In this context, to reach the self-sufficiency in energy and
fertilizer and to minimize the pressure on traditional biomass fuel, biogas technology
has been the best alternative energy solution, which could be achieved through the
active mobilization and economic utilization of local indigenous resources available in
the country (Alfa, 2013).

Biogas that is methane (CH4), hydrogen sulphide (H2S), carbon (IV) oxide (CO2), water
vapour (H2O) and other constituents depending on the substrates used is produced from
anaerobic digestion (AD) of organic fraction of municipal solid waste (MSW) and other

5
feedstock such as wastewater. The AD system is extensively acceptable as an efficient
process for treatment and utilization of organic waste because it has proven to be
promising method for waste recycling and energy generation (Osunde 2017). Methane is
the only valuable component of biogas and can be used directly for diverse energy
services such as heat, combined heat and power or as fuel for internal combustion
engines. However, other components most importantly carbon dioxide (CO2) and
Hydrogen Sulfate H2S are undesirable and lower the combustion enthalpy and the
combustion rate of biogas. Carbon dioxide acts as diluents on the target gas methane,
causing reduction in heating value and smaller Wobbe index compared with natural gas.
Additionally, carbon dioxide does not participate in combustion process; rather it
absorbs energy from methane combustion, leading to lower flame temperature and
speed flame propagation (White, 2010).
Upgrading raw biogas to >95% methane, positions the gas as an alternative vehicle fuel,
and reduces compression and storage requirements. The value added to biogas by
upgrading and compression is as good as compressed natural gas; however upgraded
biogas has the added advantage of lower emission profile associated with combustion
(Eze & Agbo, 2016).

1.6 Aim and Objectives of Study

General objectives:
To produce biogas from Organic waste and find an inexpensive, environmentally
friendly, and easy to operate system to remove hydrogen sulfide, Carbon IV oxide,
VOCs from the biogas.

Specific Objectives:
The specific objectives of this research were to:
i. To produce biogas from co-digestion of cow dung and food waste.

ii. To remove carbon IV oxide from the Gas using Alkaline method.

iii. Produce activated charcoal which could be used to remove H2S.

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iv. Removal of water and volatile organic compounds (VOCs) using Lime.

1.7 Scope of the Study

The research is confined to biogas production obtained from organic waste within
MAUTECH and purifying the generated raw biogas using Chemical Scrubbing
techniques.
1.8 Limitation of Study
It is beyond the capacity of an individual researcher to undertake a thorough study of
biogas plants. Hence, The study emphasizes on biogas upgrading using Chemical
Scrubbing method only. The study is not to analyse the chemical activity within the
biogas plant or other Biogas upgrading technologies. The side effects, if any, due to the
use of biogas ridumentally have not been taken into consideration.

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 CHAPTER TWO

LITERATURE REVIEW
2.1 Brief Historical Development of Anaerobic Digestion Technologies.
The first allusion to animal manure comes from Humphrey Davy, who reported early in
the nineteenth century the presence of this combustible gas in fermenting farmyard
manure. Davy is known for the invention of the miner’s safety lamp (Maramba, 1978).
However, the industrialization of anaerobic digestion began in 1859 with the first
digestion plant in Bombay. By 1895, biogas was recovered from a sewage treatment
facility and used to fuel street lamps in Exeter, England. Research led by Buswell and
others in the 1930s identified anaerobic bacteria and the conditions that promote
methane production. As the understanding of the anaerobic digestion process and its
benefits improved, more sophisticated equipment and operational techniques emerged.
The result was the use of closed tank, heating and mixing systems to optimize anaerobic
Digestion (Alfa, 2013).
In 1900 a methane (biogas) generating plant from human wastes was constructed in a
leper asylum in Matunga, India. This was the Homeless Lepers’ Asylum, now known as
the Acworth Leprosy Hospital in Wadals, India. In the years around 1940, many
municipal sewage treatment plants in the United States and elsewhere were already
employing anaerobic “digestion” as part of the treatment of municipal waste, and
thereby generating methane which was used to generate electricity for the plant. This
indicated that for pollution control, the anaerobic digestion process is proven effective
with additional benefits in the form of a supply of a useful gas (Maramba, 1978).
China is one of the countries in the world where the use of biogas started at a very early
stage. In 1920, Mr. Luo Guorui built a biogas digester called “Chinese Guorui Natural
Gas store”, which was the first hydraulic digester in China. This marked the beginning
of rural biogas systems development in China. In 1978, 7 million plants were built, but
only 3 million were working. In 2009, about 17 million biogas plants which mainly use
underground masonry plants of size 4 to 10 m3 but less than 50% success was recorded.

8
In India, Mumbai system gas was used in lights in 1897 while the gas was used in an
engine in 1907. In 1951, the KVIC national program developed floating drum design
plants for individual farmers of volume 7 to 35 m 3 with cattle dung as feed stock
(Fulford, 2011). More so, in 1961, PRAD (state sector) involved adapted Chinese dome
design as “Janata” plant (4 to 10 m3). In 1981, AFPRO (NGO sector) involved adapted
Chinese dome design as Deenbhandu plant (2 to 8 m3). As at 2009, 12 million plants
built with less than 60% success rate. In 2005, ARTI won Ashden Award for a floating
drum design made from HDPE water tanks designed for urban families of volume 1 to 2
m3 with food wastes as feed stock. In 2007 Biotech won Ashden Award for similar
system, made from glass reinforced plastics on domestic, institutional and market scales
(Maramba, 1978).
In Nepal, a demonstration plant in a school in 1955. In 1975, the Nepalese Government
program involved development and Consulting Services (Aid program) and Agricultural
Development Bank of Nepal in Biogas research development. In 1976 the Gobar Gas
Company was set up to continue the program as commercial operation. Pilot program of
95 plants which used KVIC design with metal gas drums were set up. USAID funded
R&D project also developed fixed dome design: cast-in-place with cattle dung used as
feed stock for small farmers using 4 to 20 m 3 systems. In 1986, the program was
transferred to local management. With UNDP funding and Dutch (SNV) who provided
subsidy, 189,122 plants built in 2009 with 98% success rate (Maramba, 1978).
In Kaunas – Lithuania, the Rokai pig farm biogas plant operates on a daily 60m3 of
manure from 11,000 pigs. The produced biogas is by co-generation converted into
electricity and heat. About 1,200-3,600 m3 of biogas is produced per day and 2,400 kWh
of electricity per day (Maramba, 1978).
In Indonesia, fixed dome type biogas plants of 18 m 3 capacity with biogas purification
plant have been constructed across communities. Efforts are on to develop the
technology to the level of gas bottling and electricity generation, in Taiwan, more than

9
7,500 units of methane-generating device utilizing pig manure have been constructed,
(Alfa, 2013).

In the United States, there has been considerable interest in the process of anaerobic
digestion. Digesters are aimed at meeting energy production and waste treatment,
especially with regard to animals in farms, allowing the manipulation of a material free
of odors. (Maramba, 1978).
2.1.1 Biogas Projects in Africa
Biogas projects are on the rise throughout the world. They provide a method to produce
methane used for cooking and lighting from the waste of animals and humans. In
countries such as Nepal there is a large push to increase the number of biogas plants in
the country. These projects usually use cow manure to produce the gas, but by making a
small adjustment, a household latrine can be connected to a digester increasing gas
production and providing an easy way to manage the human waste (Ocwieja, 2010).
In Rwanda, Kigali Institute of Science and Technology built sewage systems for
overcrowded prisons (10,000 people) using underground masonry plants with 100 m3
volume, linked to make 1,400 m3. This development saved 50% of wood for cooking
(Fulford, 2011).
In 2006, Biogas Technology West Africa Ltd won the Ashden Award by building
sewage systems for hospitals, schools, colleges, etc. using underground masonry dome
systems of 60 to 160 m3 volume. The water recovered was used to flush the toilets while
gas was collected and used for cooking (Fulford, 2011).
In Nigeria, research into biogas technology and its practical application is on-going,
though, has not really received the deserved attention. The Sokoto Energy Research
Centre, Usman Danfodio University, Sokoto, has carried out a number of pilot projects
on construction of household size digesters. In addition to this the centre has constructed
biogas digester plants of 20 m3 capacity at these locations: National Animal Production
Research Institute (NAPRI-Zaria), Zaria prisons, Kiri-kiri Prisons-Lagos, May flower
School-Ikene, Ogun State, Ojokoro-Lagos and Maiduguri (Alfa, 2013).

10
The number of biogas plants in Africa was small with only a few countries making an
effort to increase access to biogas technology. There is a new African initiative to
increase the number of biogas plants that was launched in 2007. Alfa (2013) stated that
the goal of this initiative is to provide 2 million households by 2020 with biogas
digesters. However, the number of biogas plants currently in Africa is unknown with
most units installed in Tanzania (around 4,000) (Ocwieja, 2010). It has also been
estimated that only 60% of these plants have remained in operation. The reasons for
failure or unsatisfactory performance of these biogas systems can often be found in the
mistakes made during the planning stages. Other reasons for failures include lack of
interest and understanding by the community, construction faults, insufficient
maintenance on the system, misconception of benefits of the system, lack of training
new owners on the system, and budgeting errors (Alfa, 2013).
2.2 Organic Wastes
Organic wastes are material which are of plant and animal origin. They include the
remains of dead plants and animals such as stem, leaves, twigs, roots, feathers, hair,
blood and opals, as well as waste generated by animals e.g. dung. They are said to be
biodegradable i.e. they can be broken down by micro-organisms into smaller molecules
(Feijoo, 1995 cited in Abafor, 2017). The bacteria act on the complex molecules such as
proteins, fats and carbohydrates and break them down to simpler molecules like
ammonia, carbon dioxide and nitrides. They are considered as nuisance on the
environment due to the gradual degradation thus defacing the environment, the odor
they produce and their effect on soil pH, etc. (Yan, 2009 cited in Abafor, 2017) in There
is also the issue of depletion in available oxygen due to increase in biological oxygen
demand (BOD) since as decomposition occurs, oxygen is used up (Okonkwo and
Onokwai, 2016, cited in Abafor, 2017).
2.3 Biogas
Biogas originates from bacteria in the process of biodegradation of organic material
under anaerobic condition. It is composed majorly of CH 4 (methane 50-70%) and CO2
(30-40%). Additionally it consists of traces of H2S, N, CO, O etc. The content of CH 4

11
and CO2 is a function of the matter digested and the process conditions like pH,
temperature, ionic strength or salinity, nutrients and inhibitory substrates. Biogas burns
with an almost odorless blue flame with heat of combustion equivalent of 21.5 MJ/M 3.
Relative density of biogas compared to air of about 0.8. Auto-ignition temperature in the
range of 650 °C – 750 °C compared to petrol 500 °C – 600 °C and 800 °C – 850 °C
Huge volumes of agricultural wastes in the form of livestock manure, corn chaff,
cassava peelings rice husk, ground nut shells, sawdust, bagasse, human excreta and the
resultant gas (BIOGAS) can be converted into potential sources of energy for food
processing activities. This is achievable with the use of biodigester. This is sustainable
in Nigeria as about 70% of the population are involved in agricultural activities and
producing diverse varieties of plant and animal products. Presently biogas is not widely
used in Nigeria’s rural economy due to poor knowledge of its energy potential as well as
limited resource to purchase the required equipment for its conversion. Furthermore,
even if the gas is produced, it may not be in a form that can be easily transported or
converted into electricity, which is necessary to power food processing equipment
(Ossai, 2012).
2.4 Methane
The importance attached to biogas is due entirely to the presence of methane in
the gas. It is the major constituent of the gas making up (45–80 %) of the biogas
produced. It is a member of the alkane or paraffin series of hydrocarbons with a general
formula CnH2n+2. It has a molecular formula of CH4, with a molecular mass of 16 g. It is
also called a marsh gas because it is formed by anaerobic decomposition of vegetable
matter in swampy areas. Coal miners know it as fire damp because mixtures with air are
combustible. It is a major constitute of natural gas and coal gas. Methane is a gas at
room temperature with a boiling point of 16°C and a melting point of 180 OC. It is a
colourless, odourless, and tasteless gas, it has a density of 0.65 g/dm3 at 20 OC, and is
therefore less dense than air. It has an upper flammability limit of 15% by volume of air,
and a lower flammability limit of 50% by volume of air. (Abafor, 2017)

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2.5 Typical Biogas Compositions and Yields
As previously stated, biogas is typically composed of between 40% and 70% methane,
between 30% to 60% carbon dioxide, and from 100 to over 3,000 ppm of hydrogen
sulfide. The actual biogas yield and composition is dependent on the input feedstock, the
retention time in the anaerobic digester, and the type of digestion system used. The
theoretical biogas composition is dependent on the input feedstock, the retention time in
the anaerobic digester, and the type of digestion system used. The theoretical biogas
composition is depending solely on the input substrates, and the overall biogas reaction
is simplified into:
Therefore, using equation (2.1) with a simple molecule such as glucose, the overall
reaction would be:

( a b
) (
n a b
)
n a b
C n H a O b+ n− − H 2O → n− − + C O 2+ + −
4 2 2 8 4 2 8 4 ( ) (2.1)

Therefore, using equation (2.1) with a simple molecule such as glucose, the overall
reaction would be:

C 6H12O 6 3CO 2 + 3CH 4

(2.2)

Equation (2.2) shows that with a very straight forward system using glucose, the
biogas yield would be 50% CH4 and 50% CO2. Table 2.1 reports the theoretical
biogas yields and biogas compositions based on different input substrates, and the
values reported in Ward et al, (2008) are compared to those obtained using
equation (2.1).
Table 2.1 - Biogas Yields and Compositions based on Substrates:

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Substrate Representativ Biogas CH4(%) CH4 CO2 CO2
e molecule yield Ward Eqn (%)War Eqn
Nm3/t total (2.1) d (2.1)
solids
Carbohydrates C6H12O6 790-800 50 50 50 50
Raw Protein C6H14O2N2 700 70-71 71 29-30 29
Raw Fat C55H98O6 1,200-1,250 67-68 70 32-33 31
Lignin - 0 0 0
Source: White, (2010)

One experimental method that has been utilized to determine the overall methane
yield of various feedstock materials is the biochemical methane potential (BMP) assay,
which provides the potential extent and rate of methane production from a specific
feedstock. The BMP assay consists of placing feedstock samples into bottles with
an inoculum and nutrient solution. The bottles are sealed, and the gas production and
composition is analyzed periodically. Many different input feedstock have been studied
using this method, and a select number are shown

Table 2.2 - Theoretical Methane Yield of Various Feedstocks, reproduced:

Methane Yield
Feedstock (m3/kg volatile solids)
Banana peel 0.277
Rotten tomato 0.373
Onion outer peel 0.400
Potato peel 0.267
Cooked meat 0.482
Mixed food waste 0.472
Yard waste (grass) 0.209
Pig manure 0.356
Dairy cattle manure 0.148
Beef cattle manure 0.328
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 Primary sewage sludge 0.590
Source: White, (2010)

2.6 Biomass Energy Resources in Nigeria

Presently biogas production and utilization as an energy source is still at the embryonic
stage in Nigeria. Huge volumes of wastes generated in the form of wood biomass,
forage grasses and shrubs, residues and waste (forestry, agricultural, municipal and
industrial) as well as aquatic biomass are still dumped open landfills. Biomass

potential of Nigeria has been estimated to be 8 x 102 M.J. Fuel wood remains the
predominant energy sources in the household sector with about 70 – 80% depending
on it as their cooking fuel, with an estimated 80 million cubic metre (43.4 x 109 kg) of
fuel wood used annually. Crop residues and wastes estimated at 6.1 million tones are
generated annually, while an estimated 277,500 tonnes of animal waste are generated
daily. Diverting these wastes from the environment through a controlled digestion
process is a viable option towards reducing the greenhouse gas emissions, as well as
provides a more attractive method of waste management and energy production. This
is achievable via the application of biogas technology using bio-digester or biogas
plant.

Table 2.3 Nigeria biomass potential and energy capacity

SOURCE OF POTENTIAL ENERGY

ENERGY RESERVE CAPACITY
m3/year

Fuel wood 80 million 6.0 x 109 MJ

Saw dust 1.8 million tons/year 31,433, 00 MJ

Crop residue 83 million tons/year 5.3 x 1011 MJ

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Animal waste 227,500 tons daily 2.2 x 109 MJ

Source: Ossai, 2012

2.7 Biogas Production

Biomass for anaerobic digestion (AD) is an ancient form of energy extraction method
which continues to support domestic activities. The use of AD technology has been
expanded in recent times following the widespread concerns of researchers for the use
of sustainable renewable energies. Due to several effects of greenhouse gas (GHG) on
climate change as a result of fossil fuel consumption has led to the growing interest in
biogas production to curb the situation. The renewable energy sources have been an
energy alternative method to fulfill human energy demands without causing any adverse
impacts to the environment. Based on the underlined factors, the AD technology fits the
purpose of mitigating the environmental impacts on a global scale. Anaerobic digestion
operates as a renewable energy source and has proven, both technologically and
sustainably attractive to produce efficient energy. The technology has sequence of
operational principles with a lot of mounted components and parameters (Alfred, 2018).
Biogas production is a complex process, where many different microorganisms are
involved. Organic materials are food for organisms, and a mix of different raw
materials will result in a greater diversity of microorganism. Anaerobic digestion is
the controlled degradation of organic waste in the absence of oxygen and in the presence

of anaerobic micro-organisms. With more than 1016 bacteria/ml, there is an

extensive diversity of different bacteria in an anaerobic digester (Brendeløkken,
2016).
The digestion process is carried out using an airtight reactor and other equipment used
for waste pre-treatment and gas retrieval. The process generates a product called
"biogas" that is primarily composed of methane, carbon dioxide, and compost products

16
suitable as soil conditioners on farmlands. There are other fractions of gas elements,
which are ammonia (NH3), hydrogen sulfide (H2S), and hydrogen (H).
Anaerobic digestion is a complex system that involves a variety of biological activities
in the process of gas production. The microorganism is a part of the controlling factors
that influence the optimal performance for biogas realization. The process steps in
anaerobic digestion are sequentially connected to one another. Each phase has different
symbiotic bacteria reaction. Therefore, one end process marks a beginning phase for
another. (Alfred, 2018). Alfa (2013) stated that the process of anaerobic digestion can be
further divided into four stages: pretreatment, digestion, gas upgrading and digestate
treatment. The final stage which is the upgrading of the biogas is necessary because it
may contain impurities that can damage boilers or engines depending on what the gas is
used for. Hydrogen sulfide and water vapor need to be removed for boilers and
combined heat and power units.

17
Removal of carbon dioxide will be required if the gas is to be used as natural gas or
vehicle fuel.

Figure 1: Biochemistry of biogas production (Brendeløkken, 2016).

18
Figure 2: Anaerobic digestion process (Alfred., 2018)

19
2.7.1 Hydrolysis

The first step of the process is called hydrolysis. This part of the process consists
of different reactions where protein, sugars and fat are separated into smaller
organic compounds such as amino acids, short-chain sugars, fatty acids and
glycerine. The microorganisms are not able to use protein, sugar and fat directly,
and the organic molecules are therefore separated into smaller compounds by
enzymes (Brendeløkken, 2016). The enzymes responsible for degrading the organic
materials are amylase. The amylase breaks down carbohydrate into sugars, lipase
catalyses the breakdown of lipid into glycerol whereas long-chain fatty acids, and
protease protein are both broken down into amino acids. This stage plays an
imperative role in ensuring that enough chemical reaction is taken place to prepare
the soluble contents to the next chemical stage. The hydrolysis steps consist of
unique procedures such as enzymes reaction, adsorption, and diffusion.
Substantially, all these chemical enhancements assist for smooth and higher
methane production. However, the seeming challenge associated with hydrolysis is
commonly found in organic waste but has short been answered by reagent chemical
application. These products are then finally converted into methane during the
methanogenesis (Alfred, 2018). An approximate chemical formula for the
mixture of organic waste is C6H10O4. A hydrolysis reaction where organic
waste is broken down into a simple sugar, in this case glucose can be represented
by the following (Alfa, 2013):

C6H10O4 + 2H2O C6H12O6 + 2H2

(2.3)

2.7.2 Acidogenesis

In the second stage, acid producing bacteria break down products from the
hydrolysis into smaller compounds. Amino acid, sugars and fatty acids are

20
broken down to various organic acids, alcohols, ammonia, hydrogen and carbon
dioxide. The breakdown of the same compound might result in different products
when different organisms break it down (Brendeløkken, 2016). The accumulation
of electron sinks, such as lactate, ethanol, propionate, butyrate and higher VFAs,
may promote an increased hydrogen concentration in the medium, which cannot be
consumed directly by the methanogens and should be further degraded by the
obligate hydrogen producing acetogenic bacteria. This process is referred to as
acetogenesis (Marisa et al., 2019).

C 6H12O6 ↔ 2CH3CH2OH + 2CO2

(2. 4)

C6H12O6 + 2H2 ↔ 2CH3CH2COOH + 2H2O (2.5)

2.7.3 Acetogenesis

The intermediary products, which cannot be broken down directly to methane are
converted into acetate, hydrogen and carbon dioxide ((Brendeløkken, 2016).The
critical element in acetogenesis is hydrogen, and this is because without the presence of
H2 concentration no chemical reaction could take place (Marissa et al., 2019). The
temperature in acetogenesis is quite an important parameter since it affects the
thermodynamics of acetogenic reactions. According to Marissa et al, (2019) the
interspecies electron transfer in methanogenic propionate degrading consortia is
influenced by the chemical reactions at the previous steps. The formation of hydrogen
from organic acids becomes stronger at higher temperatures whereas, in methanogens
phase, H2 consumption becomes less energetic. Biological Oxygen Demand (BOD)
and Chemical Oxygen Demand (COD) are reduced through these pathways (Alfa.,
2013).

In general, for reactions producing H2, it is necessary for hydrogen to have a low
partial pressure for the reaction to proceed.

21
 CH3CH2COO- + 3H2O ↔ CH3COO- + H+ + HCO3- + 3H2 (2.6)

Other important reactions in the acetogenic stage involve the conversion of

glucose (equation 2.7), ethanol (equation 2.8) and bicarbonate (equation 2.9) to acetate.

C6H12O6 + 2H2O ↔ 2CH3COOH + 2CO2 + 4H2 (2.7)

CH3CH2OH + 2H2O ↔ CH3COO- + 2H2 + H+ (2.8)

2HCO3- + 4H2 + H+ ↔ CH3COO- + 4H2O

(2.9)

The transition of the substrate from organic material to organic acids in the acid
forming stages causes the pH of the system to drop. This is beneficial for the
acidogenic and acetogenic bacteria that prefer a slightly acidic environment, with a
pH of 4.5 to 5.5, and are less sensitive to changes in the incoming feed stream. On
the other hand, this drop in pH is problematic for the bacteria involved in the next
stage of methanogenesis (Alfa, 2013).

2.7.4 Methanogenesis

The final step in the biogas production process, is called methanogenesis. The gas
produced in this process mainly consists of methane and carbon dioxide, but there
are some small amounts of other gases (Brendeløkken, 2016). Its dependence on
process conditions such as feedstock composition, pH, temperature, and retention
time cannot be underemphasized. Methanogenesis is a sensitive and critical step in
anaerobic digestion during methane production with less substrate content (Al
Seadi et al., 2008). During this process, the already formed acetate, hydrogen, and

22
carbon dioxide from the previous stages are further transformed into CO2 and CH4
through methanogenic archaea. It is estimated that two-thirds of the total produced
methane from acetic acid (alcohol) comes from acidogenesis stage. The remaining
one-third comes from carbon dioxide reduction by hydrogen (Marissa et al, 2019).

2.8 Biogas Utilization

Biogas technology offers several advantages in the form of energy security by reducing
over dependence on fossil fuels, rural economic growth by stimulating the growth rural
industries and providing a productive avenue for using agricultural and forestry wastes.
Furthermore, it offers environmental protection by reducing greenhouse gas emissions
and global warming. There are three basic ways of utilizing biogas generally; production
of heat and steam, electricity generation/co-generation and use as a vehicle fuel (Ossai,
2012).
i. Production of heat and steam
The most straight forward use of biogas is for thermal energy (heat). In areas where
fuels are scarce, small biogas systems can provide the heat energy for basic cooking and
water heating. Gas lighting systems can also use biogas for illumination. Conventional
gas burners are easily adjusted for biogas by simply changing the air-to-gas ratio. The
demand for biogas quality in gas burner is low, only requiring a gas pressure of about 8
to 25 bar and maintaining H2S level below 100 ppm to achieve a dew point of 150 ⁰C
(Ossai., 2012). Cooking is by far the most important use of biogas in the developing
world. Biogas burners or stoves for domestic cooking work satisfactorily under a water
pressure of 75 to 85 mm. The stoves may be single or double varying in capacity from
0.22 to 1.10 m3 gas consumption per hour (Alfa, 2013).
ii. Lighting
Biogas can be used for lighting in non-electrified rural areas. Special types of gauze
mantle lamps consuming 0.07 to 0.14 m3 of gas per hour are used for household lighting
(Ossai, 2012).
iii. Refrigeration

23
Biogas can be used for absorption type refrigerating machines operating on ammonia
and water, and equipped with automatic thermo-siphon. Since biogas is only the
refrigerator's external source of heat, the burner itself has to be modified. Refrigerators
that are run with kerosene flame could be adapted to run on biogas (Alfa, 2013).

iv. Electricity Generation or Combined Heat and Power (CHP)

Combined heat and power systems use both the power producing ability of the fuel and
the inevitable waste heat. Some CHP system produces primarily heat, and electrical
power is secondary (Bottoming cycle). Other CHP system produces primarily electrical
power and the waste heat is used to heat process water (Topping cycle). In either case,
the overall (combined) efficiency of the power and heat produced and used gives a
much higher efficiency than using the fuel (biogas) to produce only power or heat
(Ossai,2012). Generating electricity is a much more efficient use of biogas than using it
for gas light. From energy utilization point of view, it is more economical to use biogas
to generate electricity for lighting. In this process, the gas consumption is about 0.75 m 3.
per kW hour with which 25 40-watt lamps can be lighted for one hour, whereas the
same volume of biogas can serve only seven lamps for one hour (Alfa, 2013).
v. Vehicle fuel
Gasoline vehicles can use biogas as a fuel provided the biogas is upgraded to natural gas
quality in vehicles that have been adjusted to using natural gas. Most vehicles in this
category have been retro-fitted with a gas tank and a gas supply system in addition to
the normal petrol fuel system. However, dedicated vehicles (using only biogas) are more
efficient than those retro-fits (Ossai, 2012) Biogas-fueled Engines. According to Alfa
(2013) Biogas can be used to operate four stroke diesel and spark ignition engines.
Biogas engines are generally suitable for powering vehicles like tractors and light duty
trucks as has been successfully experimented in China. When biogas is used to fuel such
engines, it may be necessary to reduce the hydrogen sulfide content if it is more than 2
percent. Using biogas to fuel vehicles is not so much of an attractive proposition as it
would require carrying huge gas tanks on the vehicle. One of the uses of biogas, which

24
has wide application in Nepal, is to fuel engines to run irrigation pumps. A dual-fuel
engine is available in India, which will run on a mixture of biogas and diesel (80%
biogas and 20 % diesel).

2.9 Limitations of Biogas Utilization

The limitation of biogas utilization is caused by the composition of the biogas. Biogas
is a gaseous fuel consisting of approximately 60% methane, 35% carbon dioxide and
traces of other gases like H2S, water vapor, CO, N, O etc. The useful part of the
energy of biogas is the calorific value of its CH4 content. The other components
do not participate in combustion process but rather absorb energy from the
combustion of CH4. The gaseous nature of biogas and the accompanying impurities
limits its utilization as fuel. Firstly, biogas has a low critical point. The critical point of
a gaseous substance is the thermodynamic state at which the liquid and gas phases of a

substance co-exist in equilibrium. The critical point of methane is – 82.5 OC and

46.7 bar. This means that biogas cannot be liquefied at a temperature above -82.5
OC, which is a major limitation to its utilization.

Second problem limiting biogas utilization as fuel is the presence of three undesirable
components- carbon dioxide, water, and hydrogen sulfide. The problem with the high
amounts of carbon-dioxide is dilution of methane. It lowers the calorific value of
biogas. If the biogas is to be stored, a large amount of space would be wasted on storing
carbon-dioxide. It also causes problems of freezing at valves and metering
points, and in some cases its compressions lead to the creation of carbonic acid
which can deteriorate metering mechanism and storage components. In the case of
water vapor, it tends to condense in a compressed state, therefore, taking up space in
the storage container. Water vapour also reacts with hydrogen Sulphide in biogas and
creates a very corrosive acid. The presence of H2S gas in biogas makes it corrosive to
metal parts: iron and galvanized parts are subject to surface attack. In combustion

25
 H2S combines with water vapour and badly corrodes the exhaust side of burners, gas;
lamps and engine especially in internal combustion engines. These problems
mentioned above are the bottleneck to raw biogas utilization in internal
combustion engines, thus the need for purification to meet the minimum compressed
natural gas fuel specification (Ossai, 2012).

Table 2.4: Critical Point Various Gases

H2 N2 NH3 O2 CH4 CO2 H20

Temperature -239.9 -147.1 -132.4 -118.57 -825 31 100.4

(0C)

Pressure (bar) 13.1 34.2 113.9 50.8 46.7 73.55 90.1

Source: Adapted from Ossai, (2012).

26
Table 2.5: Energy content of various gases

Combustible MJKg-1 MJm-3

Methane 50.0 35.9

Purified Biogas 45.0 32.0
(90%)
Mean Biogas (60%) 30.0 21.5
Butane 45.7 118.5
Propane 46.4 90.9
Methanol 19.9 15.9 x 103
Ethanol 26.9 21.4 x 103
Gasoline 45.0 33.3 x 103
Diesel 42.1 34.5 x 103

Source: Ossai, 2012

2.7 Biogas Upgrading and Purification

Biogas upgrading refers to the removal of carbon dioxide from the gas stream, thereby
drastically increasing the percentage of methane in the biogas stream. Biogas
purification refers to the removal of contaminants, and in the case of biogas derived
from AD the main contaminant is hydrogen sulfide (White, 2010). Biogas can be used
for all appliances designed for natural gas, subject to some further upgrading, as not
all gas appliances require gas with the same quality standards. For instance, when
used for heating in boilers, it is preferable to remove the hydrogen sulfide because it
forms sulfurous acid in the condensate which is highly corrosive. It is also
recommended to condense the water vapor in the raw gas because water vapor can
cause problems in the gas nozzles. Removal of water vapor will also remove

27
hydrogen sulfide (Alfa, 2013). Removing carbon dioxide results in enriched biogas
with higher methane content, which has a higher energy content per unit volume.
Upgraded biogas is often referred to as biomethane (Brendeløkken, 2016).

Removal of carbon dioxide can be done by various techniques, such as

adsorption, absorption, membrane or cryogenic upgrading. This may be
achieved by applying different technologies, as illustrated in Figure 2 (Thrän, et
al., 2014).

Figure 2: Technologies used for upgrading of biogas (Thrän et al., 2014)

28
2.10 Upgrading of Biogas to Natural Gas Quality
For upgradation of biogas to be used as transportation fuel, impurities or
contaminants in it like hydrogen sulfphide, carbon dioxide and moisture must be
reduced as maximum as possible (Shah et al., 2016). The most common technologies
are the water scrubber technology and the PSA-technology.Gas upgrading is normally
performed in two steps where the main step Sulfatreat ® H2S-removal is the process
that removes the CO2 from the gas. Minor contaminants are normally removed before
the CO2 removal and the water dew point can be adjusted before or after the
upgrading (White, 2017).

2.10.1 Water Scrubber Technology

Water absorption method is a physical process used to remove carbon dioxide and
hydrogen sulfide from biogas as both gases are more soluble in water than methane.
This technique is simple, rural and eco-friendly and cost effective. In this process
pressurize water from top and pressurized biogas from bottom is sent across the
scrubber column in a counter- current direction (Ossai, 2012).
Two types of water absorption processes are commonly used for upgrading of gas
from anaerobic digestion, single pass absorption and regenerative absorption. The
major difference between the two processes is that the water in the single pass process
is used only once. Water can also be recycled and in this case a stripper column has to
be integrated in the process (regenerative absorption). Cleaned sewage water has a
sufficient quality for use in the absorption column. After the flash tank, the water is
depressurised by a regulator valve and returned to the sewage water treatment system
(White, 2017).

29
2.10.2 PSA (Pressure Swing Adsorption) Technology
Pressure Swing Adsorption, or PSA, is a method for the separation of carbon dioxide
from methane by adsorption/ desorption of carbon dioxide on zeolites or activated
carbon at different pressure levels. The adsorption material adsorbs hydrogen sulphide
irreversibly and thus is poisoned by hydrogen sulfide. For this reason a hydrogen
sulphide removing step is often included in the PSA process.
The upgrading system consists of four adsorber vessels filled with adsorption
material. During normal operation each adsorber operates in an alternating cycle of
adsorption, regeneration and pressure build-up. During the adsorption phase biogas
enters from the bottom into one of the adsorbers. When passing the adsorber vessel,
carbon dioxide, oxygen and nitrogen are adsorbed on the adsorbent material surface.
The gas leaving the top of the adsorber vessel contains >97% methane (White, 2017).
Before the adsorbent material is completely saturated with the adsorbed feed gas
components, the adsorption phase is stopped and another adsorber vessel that has
been regenerated is switched into adsorption mode to achieve continuous operation.
Regeneration of the saturated adsorbent material is performed by a stepwise
depressurisation of the adsorber vessel to atmospheric pressure and finally to near
vacuum conditions. Initially the pressure is reduced by a pressure balance with an
already regenerated adsorber vessel. This is followed by a second depressurisation
step to almost atmospheric pressure. The gas leaving the vessel during this step
contains significant amounts of methane and is recycled to the gas inlet. Before the
adsorption phase starts again, the adsorber vessel is repressurized stepwise to the final
adsorption pressure. After a pressure balance with an adsorber that has been in
adsorption mode before, the final pressure build-up is achieved with feed gas (White,
2017).
2.10.3 Membrane Separation
Membrane separation is based on purification permeability differential of gases.
There are two techniques under membrane separation method namely: high pressure
gas separation and gas liquid adsorption (Ossai., 2012).

30
2.10.4 Cryogenic Separation
This method is based on the fact that CO2 contaminant can be separated form
methane from the fact that each contaminant liquefies at different temperature and
pressure domain and this process operate at temperature around -100 0C and high
pressure almost 40 bar. The main advantage of cryogenic separation is the high purity
of the upgraded biogas (99% methane) as well as the large quantity that can be
efficiently processed. The main disadvantage of this method is that cryogenic process
require costly equipment mainly compressors, turbine and heat exchanger and so the
overall cost of plant increases (Sharma et al., 2017).
In one variation, raw biogas is compressed in multistage to about 80 bar with cooling.
In order to avoid freezing during cooling process, the compressed gas is dried.
Cooling was achieved by chillers and heat exchangers. The condensed CO2 which is
removed in a is further processed to recover dissolved methane which is then recycled
to the gas inlet, thereby increasing the purity to more than 97% (Eze and Agbo., 2017)
.
2.10.5 Chemical Absorption Techniques:
Research had shown that chemical absorption process can be used in purification of
biogas. Chemical absorption involves formation of reversible chemical bonds
between the solute and the solvent. Chemical solvents generally employ either
aqueous solutions of amines (i.e. mono-, di- or tri-ethanolamine) or aqueous solution
of alkaline salts (i.e. sodium, potassium and calcium hydroxides) which is used to
scrub carbon (IV) oxide. For scrubbing of hydrogen sulphide, iron (II) oxide
suspensions are used in absorption treatments for the removal of hydrogen sufide.
Chemical absorption method completely removes hydrogen sulphide and the process
is commonly used in industrial applications, including natural gas purification
(Osunde, 2017).

31
2.11 Need of Removing H2S from Biogas
In the fermented slurry Hydrogen Sulfide (H2S) is present in dissolved form and due
to its presence composition of biogas may change during biogas production
process. One possible remedy to minimize H2S is, use of the material having less
amount of sulfur, dilute the mixture with water and stir the slurry vigorously.
H2S can corrode the metallic components. The effect of H2S on certain
components made of nonferrous metal for example- pressure reducing valve, flow
meter etc. is detrimental when it is present in biogas. Combustion of biogas
containing H2S produces sulfur dioxide (SO2). When SO2 combines with water
.

vapor, it produces sulfuric acid (H2SO4). This H2SO4 can damage exhaust
7
pipes of
engines, valves etc. by corroding them. If engine is run using biogas containing
H2S, its operating time period to the first routine overhaul may decrease by 10 to
15%. The gaseous SO2 also dissolves in engine oil causing the oil to become acidic
and lose its ability to lubricate, damaging the engine and shortening time
9
between oil changes. SO2 is considered more dangerous than H2S because it is
hazardous for health and environment, as it produces smog and acid rain in
2
cattle
dung based biogas, H2S quantity observed is mostly less than 1% on volume basis
which is not much detrimental. If concentration of H2S is found to be more than 1%,
may result into corrosion of exhaust pipes and engine. Presence of water vapor in
biogas also results into corrosion and reduced heating value of the fuel. Requirements
for H2S removal for biogas vary depending on the biogas utilization technology.
H2S levels below 1000 ppm are necessary for use in boilers to produce heat.
Levels less than 250 ppm are necessary to avoid much more corrosion and

deterioration of lubricants8 which may turn to be costlier.The H2S limit for

electricity production by internal combustion engines is 100 ppm. Compressed
bio-methane (CBM), equivalent to compressed natural gas (CNG), for its use as a

fuel for automobile engine should have quantity of H S below 16 ppm10. If biogas

32
is to be used as natural gas and injected into the grid, the hydrogen sulfide content in
it must be reduced to a level of less than 0.006 gm/m (Shah et al, 2016) .

2.12 Need of Removing CO2 from Biogas:

Carbon dioxide is present in raw biogas with very high concentration. Its presence
may result into reduced energy content per unit mass /volume making it suitable
only for those applications in which low quality energy is needed. Presence of
carbon dioxide in biogas lowers the power output from the engine. CO2
occupies additional space in storage cylinders requiring frequent refilling of fuel
tank of vehicle as well as results into more energy consumption of biogas.
Presence of carbondioxide in biogas can result into problem of freezing at metering
points and valves due to ice formation. Since carbon dioxide does not liquefy and
tends to form dry ice upon compression, storage of biogas in medium pressure tanks
would produce lumps in the compressor. So removal of carbon dioxide from biogas is
essential to increase use of biogas for wider range of applications.
Removal of CO2 from biogas can result into improved heating value of the gas by
about 80% on a volume basis and approximately 225% on a weight basis. Burning of
Methane is faster compared to biogas resulting into improved power and thermal
efficiency of the engine. If CO2 is absent in biogas, extra volume of air can be
inducted in engine cylinder. Volumetric efficiency of the engine may get improved
due to this supply of extra air.
2.13 Need of Removing Moisture from Biogas:
Presence of moisture in biogas to be used as fuel may corrode metallic parts of engine
and fuel supply system. Also this moisture may react with SO 2.This reaction produces
sulfuric acid which may corrode engine pipe lines carrying exhaust gases and
combustion system. The carbon dioxide reacts with the moisture present into biogas
to form a weak acid which will readily attack metals.

33
2.14 Basic of Techniques used For Removal of Impurities from Biogas
In purification of biogas, methane content is to be raised. Primary options are
pressurized water scrubber, chemical scrubbing .Other processes like pressure swing
adsorption, cryogenic separation and membrane separation involve higher installation
cost. In this work for removal of carbon dioxide, use of chemicals (mainly alkanine)
only is considered.

Removal of H2S: The Oxidation Process:

Removal of sulfur from biogas involves oxidizing hydrogen sulfide with atmospheric
oxygen. A small amount of air (3-6% volume of produced biogas) can be introduced
directly into a bio-reactor filled with digested matter. This can be done by pumps that
supply suitable amounts of air. Chemical reaction for this oxidation process can be
stated as shown below:

2 H2 S + O 2 2S + 2H 2O
(2.10)

The Lime Process:

Desulphurization of biogas using solid quick lime or liquid slaked lime is very old
and familiar process and yet has not been used on a large scale. To handle dissolved
or suspended slaked lime in large quantity, specially designed equipment is required.
If biogas contains more CO2, removal of H2S up to satisfactory level becomes more
difficult. The CO2 quickly reacts with quick and slaked lime. During the process
Ca(HCO3) 2 is formed which may react with Ca(SH) 2 .This may produce H2S again. If
quick lime is available, this process can be used for desulphurization.

By Ferrous Materials:
Ferrous materials available in the form of natural soils or certain ores are often used to
remove H2S. They are placed in a closed air tight chamber. The gas to be filtered for

34
purification enters from the bottom side of the chamber, passes through the ferrous
absorbing agent and comes out from top of the vessel which will have no H2S.
This ferrous absorbing material must have iron in the form of oxides or hydroxides.

2Fe(OH) 3 + 3H2S Fe2S3 + 6H2O (2.11)

Fe(OH) 2 + H2S FeS + 2H2O (2.12)

The process gets finisher very quickly and the greater part of iron remains as a sulfide.
Hydrogen sulfide can be removed using catalyst iron oxide in the form of oxidized
steel wool or chips of iron cut from lathe operation of any workshop. When raw
biogas comes into contact with steel wool / chips, iron oxide gets converted to
elemental sulfur. The chemical equation for this process is as shown below:

Fe2O3 + 3H2S Fe2S3 + 3H2O (2.12)

2Fe2S3 + 3O2 2Fe2O3 + 6S (2.13)

Wet Technique:

In wet technique used for sulfur removal from biogas, solution of NaOH can be used.

2NaOH + H2S NaHS + 2H2S (2.14)

Hydrogen sulfide reacts with sodium carbonate present in solution, forming sodium
hydrosulfide as described by reaction:

HS + Na2CO3 NaHS + NaHCO3 (2.15)

35
The hydrated iron oxide introduced in to solution reacts as follows:

Fe2O3 + 3NaHS+ 3NaHCO3 Fe2S3 + 3H2O + 3Na2CO3 + 3H2O (2.16)

Regeneration:

By reacting the sulphidised absorbent with oxygen present in air, the iron can be
brought into the active oxide form for the up gradation of the gas.

2Fe2S3 + 3O2 + 6 H2O 4Fe(OH)3 + 3S2 (2.17)

2FeS+ O2 + 2H2O 2Fe (OH) 2 + S2 (2.18)

This way absorbent used during the process can be regenerated. After a certain time,
the absorbent becomes coated with elementary sulfur and its pores become clogged,
so regeneration can be done only for few times. Likewise aqueous solution of copper
sulfate (100 gm of CuSO4 in 1 litre of water) can be used to remove hydrogen sulfide.

Removal of CO2:
One can use water / caustic scrubbing, solid /liquid absorption and pressure swing
adsorption process to remove carbon dioxide from raw biogas. Cleaning the raw
biogas using water under pressure is easiest and cheapest process of removing carbon
dioxide. To absorb CO2 from biogas, much more water is required for the process.
The corrosive acidic spent water needs special attention. Removal of CO 2 by different
chemicals is as shown below:
Caustic scrubbing is carried out by devising CO 2 in the biogas to react with caustic
solutions forming an irreversible carbonate and subsequently reversible bicarbonate.
For this, solution of NaOH and water in 40: 60 ratios (by weight) can be prepared in a

36
container. When NaOH and water are mixed together enormous amount of heat will
be generated due to exothermic reaction. When heat gets disappeared, raw biogas may
be allowed to pass through the solution. This will reduce carbon dioxide present in
biogas.

2NaOH + CO2 Na2CO3 + H2O (2.19)

In alternate arrangement, solution of limestone and water in 40:60 ratios (by weight)
can be prepared in a container. When limestone and water are mixed together
enormous amount of heat will get generated due to exothermic reaction. When heat
gets disappeared, raw biogas can be allowed to pass through the solution. This will
reduce carbon dioxide present in biogas.

Ca(OH) 2 + CO2 CaCO + H2O. (2.20)

In similar way, solution of potassium hydroxide with water (40:60) can be used to
remove CO2 from Biogas. The chemical reaction of the process is as shown below:

2KOH + CO2 K2CO3 + H2O (2.21)

Based on the easy availability of chemicals, the potassium carbonate technique for
separation of CO2 can be used. This process is based on reversibility of the following
reaction.

K2 CO3 + H2O + CO2 2KHCO3 (2.22)

At low temperature this process goes ahead towards right and takes place in an
absorber where biogas is passed through potassium carbonate solution. The saturated

37
solution can be regenerated by boiling wherein the reverse reaction prevails yielding
back the potassium carbonate as well as CO2 which can be collected. This method is
economically not that attractive. When CO 2 gets dissolved in water it produces
Carbonic Acid. To absorb and hence to reduce CO2 present in biogas, certain bases
are to be used for acid –base neutralization reaction. With the use of chemicals like
Calcium Oxide, Calcium Hydroxide, Ammonium Hydroxide following chemical
reaction may occur:

CaO + H2 CO3 CaCO3 + H2O (2.23)

Ca(OH) 2 + H2CO3 CaCO3 + H2O (2.24)

NH 4OH + H2CO3 NH4CO3 + H2O (2.24)

2NH4OH + H2CO3 (NH4)2CO3 + 2H2O (2.25)

When one has to use such chemicals for commercial production, it becomes essential
to regenerate those chemicals which were spent during the process. When CaO
/Ca(OH) 2 is used for chemical reaction with H 2CO3 , CaCO3 is produced .When this
CaCO3 is heated to 825°C , Calcium Oxide and Carbon Dioxide gets produced on
dissociation. This way Calcium Oxide is prepared from lime stone (Calcium
Carbonate). As this process require much more time and also requires very high
temperature it is not viable commercially.
By heating ammonium carbonates /bicarbonates up to 60 to 80 °C for 5 to 10 minutes,
it is possible to obtain ammonium hydroxide. Without carrying out regeneration, one
can use it as chemical fertilizer.
Removal of Moisture from Raw Biogas
To remove moisture from raw biogas, silica gel can be used as it has very good
moisture absorbing capacity. In market silica gel is available as white / blue silica gel.

38
White silica gel is cheaper compared to blue silica gel due to its inferior properties
compared to that of blue silica gel. Silica gel will absorb moisture from biogas. These
silica gel crystals must be replaced based on purity of biogas obtained in terms of
moisture content in it. For lab scale unit, saw dust also can be used to remove
moisture from biogas.

2.14.1 Activated Carbon for the Removal of Hydrogen Sulfide

An effective method for the removal of hydrogen sulfide from biogas is the use
of activated carbon. Industrially, activated carbon is often used to remove organic
vapors and odorous components from air and other gas streams. Activated carbon
can be manufactured from a multitude of carbonaceous materials. In the 1980s,
approximately 36 % of activated carbons manufactured were made from wood,
followed by 28 % from coal (more than 90 % of which is bituminous and
subbituminous), 14 % from lignite, 10 % from coconut shells, 10 % from peat, and
the remainder from various carbon sources. In general, coal and coke based
activated carbons are used for gas phase adsorption and wood based activated
carbons are used for aqueous phase adsorption. Activated carbon is made in two
stages, the first being the pyrolysis of the carbon at a temperature below 800 °C,
followed by either a chemical or physical activation process. A third step,
impregnation, can also be undertaken to enhance the carbons ability to adsorb
specific compounds. During the pyrolysis stage of carbon production from wood,
the initial components which are volatized from the carbon are oxides of carbon and
acids such as acetic acid (starting at around 170°C). As the temperature reaches
approximately 270 °C, the volatized species are more complex, such as tars and
methanol. Usually the carbon material produced from simple pyrolysis has a low
capacity due to under-developed pores, a by extension, a relatively low surface area.
The chemical activation process involves treating the raw carbonaceous material with

39
a chemical agent, usually phosphoric acid, zinc chloride or sulfuric acid. The
carbon is then pyrolyzed between 400°C and 600°C. The carbon is then washed
to remove the excess activating agent, and again heated, this time to around 800°C.
The activating agent dehydrates the carbon, creating the required porous
structure, while also reducing the formation of tars, methanol and acetic acid. The
physical activation process involves subjecting the pyrolyzed carbon to an
appropriate oxidizing environment, usually at between 800 °C and 1100 °C with
typical gasses being steam, carbon dioxide, air, or any mixture; of the three. Pure
oxygen is rarely used due to uniform heating control issues and the production of
non-uniform carbon. Often steam is added to flue gasses containing carbon
dioxide to facilitate the activation process. Once created, activated carbons are
often classified based on their physical structure. Powdered activated carbons, as
the name suggests, are made up of fine particles, which have large external surface
areas and therefore a very small diffusion distance. It is for this reason that they
are often employed in aqueous adsorption applications. Larger than powdered
carbons are granular activated carbons, and since their particle size is bigger, they
have a relatively smaller external surface area when compared to powdered
carbons. Due to their size, diffusion can be an issue, and as such they are typically
used in gas phase adsorption applications where diffusion distance is a relatively
minor concern. Activated carbon can also be made into spherical particles, which
are used in processes which either require a high mechanical strength of the particle,
or in SO2 and NO2 applications, as it has been reported that the spherical
carbons have high capacity for these specific compounds. A final carbon
classification is impregnated activated carbon, which after the activated carbon has
been created, is treated with an impregnation agent. Specifically for the removal
of H2S from gas streams, carbons are impregnated with iodine, alkali and metal
hydroxides, oxides or carbonates or nitrogen groups using urea or melamine. Many
of these impregnated materials can act as a catalyst for the removal of H2S via
oxidation. Various mechanisms have been proposed by different groups;
40
however one of the most important factors is the alkaline nature of the
impregnated carbons, which leads to the dissociation of H2S to sulfide ions in the
presence of a water film:

H 2 S +H 2 O ↔HS −+ H 3 O (2.26)

Once the H2S has dissociated to HS-, the HS- is more readily oxidized by
surface adsorbed oxygen as described below to form either elemental sulfur or
sulfur dioxide. Further oxidation to sulfuric acid is possible:

HS − O * ↔S OH − (2.27)

HS − 3O * ↔SO2 OH − (2.28)

SO2 O * ↔H 2 O H 2 SO4 (2.29)

The presence of carbonate species can also help to dissociate H2S to HS-, again
either simply with the alkaline nature of the carbonate, as shown in equations
(2.30) and (2.31), or by two other reactions proposed by Chen et al., (2010)
( (2.32) and (2.33):

Na 2 CO3 + H 2 O ↔ Na 2 + HCO3 + OH −
−
(2.30)

H 2 S + OH - ↔ HS − + H 2 O (2.31)

H 2 S + CO3 2− ↔ HS − + HCO3 − (2.32)

41
 H 2 S + HCO3 − ↔ HS − + H 2 CO3 (2.33)

Along with the direct oxidation of HS- to elemental sulfur, various surface
groups can act to catalyze this oxidation. It is proposed (Mills and Steffgen, 1974)

that a pyridine group can chemisorb the HS-, which is then oxidized by
chemisorbed oxygen. It has also been proposed (Chen et al, 2010; Bangreev and

Bandosz, 2002) that sulfur species on the carbon can catalyze HS- oxidation:

HS − + S x ↔ HS x S − (2.34)

1
HS x O2 ↔ HS x S − O * (2.35)
2

HS S − O * + HS − ↔ HS − –
x x + 1 S + OH (2.36)

1
HS x S − O *+ O2 ↔ HS x−1 S − + OH − SO2 (2.37)
2

1
SO 2 + O2 + OH − ↔ SO4 2− + H (2.38)
2

2H 2 S + SO2 ↔ 3S + 2H 2 O (2.39)

where Sx is elemental sulfur or a sulfur polymer and O* is dissociatively

adsorbed oxygen. Chemisorption of H2S on hydroxide salts KOH in (Cui et al,
2009; Bangreev and Bandosz, 2002; Yan et al, 2002) and NaOH is also possible:

NaOH + H 2 S ↔ NaHS + H 2 O (2.40)

42
2NaOH + H 2 S ↔ Na 2 S + H 2 O (2.41)

These chemisorbed species can be further oxidized as proposed, which indicates

again that if there is water and oxygen present, the alkali groups can act as a
catalyst for the oxidation of H2S to elemental sulfur:

1
NaHS + O2 ↔ S +NaOH (2.42)
2

1
Na 2 S + O2 + H 2 O ↔ S + 2NaOH (2.43)
2

The alkali hydroxides can be deactivated either through a reaction with carbon
dioxide (2.44), or can react directly with H2S to form sulfides (2.45):

2NaOH + CO2 ↔ Na 2 CO3 + H 2 O (2.44)

2NaOH + H 2 S + 2O2 ↔ Na 2 SO4 + 2H 2 O (2.45)

Sulfur dioxide, created in (2.28) and (2.37) can also react with alkali carbonates
or alkali hydroxides to form sulfates:

1
Na 2 CO3 + SO2 + O2 ↔ Na 2 SO4 + CO2 (2.46)
2

2NaOH + SO2 ↔ Na 2 SO3 + H 2 O (2.47)

1
Na 2 SO3 + O2 ↔ Na 2 SO4 (2.48)
2

43
 Metal oxides, such as calcium oxide or magnesium oxide, present on the carbon
surface can also catalyze the oxidation of H2S to elemental sulfur (Bangreev and
Bandosz, 2002):

CaO + H 2 O ↔ Ca(OH) 2 (2.49)

Ca(OH) 2 + 2H 2 S ↔ Ca(HS) 2 + 2H 2 O (2.50)

Ca(HS) 2 + O2 ↔ 2S + Ca(OH) 2 (2-51)

Although the oxidation of H2S to elemental sulfur on impregnated activated carbon

can follow a multitude of pathways, there are a couple of commonly required
conditions. First, there must be water present and the carbon must be alkaline in
nature in order to allow for the dissociation of the H2S and second, oxygen must

be present to oxidize the intermediary sulfur species, be they HS-, HSxS-, NaHS,
Na2S or Ca(HS)2 to elemental sulfur.

Table 2.6: Showing Bureau of Indian Standard (BIS) for biogas to be used as
Automobile fuel:

Biomethane (as fuel for Automobile Application As Per

Content Bureau Of Indian Standard )
Methane % 90 (Minimum)
Carbon Dioxide% 4 (Max w/v)
Hydrogen Sulphide 30.3(mg/m3 Max.)
ppm
Oxygen % 0.5 Max (v/v)
Moisture % 16 (mg/m3 Max.)
Source: Shah et al., 2016.

44
 CHAPTER THREE

MATERIALS AND METHODS

3.1 Materials
Materials needed in the course of this work include, bioreactor, weighing balance, pH
meter, plastic syringes, Measuring cylinders, volumetric flask, beakers, titration stand,
round bottom flask, furnace, electric oven, Mercury in glass thermometer (0-100 OC),
Electronic weighing balance, Bunsen Burner, hose pipe, water trough, Faro water
dispenser container.

Other materials and reagents needed for this research and their usage include:

1. Activated Charcoal To be used for

purification of
hydrogen sulfide
2. Calcium Oxide To be for purification
of carbon dioxide and
water vapor
3. Iron sponge Act as base support
for reagents
4. Silica gel To be used for water
vapor purification
5. Iron fillings To be used for
purification of
hydrogen sulfide
6. Transparent Will Serve as housing
cylindrical for the filters
polyethene case
7. Laboratory oven For drying the

45
 activated charcoal
8. Burning sink For burning the
coconut shell
9. Sodium hydroxide For activating the
pellets charcoal chemically.
10. Draining tray For removing
moisture from the
charcoal
11. Sterilized water For washing
12. bioreactor For generating biogas
13. Vehicle tube For storage of raw
and purified biogas.

46
3.1.1 Anaerobic Digesters Design:
The anaerobic digester to be used is 20-liter water dispenser container with
charging point and main digestion chamber; it also had gas discharge/gas measuring
point (www.paksc.org)

3.1.2 Chemical Scrubber Design

47
 ACTIVATED CHARCOAL +
STEEL WOOL

Above is the potential biogas scrubber to be used the upgrading process. Adopted
from Shah et al, 2016.

48
Source: Shah et al., 2016.

49
3.2 METHODS
3.2.1 Sample collection
Freshly produced cow dung need to be collected in a clean polyethene bag and
transferred to the Chemistry/biochemistry Techniques laboratory for processing. Also
kitchen waste would be obtained from Usman Nagogo hostel.

3.2.2 Slurry Preparation and Charging the Digester

Slurry need to be done by mixing cow dung and food waste with water in a ratio of
1:2. The slurry will then be conveyed into the digester. Continuous stirring is needed
to allow for homogenized mixture and for effective anaerobic digestion to take place.
The expected time for production is about three to six weeks depending on the
physical and environmental condition specifically, temperature.

3.2.3 Gas collection and Storage

After the digester must have produced biogas. The gas will be collected from the
digester through a 10mm diameter flexible host connected from the digester to the
bottom of the gas collection system and then stored in a Car tube.
3.2.4 Upgrading of biogas
The biogas produce will in turn be allowed to pass through dry lime, potassium
hydroxide steel wool impregnated with activated charcoal to remove hydrogen sulfide
and carbon dioxide respectively. The purified gas will then be stored in a Car tube
which can then be taken to the Gas Chromatography for methane content analysis.
3.2.5 GC Method
3.2.5.1 Sample preparation and introduction
Samplers will be used to collect the sample at low pressure and under 0.5 % carbon
dioxide content. Sample will then be prepared using draining water of gas law
method. Selflock tubes and sampling ports will be used to prevent any diffusion of the

50
gas sample if available. Alternatively, a gas tight syringe can be used to introduce the
Sample into the inlet system (Creative-proteomics Blog, 2015).

3.2.5.2 GC Analysis
Putting the gas into the instrument will be followed by the use of compression release
valve to regulate the pressure between 0.2-0.39 Mpa regulating the pressure of the
entry of the chromatographic column between 0.15-0.29 Mpa, after that the of
detector should be closed. More importantly, the opening the entry of the detector.
Then the electric source will be connected. In order to protect samples from
contaminant, a special gas will be used. After that, chromatographic peak will be
taken twice for precision (Creative-proteomics Blog, 2015).

51
52
Ward A.J, Hobbs P.J, Holliman P.J, Jones David. L. (2008) Optimisation of
the anaerobic digestion of agricultural resources. Bioresour. Technol.
99 (2008) 7928-7940.

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