Dawit Thesis 2020

EXPERIMENTAL INVESTIGATION OF UPGRADING BIOGAS PRODUCTION
USING CORN COB DERIVED BIOCHAR
M.Sc. THESIS
BY
DAWIT HAILU, 2023
ADVISOR
DR. DAWIT GUDETA (ASSOCIATE PROFESSOR)
WACHEMO UNIVERSITY
HOSA’INNA, ETHIOPIA
FEBRUARY 2023
EXPERIMENTAL INVESTIGATION OF UPGRADING BIOGAS PRODUCTION

USING CORN COB DERIVED BIOCHAR
BY
DAWIT HAILU
A THESIS SUBMITTED TO THE DEPARTMENT OF MECHANICAL ENGINEERING

INSTITUTE OF ENGINEERING AND TECHNOLOGY
SCHOOL OF GRADUATE STUDIES
WACHEMO UNIVERSITY
HOSA’INNA, ETHIOPIA
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF

MASTER OF SCIENCE IN MECHANICAL ENGINEERING
(THERMAL ENGINEERING)
FEBRUARY 2023
HOSAINA, ETHIOPIA
2
DECLARATION
I hereby declare that this MSc. thesis entitled “Experimental Investigation of Upgrading
Biogas Production Using Corn Cob Derived Biochar” in partial fulfillment of the
requirement for the award of the degree of Master of Science in thermal engineering is my
original work under the supervision of Dr. Dawit Gudeta. The matter embedded in this
thesis has not been submitted for the award of a degree or diploma in any other university.
All relevant resource information used in this paper has been duly acknowledged.
Dawit Hailu Takore

Candidate Signature Date
This is to certify that the above statement made by the candidate is correct to the best of my
knowledge and belief. This thesis has been submitted for examination with my approval.
Dr. Dawit Gudeta

Advisor Signature Date
i
APPROVAL OF BOARD OF EXAMINERS
We, the undersigned, members of the Board of Examiners of the final open defense by
Dawit Hailu Takore have read and evaluated his thesis entitled “Experimental Investigation
of Upgrading Biogas Production Using Corn Cob Derived Biochar” and examined the
candidate. This is, therefore, to certify that the thesis has been accepted in partial
fulfillment of the requirement of the Degree of Master in Thermal Engineering.
This is, therefore, to certify that the thesis has been accepted in partial fulfillment of the
requirement of the Degree of Master in Thermal Engineering.
Dawit Hailu Takore

Name of student Signature Date
Advisor Signature Date
External Examiner Signature Date
Internal Examiner Signature Date
Chair Person Signature Date
Head of Department Signature Date
School Dean Signature Date
Post Graduate Dean Signature Date
ii
ACKNOWLEDGMENTS
First and foremost, I thank the almighty GOD for the strength and the calm through the
onerous times during my work.
I would like to express my deepest gratitude to Dr. Dawit Gudeta, for his invaluable
comments and excellent supervision. I sincerely thank him for taking me under his wing
and providing as much as possible facilities and supports for my research. I thank him for
being so patient and considerate during my study. I have gained and continued to learn
from him as an excellent role model with an intelligent brain, strong character, and
commitment.
My gratitude also goes to Wachemo University for sponsoring me to attend my Graduate
School Program. I am also greatly indebted to thank Wachemo University for financial
support during my study period.
I also extend my appreciation to Chemical Engineering Laboratory assistants at Wachemo
University, Mr., and Mr. (MSc) to support me in one way or the other in realizing this
thesis.
Finally, I would also like to extend my thanks to the entire students of the Thermal
Engineering Department for their support in one way or the other in completing this work.
iii
ABSTRACT
Today, energy is one of the fundamental needs of society and provides services in various
forms. Anaerobic digestion (AD) is a mature technology to both manage waste and
generate biogas for energy services. However, the raw biogas produced is often of low
quality and the process is slow and operates over very long durations. Also, raw biogas is
mainly a combination of carbon dioxide, methane, and unwanted gases that causes a
reduction in energy efficiency from it. The deficiency with using biogas is due to the
presence of CO2 in biogas which is a non-combustible gas. The presence of CO2 lowers the
calorific value and the specific energy density of biogas. Furthermore, it reduces its flame
speed and the extent of flammability in comparison to natural gas. So that alternative
approaches are required to upgrade the biogas to methane-rich biogas by reducing the
CO2 and other contaminants within the digester. Biochar with its beneficial characteristics
for a wide range of applications has become an innovative aspect of this study. The present
study was aimed to investigate the utilization of biochar in AD produced within slow
pyrolysis at a temperature of 450℃.
The specific objectives of this work included the study on the effect of biochar on the
enhanced production ability of biogas from mesophilic anaerobic digestions of cow dung
(CD) through experimentation. To accomplish these objectives, the AD experiments were
conducted in plastic bottles of 1 liters capacity used as a digester at mesophilic
temperature (37℃ ± 1℃) with a working volume of 0.8L each and were fed on a batch
basis. The control and digesters amended with corn cob derived biochar (CC-BC) at four
different concentrations (4, 6, 8, and 10 g/800 mL of media) labeled as ADM 0 (control),
ADM1, ADM1.5, ADM2, and ADM2.5 were investigated. Each experimental condition was
conducted in duplicate, with all digesters placed in a water bath. Five samples, one
without biochar and four with the addition of biochar were prepared with inoculum. To set
the TS value to 8%, water was added to the prepared samples.
The experimental result showed that the cumulative methane production obtained from all
digesters were (392.5 mL) for ADM0, (444 mL) for ADM1, (486 mL) for ADM1.5, (647 mL)
for ADM2, and (540 mL) for ADM2.5. Compared with the ADM0 without any biochar, the
cumulative methane production in the AD with (8, 10, 6 and 4 g/800 mL) CC-BC450 was
increased to 39.33%, 27.31%, 19.23%, and 11.59% respectively.
Keywords: Anaerobic Digestion, Biogas Production, Slow pyrolysis, Biochar, Upgrading
iv
TABLE OF CONTENTS
Contents Page
DECLARATION.....................................................................................................................i
APPROVAL OF BOARD OF EXAMINERS........................................................................ii
ACKNOWLEDGMENTS.....................................................................................................iii
ABSTRACT..........................................................................................................................iv
TABLE OF CONTENTS.......................................................................................................v
LIST OF TABLES..................................................................................................................x
LIST OF FIGURES...............................................................................................................xi
ABBREVIATIONS.............................................................................................................xiv
NOMENCLATURES...........................................................................................................xv
CHAPTER 1: INTRODUCTION...........................................................................................1
1.1 Background of the Study..............................................................................................1
1.2 Problem Statement........................................................................................................3
1.3 The Objective of the Study...........................................................................................4
1.4 Scope of the Study........................................................................................................4
1.5 Limitations of the Study...............................................................................................4
1.6 Significance of the Study..............................................................................................5
1.7 Research Focus.............................................................................................................5
CHAPTER 2: LITERATURE REVIEW................................................................................6
2.1 Introduction...................................................................................................................6
2.2 Biogas...........................................................................................................................6
2.2.1 Biogas composition...............................................................................................6
v
2.2.2 Biogas characteristics.............................................................................................7
2.2.3 Sources and potential feedstock’s for biogas production......................................8
2.3 Anaerobic Digestion.....................................................................................................9
2.3.1 The biochemical process of anaerobic digestion...................................................9
2.3.2 The biochemistry of the anaerobic digestion process..........................................10
2.4 Impact of Process Parameters on Biogas Production.................................................12
2.4.1 Effect of pH value................................................................................................12
2.4.2 Effect of temperature...........................................................................................13
2.4.3 Effect of total Solid..............................................................................................14
2.4.4 Hydraulic retention time......................................................................................14
2.4.5 Seeding................................................................................................................15
2.4.6 Summary of factors affecting the anaerobic digestion process...........................15
2.5 Challenges in Anaerobic Digestion............................................................................15
2.6 A Conventional Approach for Alleviating the Challenges with AD..........................15
2.7 Biogas upgrading.......................................................................................................16
2.7.1 Challenges in small-scale biogas upgrading........................................................16
2.7.2 Upgrading biogas within AD (An approach used in this study)..........................17
2.7.3 Biochar.................................................................................................................17
2.8 Effect of Biochar on the Anaerobic Digestion System...............................................20
2.8.1 Biochar as ammonium adsorbents.......................................................................21
2.8.2 Biochar concentration in AD...............................................................................22
vi
2.9 Summary of literature and gaps..................................................................................25
CHAPTER 3: MATERIALS AND METHODS..................................................................27
3.1 Introduction.................................................................................................................27
3.2 Materials.....................................................................................................................27
3.3 Equipment and measuring instruments.......................................................................29
3.4 Preparation of Raw materials......................................................................................29
3.4.1 Preparation of CC-BC.........................................................................................29
3.4.2 Pyrolysis of corn cob...........................................................................................30
3.4.3 Characterization of CC-BC.................................................................................30
3.4.4 Preparation and characterization of cow dung and inoculum..............................31
3.4.5 Inoculum preparation...........................................................................................32
3.4.6 Media preparation................................................................................................33
3.5 Lab-scale Biogas Production Experiment...................................................................34
3.6 The Modified Gompertz Model..................................................................................34
CHAPTER 4: SIZING DIGESTER......................................................................................35
4.1 Introduction.................................................................................................................35
4.2 Customers Energy Demand for Cooking....................................................................35
4.2.1 Amount of biogas required..................................................................................35
4.2.2 Cow dung and number of cow requirement.........................................................36
4.3 Sizing of Anaerobic Digester......................................................................................37

4.3.1 Volume calculation of digester chamber.............................................................37
vii
4.3.2 Volume calculation of hydraulic chamber...........................................................42
CHAPTER 5: EXPERIMENTAL SETUP AND TEST PROCEDURES............................44
5.1 Introduction.................................................................................................................44
5.2 Details of Experiment.................................................................................................44
5.3 Experimental setup and procedures for corn cob pyrolysis........................................44
5.4 Experimental setup and procedures for CC-BC characterization...............................46
5.4.1 Iodine number test...............................................................................................46
5.4.2 Moisture content and Total solid.........................................................................46
5.4.3 Volatile matter.....................................................................................................48
5.4.4 Ash content..........................................................................................................49
5.5 Experimental setup and procedures for substrate characterization.............................49
5.5.1 Total solid (TS)....................................................................................................50
5.5.2 Volatile matter.....................................................................................................51
5.6 Experimental setup and procedures for Anaerobic digestion.....................................51
5.7 Measuring yield and quality of biogas.......................................................................52
CHAPTER 6: RESULT AND DISCUSSION......................................................................54
6.1 Introduction.................................................................................................................54
6.2 Characteristics of CC-BC at Different Operating conditions....................................54
6.3 Characteristics of the substrates used.........................................................................55
6.4 Lab-scale biogas production.......................................................................................56

6.4.1 Measurement of Biogas production.....................................................................57
viii
6.5 Effect of CC-BC450 on Biogas and Methane Production..........................................58
6.5.1 Identification of biochar concentration for highest biogas production................58
6.5.2 Identification of biochar concentration for highest CH4 production...................59
6.6 Analysis of the cumulative CH4 with the Modified Gompertz Model.......................62
6.7 Evaluation against literature data................................................................................66
CHAPTER 7: CONCLUSION AND RECOMMENDATIONS..........................................67
7.1 Introduction.................................................................................................................67
7.2 Conclusions.................................................................................................................67
7.3 Recommendations.......................................................................................................68
REFERENCES.....................................................................................................................69
APPENDICES......................................................................................................................76
Appendix A: Biochar Production Data Sheet...................................................................76
APPENDIX B: Biochar Sample Characterization, Surface Area Data Sheet..................76
Appendix C: Biochar Sample Characterization, Proximate Data Sheet...........................77
Appendix D: Anaerobic digestion experiment results.....................................................78
Appendix E: Experimental setups, Materials and Equipments.........................................83
ix
LIST OF TABLES
Table 2-1: Composition of biogas and natural gas (Kadam and Panwar, 2017)....................7
Table 2-2: Impact of Carbon dioxide and other trace elements on biogas utilization............7
Table 2-3: Characteristics of biogas from AD.......................................................................8
Table 3-1: List of materials used in the study......................................................................28
Table 3-2: Equipment’s and measuring instruments used in this study...............................29
Table 4-1: Biogas requirement on daily and monthly basis.................................................36
Table 4-2: Feedstock requirement on daily and monthly basis............................................36
Table 4-3: Assumptions for volume and geometrical dimensions (Mukumba et al., 2017)
41 Table 5-1: Experimental conditions used for anaerobic batch experiments....................52
Table 6-1: CC-BC characterizations produced at 450℃ and 60 minutes............................55
Table 6-2: Intial characteristics of the substrate...................................................................56
Table 6-3: Modified Gompertz equation parameter values for CH4 production (per 800 ml
working volume)...................................................................................................................65
Table 6-4: A comparison of the current experimental results with the literature data on the
batch lab-scale methane production with the addition of different types of biochar...........66
x
LIST OF FIGURES
Figure 1.1: Electricity and population distribution (Mondal et al., 2018)..............................1
Figure 2.1: Examples of substrates anaerobically digested to generate biogas......................8
Figure 2.2: The fundamental process of AD (Sunyoto, 2019).............................................10
Figure 2.3: Process schematic for an AD process integrated with pyrolysis........................17
Figure 2.4: Biochar (https://www.google.com/lewisbamboo.com).......................................18
Figure 2.5: The characteristics, functions, and applications of biochar (Sunyoto, 2019)....19
Figure 2.6: Biochar production methods and biochar yields (Igalavithana et al., 2018)......20
Figure 3.1: Study strategies..................................................................................................27
Figure 3.2: Corn cob and Biochar.........................................................................................28
Figure 3.3: Corn cob before and after sizing........................................................................30
Figure 3.4: Inoculum preparation.........................................................................................32
Figure 3.5: (A) Inoculum, biochar, and cow dung slurry, and (B) Preparing mixture.........33
Figure 3.6: (C) Pouring the mixture, and (D) Adding biochar with various concentrations
.............................................................................................................................................33
Figure 4.1: Cross-section of a digester................................................................................38
Figure 4.2: The geometry of the cylindrical-shaped biogas digester....................................38
Figure 4.3: Geometrical dimensions of the hydraulic chamber............................................42
Figure 0.1: General experimental procedures of the present work.......................................44
Figure 5.2: Loading of sample to the crucible and then to furnace for CC-BC production 45
xi
Figure 5.3: Unloading of a sample from furnace and weight of CC-BC.............................45
Figure 5.4: Iodine number determination for CC-BC..........................................................46
Figure 5.5: Adjusting muffle furnace and loading sample for TS of CC-BC450................47
Figure 5.6: Weigh of crucible and sample for TS of CC-BC450.........................................47
Figure 5.7: Weight of crucible and sample after drying for TS of CC-BC450...................48
Figure 5.8: Adjusting furnace and loading of sample for VS of CC-BC450......................48
Figure 5.9: Weight of crucible and sample after ignition for VS of CC-BC450..................49
Figure 5.10: Ash content of CC-BC450...............................................................................49
Figure 5.11: Weight of crucible after cleaning, heating and adjusting oven for TS of CD.
50 Figure 5.12: Weight and Loading of the crucible with the substrate for TS of CD........51
Figure 5.13: The experimental set up of batch anaerobic digestion.....................................52
Figure 5.14: Measurement of biogas using the water displacement method........................53
Figure 6.1: Effect of temperature and time on SSA of CC-BC............................................54
Figure 6.2: Daily biogas production of cow dung................................................................57
Figure 6.3: Cumulative biogas production...........................................................................58
Figure 6.4: The time course of methane production rate for the tested conditions..............59
Figure 6.5: Cumulative methane production with various concentration of biochar...........60
Figure 6.6: Maximum biogas and CH4 vs CC-BC concentrations.......................................61
Figure 6.7: Percentage of methane by volume and its increament per digesters..................61
Figure 6.8: Methane production (mL) without CC-BC to CD in an 800 mL of a 1 L lab-

scale bioreactor in batch fermentation..................................................................................62
xii
Figure 6.9: Methane production (mL) with a dosage of 4g CC-BC to CD in an 800 mL of a
1 L lab-scale bioreactor in batch fermentation.....................................................................62
Figure 6.10. Methane production (mL) with a dosage of 6g CC-BC to CD in an 800 mL of

a 1 L lab-scale bioreactor in batch fermentation...................................................................63
Figure 6.11: Methane production (mL) with a dosage of 8g CC-BC to CD in an 800 mL of

a 1 L lab-scale bioreactor in batch fermentation...................................................................63
Figure 6.12. Methane production (mL) with a dosage of 10g CC-BC to CD in an 800 mL
of a 1 L lab-scale bioreactor in batch fermentation..............................................................64
Figure 6.13: Comparison of methane production (mL) at a different dosage of CC-BC to

CD in an 800 mL of a 1 L lab-scale bioreactor in batch fermentation.................................64
xiii
ABBREVIATIONS
AD Anaerobic digestion
BC Biochar
CO2 carbon dioxide
CC-BC350 Corn cob biochar made at 350 ºC
TS Total Solids
VS Volatile Solids
HRT Hydraulic Retention Time
CD Cow dung
gVS Grams of volatile solids
MC Moisture content
AC Ash content
C/N Carbon to Nitrogen ratio
CH4 Methane
MJ Mega joules
Nm3 Newton cubic meter
VFAs Volatile fatty acids
LHV Lower heating value, KJ/kg
ASTM American society for testing and materials
IBI International biochar initiative
HTC Hydrothermal carbonization
GAC Granulated activated carbon
PAC Powdered activated carbon
OLR Organic loading rate
COD Chemical oxygen demand
ADM Mesophilic anaerobic digestion
APHA American public health association
AS Activated sludge
NA Not analyzed
WDM Water displacement method
xiv
NOMENCLATURES
CTswt Concentration of TS in fresh discharge by weight [kg TS/kg
discharge]
D Digester diameter [m]
DH Hydraulic chamber diameter [m]
Dpd Discharge per day [kg/day]
f1 Upper dome height [m]
f2 Sludge layer thickness [m]
H Distance between ground surface level and dome top [m]
h3 Hydraulic chamber height [m]
H Height of fermentation chamber [m]
H1 Height of gas layer inside V3 [m]
N Number of biomass units or Cows
R1 Upper dome radius [m]
R2 Bottom radius [m]
S1 Area of upper dome [m2]
S2 Area of sludge layer dome [m2]
Td Total discharge [kg/day]
Tir Total influent required [kg/day]
Tsfc Ts of favorable concentration [kg TS/kg influent]
Tsfd Ts of fresh discharge [kg/day]
V1 Upper dome volume [m3]
V2 Sludge layer volume [m3]
V3 Fermentation chamber volume [m3]
Vc Volume of gas collecting chamber [m3]
Vf Volume of fermentation chamber [m3]
Vgs Volume of gas storage chamber [m3]
VH Volume of hydraulic chamber [m3]
V Total volume of bio-digester or bio-reactor [m3]
Vs Volume of sludge layer [m3]
Vgs volumetric gas storage production rate [m3/day]
Vgs,TS Volumetric gas storage production rate for TS [m3/day]
Wa Daily water addition [kg/day]
xv
Wvd Working volume of the digester [m3]
Ydg Volumetric gas yield by TS mass [m3/kg Tsfd]
Ydg,total Total Volumetric gas yield [m3/kg Tsfd]
xvi
CHAPTER 1: INTRODUCTION
1.1 Background of the Study

Today, energy is one of the fundamental needs of society and provides services in various
forms like power for transport, lighting, and heating for cooking, water pumping, and some
other services (Pedrasa et al., 2010). Due to an increasing number of populations,
industrialization, the availability of contemporary agricultural machinery, and way of life,
the energy demand is increasing at an alarming rate. To satisfy the energy need, massive
quantities of fossil fuels are utilized with an antagonistic impact on the environment
(Mezmur and Bogale, 2019).
The Ethiopian energy sector continues to predominantly depend on conventional biomass
energy and faces the difficulties of limited access to modern energy sources to fulfill the
growing demand. Having access to modern energy sources is essential for economic
development and livelihood improvement (Reddy, 2015). Access to modern energy
supports both income generation activities and the national development agenda through
improving education, reducing indoor air pollution, and ensuring environmental
sustainability. While Ethiopia has seen dramatic economic growth in recent years,
sustaining and continuing this growth into the future will require expansion of energy
supply.
In Ethiopia, the current power generation for the electric grid depends almost entirely on
hydropower. There are stark differences in the rate of electricity access in urban and rural
areas.
Electricity access in Population distribution in

Ethiopia Ethiopia
8% 5% 17 %
87%
83 %
Rural Urban No access Rural Urban
Figure 1.1: Electricity and population distribution (Mondal et al., 2018)

In rural areas of Ethiopia, the primary source of energy for cooking applications is biomass,
which accounts for 91% of the energy consumed. About 7% of total primary energy is
supplied by petroleum and electricity account for merely 2% of total energy use. The
consumption of biomass accounts for over 98% of the total supply in the residential sector.
Electricity is mostly used by urban households, small industries and due to the dependence
on biomass for cooking, the increase in CO2 emissions from 5.1 million tons in 2005 to 6.5
million tons have seen in 2010 (Mondal et al., 2018).
Considering all the continents 590–880 million tons of methane is released into the
atmosphere through microbial activity each year. About 90% of the emitted methane
derives from the decomposition of biomass and the remainder is of fossil origin (e.g.
petrochemical processes) (E. Aravindaraj et al., 2017). The reactivity of methane was
investigated and reported that, it has more than 20 times the global warming potential of
carbon dioxide and that the concentration of it in the atmosphere is increasing by 1-2% per
year(Kumar et al., 2004). In Ethiopia, where more than 83% of population is living in a
rural area and most of them are farmers. Thus, by using animal waste, and agricultural
waste, it is possible to generate energy for rural communities.
Single family biogas technology has enjoyed a period of rapid development, and the
technology is continuing to mature, with more varieties. Biogas is produced when organic
material is decomposed under anaerobic conditions in a digester. Biogas, a high-quality
fuel, improves rural life by providing both heat and light. Single-family biogas technology
provides rural inhabitants with a convenient and clean form of energy, along with useful
by- products such as organic fertilizers. The effluent resulting from aging contain high
extents of nitrogen, phosphate, potassium. These fertilizers can stimulate the growth of
crops and promote root development, increase the brawniness of the stems, increase the
size and yield of the plants, increase the size of individual grains, and accelerate the
maturity of crops.
Environmental sanitation and health standards are increased as biogas digestion destroys
harmful pathogens such as bacteria and parasites. Feces that have not gone through biogas
digestion contain many parasite eggs and bacteria which are the main vectors for diseases
in daily life. After digestion, the number of parasite eggs is reduced by at least 95% and the
bacteria remaining in the feces will die quickly (Sun Jinshi, 2007).
Typically, impurities such as CO2, H2S and NH3 are produced during the AD. The
impurities lower the caloric content of biogas and cause utility corrosion. Therefore,
attempts to remove impurities from raw biogas are also needed. Biogas production shows
2
an increasing trend in recent years. So, biogas upgrading had been researched extensively
in recent years (Mezmur
3
and Bogale, 2019). However, current costs for conventional upgrading technologies are too
high to justify investments at the low biogas flows obtained from small scale biogas
production (Bauer et al., 2013). To reduce this cost, simple and energy-efficient CO 2 and
other contaminants reduction systems are required. One promising method in the reduction
of biogas impurities is adsorption using biochar.
Biochar is a charcoal product produced from plant-derived biomass that is subjected to
thermal treatment in the partial or total absence of oxygen. The thermal treatment changes
the microstructure of the particles to form an aromatic-aliphatic region and a crystalline
region, which are made up of different pore sizes based on their internal diameter. These
pores are responsible for the adsorptive behavior of biochar for compounds such as
phosphate, nitrate, nitrite, ammonium, metals, pesticides, and carbon dioxide. The sorption
mechanisms of a biochar material are similar to other adsorbents (activated carbon, zeolite,
and bentonite (Zhang et al., 2012). Different types of biochar have been used in the study
of the reduction of biogas impurities such as H2S and ammonia. However, up to now, there
are limited studies on the reduction of biogas impurities such as carbon dioxide. In this
study through various considerations, increasing methane yield from anaerobic digestion of
cow dung with corn cob derived biochar was proposed and has been tested.
1.2 Problem Statement

According to the present scenario of Ethiopia, most regions of the country particularly rural
areas don’t have access to electricity and there is no balance between demand and supply
for those regions having access to electricity. Due to this reason, most people use
conventional fuel such as firewood leading to depletion of conventional fuel, deforestation,
indoor air pollution, and greenhouse gas emission. Also, 90% of methane is emitted into
the atmosphere from the decomposition of biomass and contributes to global warming due
to difficulties associated with the burning of organic wastes (E. Aravindaraj et al., 2017).
Biochemical conversion of biowastes to biogas through AD has received increasing
attention in recent years.
Raw biogas is mainly a combination of carbon dioxide, methane, and unwanted gases that
causes a reduction in energy efficiency from it. The deficiency with using biogas is due to
the presence of CO2 in biogas which is a non-combustible gas. The presence of CO2 lowers
the calorific value and the specific energy density of biogas. Furthermore, it reduces its
flame speed and the extent of flammability in comparison to natural gas. So that alternative
approaches are required to upgrade the biogas to methane-rich biogas by reducing the CO2
4
and other contaminants within the digester. In this study addition of locally available biochar is
used to upgrade biogas production and increase its heating value by reducing pollutants like
carbon dioxide, hydrogen sulfide and to avoid inhibitory stages during the processes, enhancing
the quality of generated biogas to achieve higher methane concentration with fewer
contaminants, and increasing system stability to potentially enable processing of substrate.
1.3 The Objective of the Study

The general objective of this study is to upgrade biogas production (increasing biogas
quality) from the digestion of cow dung using biochar through experimentation for
household cooking applications in rural areas.
Specific objectives
The specific objectives are to:
 Estimating biogas fuel required for household consumption having ten members.
 Sizing the digester depending on the amount of biogas.
 Development of laboratory-scale biogas production unit on batch basis.
 Characterization of the substrate and establish mixture for feed.
 Produce biogas using a laboratory-scale biogas production unit and measuring
methane production.
 Investigate the effect of biochar in gas yield and in reducing pollutant.
1.4 Scope of the Study

The scope of this study was aimed at the production of biochar, utilization of biochar in
AD and to investigate the effects of biochar addition dosage on the gas yield and gas
production rate as well as gas quality in mesophilic anaerobic digestion of cow dung within
a lab-scale batch operation.
1.5 Limitations of the Study

The limitations of this study are the biochar used in the study was only limited to one type
of biochar, which was the corn cob derived biochar (prepared at 450C) and one type of
feedstock (cow dung). Considering the different characteristics, which may be possessed
by different types of biochar and feedstock, their different effects and mechanisms, may be
found in the AD.
5
1.6 Significance of the Study
This research significantly reduces the costs associated with biogas upgrading could
improve the overall economics of energy production from waste relative to other
commercial upgrading methods, reducing the barrier to entry and opening it up to smaller-
scale waste treatment facilities. AD usually creates biogas that is mainly a combination of
carbon dioxide and methane, and extra steps are required to upgrade the biogas to
renewable natural gas by removing the CO2 and other contaminants. However, by adding
biochar directly to the anaerobic digester sequesters the CO2 and may create a biogas
stream that is more than 90% methane and less hydrogen sulfide, thus reducing the need
for upgrading steps. The biochar is used to improve the operating conditions for anaerobic
digestion, and it is nutrient-rich, so the effluent left after the process is completed can serve
as a high-quality fertilizer. This approach would also offer improved process economics,
reduced barriers to entry, and reduced greenhouse gas emissions over the production of
fertilizers. More importantly, the reduction of upgrading steps alone could make many
smaller biogas projects profitable.
1.7 Research Focus

The core of this research problem under study can be best pronounced by testifying the
following research questions:-
 Why most farmers in Ethiopia did not produce and use biogas?
 What are the reasons for biogas production?
 Most of the time biogas users use biogas for cooking. Why only for short period?
 Does the addition of biochar improve methane yield?
 Which dosage of biochar with the substrate produces the highest methane?
 What are the major factors affecting methane yield?
 Does variation in the amount of biochar added to the digestion process affect biogas
production? These research questions have been addressed in the following
chapters.
6
CHAPTER 2: LITERATURE REVIEW
2.1 Introduction
This chapter reviews the fundamentals and state of knowledge relating to AD. Existing
studies of biogas technology, factors affecting biogas production and biochar utilization in
AD are reviewed and in the end, the gaps of the studies are depicted.
2.2 Biogas
Biogas originates from biogenic material and is a sort of biofuels, regularly alluded to as a
gas delivered by bacteria fermentation of organic material under anaerobic conditions
(without oxygen). As seen by Buren (1983), biogas is a combustible gas delivered by
microorganisms when organic materials are fermented in a certain range of temperatures,
moisture contents, and acidities, under airtight condition. Biogas is viewed as an
inexhaustible source of energy since the raw materials are continually recovered (Maria
Berglund, 2016).
2.2.1 Biogas composition
The principal constituents of raw biogas delivered by the anaerobic digestion are methane
and carbon dioxide with various quantities of contaminants, for example, ammonia (NH 3),
water vapor, hydrogen sulfide, carbon monoxide, and hydrocarbons. These contaminant's
presence and quantities depend largely on the biogas source, which could be anaerobic
digestion of numerous substrates and landfill decompositions. The composition of gas
fluctuates with the raw material used. Methane has a large share within the biogas
composition with (40–75)%, followed by CO2 with (25–55)% (Kadam and Panwar, 2017).
The main components of biogas are methane (50–75%) and carbon dioxide (25–50%)
(Maghanaki et al., 2013). Biogas contains methane (60–70%), carbon dioxide (30–40%),
and trace gases such as hydrogen sulfide (H 2S). The CH4 in biogas can be exploited as a
renewable energy source for the production of heat and electricity, or use as a vehicle fuel
(Awe et al., 2017).
7
Table 2-1: Composition of biogas and natural gas (Kadam and Panwar, 2017)
Composition, (%) Biogas Natural Gas
Methane 40–75 87–97

Carbon dioxide 25–55 0.1–1.0
Hydrogen sulfide (ppm) 50–5000 NA
Ammonia 0–1 NA
Water 0–10 NA
Nitrogen 0–5 0.2–5.5
Oxygen 0–2 0.01–0.1
Hydrogen 0–1 0.02
The removal of the contaminants especially H 2S and CO2 will significantly improve the
quality of the biogas for its further uses.
Table 2-2: Impact of Carbon dioxide and other trace elements on biogas utilization
Trace elements Biogas Impact on biogas utilization

Carbon dioxide, (%) 30–40 Decreasing calorific value, anti-knock
properties of engines, and corrosion.
Nitrogen, (%) 0–5 Decreasing calorific value, anti-knock
properties of engines, and corrosion.
Hydrogen sulfide, (ppm) 0–4000 Corrosion, emission, and health hazards.
Ammonia, (ppm) 100 Emission, anti-knock properties of
engines, and corrosion when dissolved.
2.2.2 Biogas characteristics

Biogas is about 20% lighter than air and has an ignition temperature in the range of 500℃
to 750℃. It is an odorless and colorless gas that burns with a clear blue flame like that of
LPG gas. The estimated calorific value of 1 m3 is about 22 MJ if burns with 60% efficiency
(Raja and Wazir, 2017). The lower heating value of biogas ranges from 15 to 30 MJ/Nm 3
and is lower than that of natural gas, which is around 36 MJ/Nm 3 (Awe et al., 2017). Each
cubic-meter of biogas has the same thermal output as 0.6–0.7 kg of diesel or the heating
capacity of 2.3 kg of coal which can heat 65 liters of water from 20℃ to boiling.
8
Alternatively, 1 m3 of biogas can light a biogas lamp (equivalent to a 60 W light bulb) for 6
to 7 hours or keep an internal combustion engine of 1 horsepower running for 2 hours or
produce 1.25 kWh of electricity (Sun Jinshi, 2007).
Table 2-3: Characteristics of biogas from AD

Parameters Unit Biogas from AD
Lower heating value MJ/Nm3 23 22 -
KWh/Nm3 6.5 - 5.0–7.5
MJ/kg 20 - -
Density Kg/Nm3 1.1 - 1.2
Ignition point ℃ 500–750 700
References (Awe et al., (Raja and Demirbas, and
2017) Wazir, 2017) Balat, M. (2009)
2.2.3 Sources and potential feedstock’s for biogas production

Biogas can be produced from any organic waste with suitable VS content through AD
under certain process parameters. All sorts of biomass can be utilized as substrates for
biogas generation as long as they contain carbohydrates, proteins, fats, cellulose, and
hemicelluloses as primary components.
Agricultural crops and residues

Sewage Animal manure and waste
Foresetry crops Biogas Marine algae

and residues
Weeds
MSW Biodegradable industrial waste
Figure 2.1: Examples of substrates anaerobically digested to generate biogas
The composition of biogas and the methane yield relies upon the feedstock type, the
digestion system, and the retention time. Only strong lignified organic substances, e.g.,
wood, are not suitable due to the slowly anaerobic degradation. The digestion of raw
material with high-fat content can provide a higher gas yield and a higher proportion of
9
methane than the digestion of raw material rich in carbohydrates (Maria Berglund, 2016).
The most widely recognized farming biomass that is utilized as substrate (feedstock) in
biogas digesters is CD, because of its natural content of anaerobic bacteria, high energy
content, high water content, and high availability (Deublein and A. Steinhauser, 2011).
2.3 Anaerobic Digestion

Anaerobic digestion is a simple technology broadly utilized for handling biodegradable,
organic waste for biogas production. AD has been considered as waste-to-energy
technology and is widely used in the treatment of different organic wastes, for example,
organic fraction of municipal solid waste, sewage sludge, food waste, animal manure, etc.
(Abubakar and Ismail, 2012).
2.3.1 The biochemical process of anaerobic digestion

The biogas production process involves multiple related biochemical processes with
microorganisms in the absence of air that work together to achieve the degradation of
organic matter into methane and carbon dioxide. The four anaerobic processes of
hydrolysis, acidogenesis, acetogenesis, and methanogenesis run simultaneously in the
biogas digester. The first stage is hydrolysis, in which the complicated components and
molecules are converted into simpler molecules and components. In this state, the
complicated carbohydrates, lipids, and proteins are transformed into simpler sugar
molecules and/or amino acids, and further fatty acids. Small amounts of biogas are formed
and gas generation increases until it reaches its peak during the fourth step of
methanogenesis. Figure 2.2 shows a simplified diagram of the biochemical process of AD
(Sunyoto, 2019).
10
Process Reaction Microbes
Protein Carbohydrate Lipid

Pseudomonas sp,
Hydrolysis
Amino acids Sugars Free long fatty

acids Lactobacillus sp;
Acidogenesis Propionibacteriu
m sp
Ammonia VFA
Acetobacter sp;
Acetogenesi Syntrobacter wolinii
Acetic acid Hydrogen, CO2 a

Methanomicrobiales,
(a) (b
b
Methanobacteriales
Methanogenesis
CH4, CO2
Figure 2.2: The fundamental process of AD (Sunyoto, 2019)
In the next stage, i.e. the acidogenesis stage, the resulting materials are transformed into
volatile fatty acids, hydrogen, and carbon dioxide. The volatile fatty acids continue to be
converted to hydrogen, carbon dioxide, and acetic acids in the acetogenesis stage, and
finally, the methanogenesis stage decomposes the hydrogen, carbon dioxide, and acetic
acid, and produces methane (Abatzoglou and Boivin, 2009; Demirbas and Balat, 2009).
2.3.2 The biochemistry of the anaerobic digestion process

The formation of methane, ammonia, hydrogen sulfide, and carbon dioxide follows
general equation when biomass is chemically broken down to produce biogas (Deublein
and Steinhauser, 2011). This equation depicted that, water content is one of very important
parameter affecting AD of solid wastes. Because water make possible the movement and
growth of bacteria facilitating the dissolution and transport of nutrient; and water reduces
the limitation of mass transfer of non homogenous or particulate substrate.
11
Cc HhOo Nn Ss  y.H2O  CH 4  n. NH3  s.H2 S  (c
x).CO2
1 (2.1)
. Where, x  (4c  h  2o  3n 
2s) 8
1
y  (4c  h  2o  3n 
2s) 4
The building blocks from which biogas is produced includes carbohydrates, fats, and
proteins as given by the following equation:
Carbohydrates: C6 H12O6  3CO2  (2.2)
3CH4
Fats:
C12 H24O6  3H2O  4.5CO2  (2.3)
7.5CH4
Proteins: 3H25O7 N3S  6H2O  6CO2  6.5CH4  3NH3  H2

S (2.4)
Some of the Sulphur binds with hydrogen to form H 2S while some remain in the residue of
the effluent. A part of the carbon dioxide molecules binds to the ammonia molecules. The
theoretical CH4:CO2 ratio of biogas is 71%:29%, but the actual ratio of methane to carbon
dioxide is highly dependent on the composition of the biomass used in the AD process. The
following steps indicate the Gibbs free energy balance when biogas is produced. The
energy is originally captured during photosynthesis and stored in the organic biomass as
described in the following steps (Deublein and Steinhauser, 2011):
CO2  H2O  solar energy  CH2O  O2 (2.5)
𝑐𝑎𝑟𝑏𝑜𝑛𝑑𝑖𝑜𝑥𝑖𝑑𝑒 + 𝑤𝑎𝑡𝑒𝑟 + 𝑠𝑜𝑙𝑎𝑟 𝑒𝑛𝑒𝑟𝑔𝑦 →
𝑐𝑎𝑟𝑏𝑜ℎ𝑦𝑑𝑟𝑎𝑡𝑒 + 𝑜𝑥𝑦𝑔𝑒𝑛
The following Gibbs free energy balance equation illustrates the release of energy and the
degradation of organic biomass into biogas (Deublein and Steinhauser, 2011):
Carbohydrate: CH2O  0.5CH4  0.5CO2 (2.6)
The solar energy stored through photosynthesis is released through the combustion of
methane and oxygen that produces carbon dioxide and water as products (Deublein and
Steinhauser, 2011):
0.5CH4  O2  0.5CO2 H2O (2.7)

This closes the energy loop of the AD process. AD bio-reactions release very little heat
during the fermentation process; thus, the digester must be heated and thermally well-
insulated. Theoretically, the energy that is released during the combustion of biomass
12
corresponds to the sum of the energy set free in the production of biogas plus the burning
of methane. This energy is equal to the energy that was needed for photosynthesis.
13
2.4 Impact of Process Parameters on Biogas Production
Biogas production systems are multifaceted and complex, due to several factors such as
pH, temperature, retention time, seeding and total solid content.
2.4.1 Effect of pH value

pH value is the main factor in AD and the development of microbes and the survival of
methanogenic bacteria during AD depends on the acidity of the environment that they
require a near-neutral pH. pH levels that are too high or too low inhibit the growth of
methanogenic microorganisms, which then reduces the production of biogas. The optimum
pH level for methanogens to form methane is between 6.7 and 7.5 (Deublein and
Steinhauser 2011). Cattle manure is suitable for AD to produce biogas as it has a pH level
of 7.5 that is within the optimal range of pH (Derikx et al., 1994). The AD process is
severely inhibited when the pH level decreases to below 6.5 (acidic) and rises above 8.5
(alkaline). The higher volatile fatty acids are converted into acetate and hydrogen by
obligate hydrogen-producing acetogenic bacteria. The accumulation of hydrogen can
inhibit the metabolism of acetogenic bacteria (Raja and Wazir, 2017).
Bah et al. (2014) investigated the effect of pH in the range of 6.9-8.9 on the anaerobic co-
digestion of palm pressed fiber and cattle manure to obtain the best condition for the
activity of methanogenic microorganisms. They found that the optimum pH range was 6.9-
7 at which, the highest methane production yield was achieved.
T. Zhang et al. (2015) examined the effect of initial pH value on methane production and
under thermophilic condition of anaerobic co-digestion of swine manure and maize stalk.
Different initial pH at five levels (6.0, 6.5, 7.0, 7.5, and 8.0) with NaOH, HCl acid and
three different manure ratios were tested. The result showed that, at different initial pH a
diverse methane production after 35 days was achived. Also the result revealed that the
optimum pH was 6.81 with 70% swine manure ratio.
Neshat et al. (2017) investigated the optimum pH for anaerobic digestion of cotton stalk,
and cattle manure, either as sole substrate or co-substrate, was determined as 6.5. They
expected lower pH levels in co-digestion wherein the concentration of VFAs was much
higher than mono-digestion; however, because of the buffering capacity of manure, pH
level did not change significantly.
14
Zhai et al. (2018) studied the effects of different initial pH (6.0, 6.5, 7.0, 7.5, and 8.0) and
uncontrolled initial pH on co-digestion of kitchen waste with cow manure. They found that
initial pH can affect pH variation during AD, VFA concentration, alkalinity, and ammonia
concentration. They emphasized on the significance of initial pH on AD and reported pH
the optimum pH for their system was 7.5. Generally, acidification of the medium is one of
the reasons for the failure of anaerobic digestion which can take place as a result of the
presence and accumulation of VFAs at very initial stages of digestion (startup period).
2.4.2 Effect of temperature
Temperature is one of the most influential parameters which affect the performance and
stability of AD. Anaerobic digestion can take place in all temperature regimes (Mattocks,
1984): psychrophilic bacteria range (less than 288K), mesophilic bacteria range (between
302K and 313K), and thermophilic bacteria range (323K–328K). Temperature variations
can affect hydrolytic bacteria, acidogenic bacteria, and methanogenic bacteria. Deviation
from optimum temperature can cause acidification due to the accumulation of VFAs.
Methanogenic bacteria cannot also tolerate temperature fluctuations over 274 K/d.
Working at thermophilic conditions above 318 K can enhance the performance of AD
because of the higher solubility of organic compounds, higher biochemical reaction rates,
lower liquid viscosity, higher pathogen deactivation, and less odor emission (Buhr and
Andrews, 1977). Suitable operating performance, stability, and less sensitivity to inhibitors
are considered as the advantages of mesophilic operations (298–313)K.
Angelidaki and Ahring, (1994) investigated the effect of temperature in the range of 313-
337 K, on thermophilic anaerobic digestion of cattle manure with two different ammonia
concentrations (2.5 and 6.0 g/L) in continuously fed lab-scale digesters. When the
ammonia load was high, the reduction of the temperature below 328K increased the biogas
yield and better process stability, indicated by a lowering of the concentration of volatile
fatty acids in the effluent.
Adelekan and Bamgboye, (2009) suggested that anaerobic bacteria communities can
endure temperatures ranging from below freezing to above 330.2K, but they thrive best at
temperatures of about 309.7K (mesophilic) and 327.4K (thermophilic). Bacterial activity,
and biogas production, falls off significantly between about 312.4K and 324.7K and
gradually from 308K to 273K. To optimize the digestion process, the digester must be
kept at a consistent temperature as rapid changes will upset bacterial activity.
15
Sánchez et al. (2005) found biogas production to be greatest when the digester temperature
was in the range of 305K to 313K. During the process of AD to reach optimum operating
temperatures (303–310)K, some measures must be taken to insulate the digester, especially
in high altitudes or cold climates. Straw or shredded tree bark can be used around the
outside of the digester to provide insulation.
2.4.3 Effect of total Solid
Total solids concentration is a measurement that includes the combination of total

dissolved solids and total suspended solids. TS test determines how much of the cow
manure is composed of water and how much of the cow manure is solid. It also helps to
identify whether the AD process is wet or dry. In wet digestion, the total solids content in
the bioreactor is usually less than 15%, while in dry digestion the total solids in the reactor
feed are (15–40)%. Wet digestion is easier to regulate in terms of different process
parameters, for example by pH and dry matter content (Deublein and Steinhauser, 2011).
Due to the greater water content, wet digestion offers better mixing possibilities.
Mattocks, (1984) pointed that the percentage of TS should be between 5% and 12% while
other source reported that the best biogas production occurs when TS is ranged from 7% to
10% because of avoiding solids settling down or impeding the flow of gas formed at the
lower part of the digester. Therefore; dilution of organic substrate or wastes with water to
achieve the desirable total solids percentage is required. The most favorable TS value is 8
% for better biogas production (Mukumba et al., 2017).
2.4.4 Hydraulic retention time

Hydraulic retention time is the average duration of time holding slurry in the digester. The
retention time must be long enough to ensure that the number of microorganisms produced
in the digester exceeds the microorganisms removed in the effluent. If the process could
not be maintained at its optimum HRT, the unfavorable metabolic activity of
microorganisms and undesirable products will have resulted. Long HRTs can lead to the
death of microorganisms due to the shortage of nutrients; in contrast, short HRTs can result
in cell intoxication or low methane yield. At high temperatures, a reaction occurs fast and
so the degradation will also be faster and HRT will be less. A 25-day HRT is
recommended for effective AD of organic matter under mesophilic conditions (Salminen
and Rintala, 2002). The shorter HRT provides good substrate flow but delivers low biogas
yields due to the microorganisms escaping in the effluent.
16
2.4.5 Seeding
To start and accelerate fermentation processes, a small amount of digested slurry,
containing methane forming bacteria is added to the freshly charged plant. Seeding the
digester speeds up the time required for digester start-up by inputting a population of
anaerobic bacteria. Seeding the digester may be done in a few different ways. The most
preferable method of seeding the digester is to obtain biosolids from a nearby operating
digester. There may not be any digesters nearby, so this may not be possible. Another
method of seeding the digester is to obtain microorganisms from the stomachs of cattle.
2.4.6 Summary of factors affecting the anaerobic digestion process
Several factors affecting biogas production discussed in various studies should be

optimized for good biogas yield. According to all the factors that are mentioned above the
suitable condition for the production of biogas with stability can be achieved when the
temperature for the biogas production ranges from the (310–330)K, pH for the suitable
anaerobic digestion of the biogas is 6–8, TS concentration required ranges from 5%–9%
and HRT should be higher for more micro-organisms to develop in biomass.
2.5 Challenges in Anaerobic Digestion

The AD process, despite being a matured approach for organic waste management, is still
affected by three major limitations. Process stability, efficiencies, and product quality
(impacted by instabilities induced by highly degradable organic substrates), management
of effluents and emissions (volume of effluent and the degradation of input substrate that
determines emission levels of CH4 from the effluent) and the flexibility of an acceptable
substrate (related to the inability to digest highly lignocellulose biomass without
pretreatment).
2.6 A Conventional Approach for Alleviating the Challenges with AD

Predictable approaches mostly implemented to reduce the challenges in the AD process are
alkaline chemical addition, two-stage digestion and co-digestion. The application of
alkaline chemicals reduces acid levels in the AD, thereby neutralizing the acidification
process (Gao et al., 2015).
Two-stage digestion is another viable approach that promotes different types of oxidation
and reduction reactions, pH optimal, and growth rate of acidogenic and methanogens. The
two-stage approach has the advantage of hydrolyzing the substrate and buffering OLR in
17
the
18
first stage. In the second stage, the hydrolyzed and the homogenized substrate can be easily
digested by the methanogens (Sunyoto, 2019).
Co-digestion is the simultaneous digestion of a homogenous mixture of two or more

substrates. Substrates as food wastes, sewage waste, cattle manure, certain energy crops,
and algae are good bases to obtain processes with good nutrient and trace element balances.
These kinds of substrates can often be implemented for “mono-substrate” digestion, while
substrates dominated by carbohydrates or fats need to be co-digested or digested in
processes modified by e.g. nutrient and trace element additions, sludge recirculation
(Alemu Gizaw Wakene, 2016). The microbial population in the digester and biogas yield is
partly dependent on the ratio of the different types of waste within the substrate mix (Lin et
al., 2012).
2.7 Biogas upgrading

The utilization of biogas produced from organic materials such as agricultural wastes or
manure is increasing. The deficiency with using biogas is also due to the presence of CO2
(a non-combustible gas) in biogas lowers the calorific value and the specific energy density
of biogas. Furthermore, it reduces its flame speed and the extent of flammability in
comparison to natural gas (Budzianowski, 2016). These challenges affect the sustainability
of biogas, and therefore, biogas upgrading which results biogas with comparative
properties to natural gas is an alternative pathway.
Seadi et al. (2008) state that after upgrading, biogas can be utilized as vehicle fuel or
injected into the natural gas network used as natural gas. The upgrading will reduce all
contaminants with certain concentration such as carbon dioxide and hydrogen sulfide,
through which the content of methane will be increased from the average 50-75% to more
than 95%.
2.7.1 Challenges in small-scale biogas upgrading

Andersson and Nordberg, (2017) reported that the value of the biogas produced at small
scale facilities can be increased by upgrading it to vehicle fuel quality. However,
commercial upgrading technologies available today are very costly for small scale
applications. To upgrade biogas on a small scale (less than 200 Nm 3/h) has been too
expensive to be interesting, due to the high specific investment costs of the upgrading
equipment. For a plant with low capacity, more or less the same number of sensors,
19
analysis equipment, control systems, and valves are needed as for a plant with a much
larger capacity. The dimensions of the pipes and valves will be smaller, but the specific
investment cost will be high.
20
2.7.2 Upgrading biogas within AD (An approach used in this study)
The existing literature suggests the need to improve the performance and biogas yields of
AD through conventional approaches and commercial upgrading technologies. But
conventional approaches do not comprehensively address the challenges in AD. Therefore,
one possible solution to address the challenges is by utilizing biochar in AD operation.
The combination of pyrolysis and AD, as shown in Fig. 2.3, is increasingly seen as a
relatively unconditional but promising approach to address these challenges. Pyrolysis can
be used to valorize high lignocellulose biomass and effluent from AD. The present focus of
this study is on the effect of biochar in AD to improve process stability through the
reduction of substrate-induced inhibition and its effect in increasing the concentration of
CH4 (upgrading) in biogas.
Figure 2.3: Process schematic for an AD process integrated with pyrolysis
2.7.3 Biochar
Biochar, the solid product of biomass pyrolysis, has been produced and utilized for several
thousand years. According to the International Biochar Initiative (IBI), biochar is a stable
and solid carbon-rich material obtained from the thermochemical conversion of biomass in
an oxygen-limited environment without any form of activation (IBI 2012).
2.7.3.1 Biochar production, properties, and application

The thermochemical conversions of biomass usually used to produce biochar are pyrolysis
and hydrothermal carbonization (HTC). Pyrolysis is the most well-known method in
21
biochar
22
production within the temperature of 200–1000℃ with little or no oxygen. Depending on
temperature and residence time pyrolysis can be fast pyrolysis, where residence time is
only seconds, and slow and intermediate pyrolysis, where residence time is from a few
minutes to several hours or even days (Mohan et al., 2006).
Figure 2.4: Biochar (https://www.google.com/lewisbamboo.com)
Two special cases of pyrolysis are Torrefaction, which is mild pyrolysis in the temperature
of 230–300℃, and gasification that happens in the temperatures above 800℃ in a
controlled oxygen/steam environment and results mainly in gaseous end-products (Mohan
et al., 2006). Biochar made from different materials with different methods have unique
properties, and one type of biochar may not be suitable for all purposes. The most
important properties governing the use of biochar are surface area, pore size distribution,
and ion exchange capacity.
23
Biochar
Physical Chemical Biological

Characteristics
-High SSA -Surface -Provision of

-High porosity nutrients
functional groups
-High alkalinity
functions
Possible
Adsorbent Microbial Micronutrient

carrier additives
applications
Possible
AD Biogas cleaning Fertilizer
Figure 2.5: The characteristics, functions, and applications of biochar (Sunyoto, 2019)
Generally, the high pyrolysis temperatures favor biochar that is effective in adsorbing
organic contaminants by increasing surface area, microporosity, and hydrophobicity. On
the other hand, biochar produced in low temperatures is better in removing inorganics and
polar organic compounds by ion exchange capacity, electrostatic attraction, and
precipitation (Ahmad et al., 2014).
Biochar production methods and estimated differences in biochar yields obtained from
different methods are shown below in fig. 2.6 (Igalavithana et al., 2018). The figure shows
that slow pyrolysis favors the production of biochar; and this is derived from solid
biomass. Hydrothermal carbonization produces hydro char from sludge materials; while
gasification favors the formation of the gaseous-phase products.
24
Feedstock
Thermochemical process
Slow pyrolysis Gasification Fast pyrolysis

Primary byproduct Primary byproduct is Primary byproduct is
is biochar. syngas. bio-oil.
Biochar=35% Biochar=10% Biochar=10%
Bio-oil=30% Bio-oil=5% Bio-oil=70%
Syngas =35% Syngas =85% Syngas =20%
- 350-800℃ - 700-1500℃ - 300-1000℃

Conditions
- <10℃ heating rate - Moderate, very fast - Very fast heating rate
- Holding time seconds heating rate - Holding time seconds
to hours - Holding time hours
Characteristics
-Medium SSA - High SSA - Medium SSA

-Medium porosity - High porosity - Medium porosity
Figure 2.6: Biochar production methods and biochar yields (Igalavithana et al., 2018).
2.8 Effect of Biochar on the Anaerobic Digestion System

Biochar with its above-mentioned valuable characteristics for a wide range of applications
therefore becomes an innovative aspect of this study. From carbon-based conductive
materials, carbon-based activated carbon (AC) and biochar can be produced from
agricultural waste. Their porous and bio-stable structure supports the formation of slow-
growing methanogens, ensuring methanogenesis (Mumme et al., 2014). Compared with
AC, biochar is more easily produced at a lower pyrolysis temperature without activation
(Luo et al., 2015). Biochar addition can also increase alkalinity, which was important to
allow the AD system to buffer against acid shock and maintain a suitable pH range, and
mitigate ammonia inhibition and facilitate CO2 sequestration during AD (D. Wang et al.,
2017); Li et al., 2017). According to recent studies (Mumme et al., 2014; Wang et al.,
2017), the alkaline nature of biochar can enhance methane production by an increase in pH
resulting from the conversion of CO2 to carbonate. Improved buffering capacity can
improve reactor stability through alleviation of pH drop caused by the accumulation of
VFAs.
25
Carbon materials such as activated carbon (AC), graphite, and biochar have been used for
stimulating microbial activity in AD. The adsorption of inhibitory compounds by AC also
enhanced the performances of the AD process (Xu et al., 2015). Despite these advantages,
the application of AC to AD has been limited since direct disposal of AC would cause
additional concerns for environmental pollution and safety (Luo et al., 2015). Biochar
could be a cost-effective material to stimulate microbial activities in AD due to its physical
and chemical properties (i.e., biostability, porous and carbonaceous surface with various
functional groups). These properties of biochar are similar to those of AC except the lower
surface area of biochar than AC (Luo et al., 2015).
Biochar provides favorable conditions for the microbial community in various ways.
Physical characteristics, especially porous structure, and surface area facilitates biofilm
formation which can improve resistance ability to various inhibitory compounds and can
enhance microbial activity (Lü et al., 2016); (Luo et al., 2015).
2.8.1 Biochar as ammonium adsorbents

The ability of biochar to remove ammonium ions from matrices with high concentration
has been addressed in a few studies. This would be beneficial in anaerobic digestion since
by adsorbing ammonium ions biochar could reduce the effects of ammonia inhibition.
Kizito et al. (2015) studied the adsorption of ammonium nitrogen from piggery manure
anaerobic effluent slurry with slow pyrolyzed wood and rice husks. The adsorption was
studied in leachate water separated from piggery slurry and in pure NH 4Cl - solution. They
found out that the maximum adsorbed amount and removal percentages by wood biochar
were 54.84 mg/g (73%) from pure solution and 44.64 mg/g (60%) from piggery slurry and
with rice husk biochar 44.64 mg/g (60%) and 39.8 mg/g (53%) respectively. The initial
ammonium concentrations were 1400 mg/L and added biochar concentrations 1–20 g/L.
Sarkhot et al. (2013) studied the effectiveness of biochar to adsorb ammonium from dairy
effluent (ammonium concentration 0–1000 mg/L, biochar dosage 5 g/L) and they found out
that up to 5.3 mg/g (18%) of ammonium was adsorbed by the biochar.
Zhu et al. (2012) studied the removal of ammonium from aqueous solution by using
activated carbons made from rice husks with initial ammonium concentrations of 40 mg/L
and showed that the adsorption varied between 2.04 and 0.97 mg/g depending on the
biochar dosage (1– 20 g/L).
26
The difference between the biochar's ability to adsorb ammonium ions can depend on
various factors.
According to (Kizito et al., 2015) increase in initial ammonium concentration, temperature,

smaller particle size, and contact time increase the adsorption. The adsorption decreased in
low and alkaline pH and the best adsorption was found in the range of 6.5–7. The decrease
in alkaline conditions can result from the conversion of ammonium to ammonia, which
cannot be adsorbed very well onto biochars. The manufacturing and feedstock also have a
significant role in biochar characteristics (Ahmad et al., 2014), and especially biochar
made in lower temperatures (250–400)℃ has been found suitable for removing inorganic
and polar contaminants.
2.8.2 Biochar concentration in AD

The amounts of biochar applied to anaerobic digesters in previous studies have some
variations and the experiments have been done in wet conditions.
Luo et al. (2015) studied the effect of addition of 0.5–1 mm biostable biochar (10 g/L) to
mesophilic anaerobic digesters inoculated with crushed granules (1 g-VS/L) and fed with
4, 6, and 8 g/L glucose shortened the methanogenic lag phase by 11.4%, 30.3%, and 21.6%
and raised the maximum methane production rate by 86.6%, 21.4%, and 5.2%,
respectively, compared with the controls without biochar.
Mumme et al. (2014) investigated the behavior of biochars from pyrolysis in AD regarding
their degradability and their effects on biogas production and ammonia inhibition. A batch
fermentation experiment (42℃, 63 days) was conducted in 100 mL syringes filled with 30
g inoculum, 2 g biochar, and four levels of total ammonium nitrogen (TAN). The effect on
biogas production was observed, which increased the methane yield by 32%.
Lü et al. (2016) evaluated the effectiveness of biochar of different particle sizes in

+
alleviating ammonium (NH4 ) inhibition (up to 7 g/L) during anaerobic digestion of 6 g/L
glucose. Compared to the control treatment without biochar addition, treatments that
included biochar particles 2–5 mm, 0.5–1 mm, and 75–150 mm in size reduced the
methanogens lag phase by 23.9%, 23.8%, and 5.9%, respectively, and increased the
maximum methane production rate by 47.1%, 23.5%, and 44.1%, respectively. These
results confirmed that biochar accelerated the initiation of methanogens during anaerobic
digestion under double inhibition risk from both ammonium and acids.
27
Shen et al. (2015) studied the effect of corn stover biochar on methane yield and quality in
anaerobic digestion (AD) of sludge. The biochar amended digesters produced high quality
biogas (biomethane) with (> 90% CH4 and < 5 ppb H2S), facilitated CO2 removal by up to
86.3%, boosted average CH4 content in biogas by up to 42.4% compared to the control
digester. The biochar addition enhanced the methane yield, and maximum methane
production rate by up to 7.0%, and 27.6%, respectively.
Yang et al. (2017) studied the effect of granular activated carbon (GAC) added into a
batch- mode anaerobic sludge digestion reactor with an attempt to improve the sludge
digestion. The results showed that with adding GAC from 0 to 5.0 g, the methane
production increased by 17.4%, and the sludge reduction rate increased by 6.1 percent
points (from 39.1% to 45.2%).
Fagbohungbe et al. (2016) studied the impact of different types of biochar and a biochar
ratio on the anaerobic digestion of citrus peel waste was investigated. Citrus peel has an
inhibitory effect on anaerobic digestion. The presence of biochar had two effects: a
reduction in the length of the lag phase and greater production of methane relative to citrus
peel waste only incubations. The microbial lag phases decreased with an increase in the
citrus peel to biochar ratios, with 2:1 having the longest lag phase of 9.4 days and 1:3, the
shortest, with a value of 7.5 days. The cumulative methane production in incubations
containing biochar and citrus peel ranged from 163.9–185.0 ml CH4 g/VS, while citrus
peel only produced 165.9 ml CH4 g/VS.
L. Zhang et al. (2018) studied the effects of 15 g of activated carbon (AC) supplementation
on anaerobic digestion (AD) of food waste in lab-scale performed in 1 L and 8 L digesters,
while pilot-scale AD was conducted in a 1000 L digester. Pilot-scale digester without AC
gave an average methane yield of 0.466 L/(g VS)/day at a composition of 53–61% v/v
methane. With AC augmentation, an increase of 41 % in methane yield was achieved in the
1000 L digester under the optimal organic loading rate (1.6 g VSFW/L/day).
Meyer-kohlstock et al. (2016) investigated biochar in anaerobic digestion effects in solid-

state fermentation of bio-waste. The influence of biochar was tested with a setup that
simulates an industrial-scale biogas plant. The result showed that both the biogas and the
methane yield increased around 5% with a biochar addition of 5% based on organic dry
matter biochar to bio-waste. An addition of 10% increased the yield by around 3%.
28
Yun et al. (2018) investigated the effect of seven carbon materials having specific surface
area of 580–824 m2/g as additives on the biogas yield. Dairy manure as substrate and
activated sludge as inoculum was used for the biogas yield. The result indicates that, the
addition of carbon significantly improve the biogas yield (380–502 mL/g TS).
Md Rashedul Islam et al. (2016) performed research work using a 1-liter capacity conical
flask and 8 % TS to find out the production of biogas from cow dung using charcoal and
gelatin as additives. Five laboratory-scale experimental set-ups were constructed using 0,
0.2, 0.4, 0.6, and 0.8% gelatin and 0.5% charcoal with cow dung as an additive at the
ambient temperature of 26℃–32℃. The total gas yield without using gelatin additive was
found to be 12 L/kg cow dung. The maximum gas yield was found from 0.2% gelatin
additive and 23% more as compared to without gelatin gas production.
Zhang et al. (2018) conducted a batch of anaerobic digestion experiments using diary
manure, anaerobic sewage sludge as inoculum, and low-cost composited accelerants
consisting of urea (0.2–0.5)%, bentonite (0.5–0.8)%, active carbon (0.6–0.9)%, and plant
ash (0.01-0.3)% to improve the methane yield and effluent utilization. Total biogas yield
(485.7– 681.9 mL/gVS) and methane content (63.0–66.6)% were found by adding
accelerants compared to those of the control group (361.9 mL/gVS, 59.4%).
Jang et al. (2018) studied the effects of dairy manure-derived biochar (M-BC) on methane
production in anaerobic digestion (AD) of dry dairy manure were investigated with three
different concentrations of biochar (0, 1, and 10 g/L) and temperatures (psychrophilic,
20℃; mesophilic, 35℃; thermophilic, 55℃). Compared with the AD without any biochar,
the cumulative methane and yield in the AD with 10 g/L biochar were increased to 27.65%
and 26.47% in psychrophilic, 32.21%, and 24.90% in mesophilic and 35.71% and 24.69%
in thermophilic digestions.
Gómez et al., (2018) studied the assessment on biogas production carried out using
samples of swine manure (SM) supplemented with char in one case and pre-treated by
microwave irradiation in the other. This experimental setup was allowed for the
comparsion of the biological degradation observed under these two different configurations
and therefore aids in understanding the effect of char particles on the process. The result
showed similar performance for both systems, with an average improvement of 39% being
obtained in methane production when compared to the single digestion of SM.
29
Cai et al. (2016) investigated the addition of various amounts of biochar to A of food
wastes at different ratios of inoculum to a substrate (ISR) to evaluate the effect of biochar
as a functional additive and to optimize the additive dosage of biochar. The biochar
treatments at ISR 2, 1, and 0.8 shortened the lag phase of digestion by (2.0–10.9)%, (43.3–
54.4)%, and (36.3–54.0)%, and raised the maximum methane production rate by (100-
275)%, (100– 133.3)%, and (33.3–100)% respectively, compared to control biochar.
Therefore, the effectiveness of biochar depended on the additive amount of biochar.
2.9 Summary of literature and gaps

This chapter demonstrated challenges of AD technology and previously taken measures
through a comprehensive literature review. The the existing literature implements
conventional process-related routes for managing AD instability but still have their
disadvantages. The use of two-stage digestion does not guarantee process stability.
Depletion of the neutralizing alkali chemical results in the increase of process acidification.
The application of additives beyond the acceptable limits inhibits the AD process. The
addition of alkali chemicals such as NaOH and CaCO 3 solutions can obviate the problem
until the system becomes stable; nevertheless, some of these chemicals can cause other
problems (Aboudi et al., 2015). The practical implementation of co-digestion requires that
all the necessary substrates are available at all times. In general these techniques may
mitigate AD instability could not improve the biogas quality (methane content in the
biogas).
Biogas upgrading is gaining global interest due to its potential to increased energy
efficiency and improved sustainability. Conventional technologies for biogas upgrading
include physical and chemical absorption, pressure swing adsorption, membrane
separation, and cryogenic cooling. However, commercial upgrading technologies available
today are very costly for small scale applications (Andersson and Nordberg, 2017). To
upgrade biogas on a small scale (less than 200 Nm3/h) has been too expensive to be
interesting, due to the high specific investment costs of the upgrading equipment. For a
plant with low capacity, more or less the same number of sensors, analysis equipment,
control systems, and valves are needed as for a plant with a much larger capacity. The
dimensions of the pipes and valves will be smaller, but the specific investment cost will be
high. In addition to this activated carbon was used in AD for adsorption of contaminants in
biogas. Despite these advantages, the application of AC to AD has been limited since direct
30
disposal of AC would cause additional concerns for environmental pollution and safety
(Luo et al., 2015) and since it
31
needs activation so that farmers in rural area may not afford cost related to activation.
Therefore, it is suggested to investigate the impurities removal using biochar derived from
sources of waste/feedstock.
Biochar could be a cost-effective material to stimulate microbial activities in AD due to its

physical and chemical properties (i.e., biostability, porous and carbonaceous surface with
various functional groups). These properties of biochar are similar to those of AC except
the lower surface area of biochar than AC (Luo et al., 2015). Compared with AC, biochar
is more easily produced at a lower pyrolysis temperature without activation. Biochar with
its aforementioned beneficial characteristics for a wide range of application, therefore,
become the innovative aspect of this study.
In the aforementioned literatures ,different types of biochar have been used in the study of
the reduction of biogas impurities such as H 2S and ammonia. However, up to now, there
are limited studies on the reduction of biogas impurities such as carbon dioxide which
affects energy quality. Most of the previous works on AD focus on the addition of biochar
by mixing completely with the substrate. However, this technique may not much effective
beacuase the slude may fill pores of biochar which affects the adsorption capacity. In this
study through various considerations, increasing methane yield from anaerobic digestion of
cow dung by mixing some of corn cob derived biochar with substrate and some without
mixing instead keeping it at the top of the media is proposed and has to be tested. It is
expected that this study will fill the gaps in the literature about AD stability, the biochar
application in AD system for impurity reduction. The thesis investigates the preparation,
utilisation of biochar in the AD and gas upgrading.
32
CHAPTER 3: MATERIALS AND METHODS
3.1 Introduction
This chapter presents a detailed methodology, and techniques to achieve the study
objectives. The present investigation will focus on the effect of corn cob derived biochar
on methane and biogas yield from fresh cow dung. Figure 3.1 shows the schematic diagram
of the overall strategies for the experimental study.
Slow pyrolysis
Experiments
Lab scale AD
Strategies
Modelling Gompertz model
Figure 3.1: Study strategies
3.2 Materials
The following materials were used for experimental evaluation for this study. Substrate:
feedstock materials for biogas production (cow dung). Cow dung is a favorable feedstock
for AD due to its high nutrient content and because the cow dung already contains the
biogas- forming bacteria when the manure is still fresh (Deublein and Steinhauser, 2011).
Inoculum: rumen fluid (intestine residue) for seeding purposes. Corn cob for biochar
production and biochar for facilitating digestion, increasing biogas quality, and reduce
process inhibitions. The samples were collected and transported to Wachemo University,
Chemical Engineering Department laboratory, and the experiment was
conducted.
33
Table 3-1: List of materials used in the study
Materials name Area collected Purpose

Corn cob Hadiya Production of biochar
Cow dung Hosana Generation of biogas
Intestinal residue Hosana city abattoir For seeding
Chemicals used Bought from Purpose
Starch, HCl Kirkos To prepare a 5% HCl solution
Potassium iodide Kirkos Preparing the iodine solution
Preparing a sodium thiosulphate
Potassium iodate Kirkos
solution
Iodine Kirkos Preparing the iodine solution
NaOH Kirkos Preparing an alkaline solution
Corn cob Biochar
Figure 3.2: Corn cob and Biochar
34
3.3 Equipment and measuring instruments
The necessary equipment’s and measuring instruments were used in this study summarized
as follows:
Table 3-2: Equipment’s and measuring instruments used in this study
Manufacturer
Equipment Application or purpose
(Model)
Mixing tank (Baldi) NA For preparing a homogenous mixture of feed
Universal hot air oven NA TS
Muffle Furnace NA VS and biochar production

pH meter PHS-1701 pH
Thermometer NA Measure water bath temperature
Digital Weight Balance NA Measure the mass of CD and corn cob samples.
Plastic bottles NA Used as Digester

Water bath NA For sustaining temperature level at 37℃
Tubes NA For the flow of gas from the digester to the airbag
Rollers NA To control gas flow lines
Airbag NA To collect biogas
Additives Superglue To form an anaerobic system inside the digester
Crucibles NA Sample holder during the experiment
Desiccator NA For cooling samples to room temperature
Graduated cylinders NA For gas measurement
3.4 Preparation of Raw materials

3.4.1 Preparation of CC-BC
The raw material (corn cob) used in this study was collected from rural areas particularly
Hadiya where a large quantity of Maize has been produced. Due to the high volatile
content in corn cob, it is suggested that corn cob is a suitable feedstock for the
thermochemical conversion process such as pyrolysis.
35
Figure 3.3: Corn cob before and after sizing
3.4.2 Pyrolysis of corn cob

The corn cob BC was prepared via the pyrolysis of the corn cob. Corn cob was placed in
crucible and introduced in an electric furnace where the temperature was set up at 350 ℃,
450℃, and 550℃ for 30min, 1, and 1.5 hours each.
3.4.3 Characterization of CC-BC

After the pyrolysis, all biochar was crushed and sieved with between 850 and 150 µm
according to ASTM D1762-84.
A. Proximate analysis
The proximate analysis was conducted with the ASTM technique. The values of moisture
content, ash content, and volatile matter of corn cob were determined according to the
standard test method ASTM D1762- 84, which was published by the American Society for
Testing and Materials, is commonly used for this purpose. The moisture, volatile matter,
and ash content calculations are as follows (ASTMD1762-84, 2011):
Moisture %   w1  w2 x 100
(3.1)
w1
Volatile matter %  w2  w3
 x100 (3.2)
w2
Ash %   w
4
x100 (3.3)
w2
36
Where, w is the weight of the air-dried sample, w is the weight of the sample after being
1 2
heated at 105℃,
w3 is the weight of the sample after being heated at 950℃ and is the
w4
weight of the residue after being heated at 750℃.
B. Surface area and pore size

Brunauer-Emmett-Teller (BET) is a method commonly used to calculate the biochar
surface area. The iodine absorption method has very rarely been used to determine the
biochar surface area (Igalavithana et al., 2018), possibly be due to the inapplicability of the
iodine absorption method for biochar surface determination. The method was originally
developed for surface area determination in organic matter-rich soils and activated C
(ASTM D4607- 94, 2007). The test method of ASTM D4607-94 (ASTM D4607-94, 2007)
explains the detailed methodology of iodine absorption. Iodine number In of the carbon
using the equation (ASTM D4607-94, 2007):
In  X A
M
(3.4)
X  12.693N1  279.246N2V 
(3.5)
Where, X = mg of iodine adsorbed by the biochar
V = volume of sodium thiosulphate solution in
ml M = mass of activated carbon in g
N1= normality of iodine solution
N2 = normality of sodium thiosulphate solution
A = correction factor, depending on residual normality Nrof the
filtrate
Nr  N V
2
50 (3.6)
3.4.4 Preparation and characterization of cow dung and inoculum
The substrate used in this study was collected from rural areas particularly around Hosana.
The collected sample was characterized using the standard methods.
Determination of total solid (TS)
The total solid content of the cow dung (CD) can be determined by the procedure given by
APHA 1995. The percent of total solids is computed using the formula (APHA 1995).
CA
%TS  x100 (3.7)
BA
37
Where, A = Weight of crucible, g
B = Weight of wet sample + crucible, g
C = Weight of dried crucible + dried residue, g
Determination of volatile solids (VS)
The volatile solids content of the sample can be determined by adopting the procedure
furnished by APHA 1995. The loss in weight is now the volatile matter present in the
samples were also calculated using (APHA 1995):
BC
%VS  x100 (3.8)
BA
Where, A = Mass of empty clean and oven-dried silica crucible,
g
B = Mass of silica crucible + sample, g
C = Mass of silica crucible + sample after ignition, g
3.4.5 Inoculum preparation

Due to the presence of higher content of anaerobic bacteria in the rumen of the animals and
the abundance of rumen waste disposal from the nearby slaughterhouse (Hosana city
slaughterhouse), the source of inoculum was intestine residue from slaughterhouse mix
with water on TS basis and large inorganic particles were removed from the sludge by
passing it through a 5-mesh sieve.
Figure 3.4: Inoculum preparation
38
3.4.6 Media preparation
Total solids concentration for the cow dung was observed greater than 16% that is the
upper threshold limit for wet digestion (Mattock, 1984). Thus, its total solid was first
determined by drying at 105℃ until a constant mass was observed on drying (24 h).
A B
Figure 3.5: (A) Inoculum, biochar, and cow dung slurry, and (B) Preparing mixture
C D
Figure 3.6: (C) Pouring the mixture, and (D) Adding biochar with various concentrations
The amount of water to be added to fresh cow dung to adjust its total solids concentration
to 8%, which is optimum for wet anaerobic digestion, was computed from the following
simple mass balance. Cow dung was mixed with inoculum with a 1:1 ratio in a mixing tank
used in all the experiments. Finally, the prepared media was feed into the laboratory scale
digester for biomethane production.
39
3.5 Lab-scale Biogas Production Experiment
The AD experiments were conducted in liter digesters at mesophilic temperature (37℃ ±
1℃) with a working volume of 0.8L. The control (ADM0) and digesters amended with
biochar at four different concentrations. Mondel et al., 2018
3.6 The Modified Gompertz Model

A modified Gompertz equation was used to correlate experimental data to quantify the
cumulative methane production and the correlation fitting was done using SPSS statistics.
To obtain lag phase, maximum production potential, and production rate under the
mesophilic condition and different dosage of biochar, modified Gompertz model using the
following equation (Luo et al., 2015):
M (t )=P xexp {−exp [ R max xe

P ]
( λ−t ) +1 } (3.9)
Where M (t ) (mL) is the cumulative methane production; P is the maximum methane potential
(mL); Rmax (mL/day) is the maximum methane production rate; λ (days) is the lag phase
(minimum time to produce biogas (days), e is Euler number which is 2.7183 and t is time.
40
CHAPTER 4: SIZING DIGESTER
4.1 Introduction
Biogas digesters are used to produce methane gas and the size of the digesters is commonly
bigger. People who live in poor conditions and are familiar with the uses and the
advantages of using methane gas wants to have a biogas digester at home for replacing the
cooking gas as the ever-increasing price of cooking gas is adding to their woes.
4.2 Customers Energy Demand for Cooking

Single-family members (ten considering new visitors) need biomass energy to produce
their daily food. To perform biogas production for cooking, the energy requirement has to
be determined. Households in rural areas mainly need energy for cooking, lighting, and
empowering of low voltage elementary appliances. Lighting and empowering of
elementary appliances require a relatively low amount of energy which can be satisfied
with electricity from photovoltaic cells. The amount and type of energy used for cooking in
the rural developing country depend on income, availability of fuel, cooking behavior, and
efficiency
of the appliances.
4.2.1 Amount of biogas required

To perform a heat requirement analysis, the biogas production rates have to be determined.
The amount of biogas required to fulfill the energy demand for cooking can be estimated
using two ways. The first method is to obtain the input heat energy; the amount of heat
energy contained in the biogas fuel must be equal to the required heat energy for cooking
per person. The amount of heat energy available in the fuel per person (Q biogas) = QT =
energy input
Qbio  mbio x LHV (4.1)
Where, Qbiogas = Heat energy available in the biogas, KJ /person,

mbiogas = Weight of biogas used in the stove, kg and
LHV = Lower heating value of fuel biogas, KJ kg.
Alternatively, taking the average value of biogas required per day per person which is a
simple method and used in this study. The reactor is designed to produce biogas that can
fulfill the energy demand of 10 people for their cooking application. The average amount
41
of biogas required to fulfill the energy demand of a person per day for cooking
applications is
0.225 m3 of biogas (Leulseged Tarekegn, 2018). Also (Khan, 2009) described that biogas
42
required for cooking is about 0.225 m3/person per day. The designed biogas reactor is
responsible to produce 2.25 m3 of biogas per day for 10 people.
The total quantity of biogas required for cooking for 10 persons will be
Vbiogas  N x0.225 m3 of biogas / person / day (4.2)
Where, N = number of persons = 10

N = 10 x0.225 m3 = 2.25 m3 /day
Table 4-1: Biogas requirement on daily and monthly basis

Time Gas requirement No of the members Total gas Considering a
in a single family needed 10% loss
Daily basis 0.225 m3/person 10 2.25 m3 2.475 m3
Monthly basis 6.75 m3/person 10 67.5 m3 74.25m3
4.2.2 Cow dung and number of cow requirement

(Kuria and Maringa, 2008) explained the standard relationships used to size the biogas
units based on a zero grazed cow as follows:
 1 cow produces 10 kg of cow dung per day.
 The solid matter content in cow dung is 18 %.
 The density of cow dung slurry is 1090 kg/m3
Let z be the number of cows, cow dung produced = 10z kg/day.
But, according to (Khan, 2009) only 70 % of dung can be collected. 30% is lost during
grazing.
Collectable cow dung (70%) = 7z kg/day
Weight of dry solid mass in cow dung = 18% * 7z kg/day
Gas production per day = gas yield (m3/kg of dry matter) * TS * 7z kg/day
2.25 m3/day = 0.34 * 0.18 * 7z
Z = 5.25 ≅ 6. Thus, six cows are required to feed the plant.
The amount of cow dung required to produce 2.25 m3 is calculated as
Daily feeding of cow dung = 7* 6 = 42 kg
This will be mixed with an equal amount of water to make a slurry.
Thus, the daily feed of slurry = 84kg = 84 kg / 1090 kg / m3 = 0.07706 m3
Table 4-2: Feedstock requirement on daily and monthly basis
Time CD (kg) single family member Total CD (kg)
43
Daily basis 42 10 420
Monthly basis 1260 10 12600
4.3 Sizing of Anaerobic Digester

Biogas digester design plays a crucial role in digester performance and some
considerations are taken into account. The following aspects were considered during the
design process: durability, airtightness, availability of local materials, and easy operation.
The main design parameters are total solid content and hydraulic retention time.
TS contained in a substrate is usually used as the material unit to indicate the biogas
production rate of the materials. The most favorable TS value is 8% for better biogas
production (Mukumba et al., 2017), and HRT.For mesophilic digestion where temperature
varies from 25-35℃, the HRT was greater than 20 days. In the thermophilic environment,
HRT is usually less than 10 days. Shortening retention time can lead to an increase in the
volatile fatty acids (VFA) (Mukumba et al., 2017), and this is why mesophilic digestion
was considered.
A surface cylindrical biogas digester was chosen because it was easy to feed, insulate,
clean, and easy to construct, relatively small amounts of slurry (a mixture of manure and
water) are added daily and remove slurry after every hydraulic retention period. This
enables gas and fertilizers are produced continuously and predictably. The anaerobic
digester has its parts which include mainly digester chamber, hydraulic chamber, gas
holder, and piping.
4.3.1 Volume calculation of digester chamber

The size or volume (VD) of the digester is determined by the length of the retention time
(HRT) and by the amount of fermentation slurry supplied daily. The size of the digester
largely depends on the amount of waste to be added. The dimensional parameters to be
considered during sizing are:
Vgs =Volume of the gas storage chamber

Vf =Volume of the fermentation chamber
VH =Volume of the fermentation chamber
VS =Volume of the sludge layer
Vc =Volume of gas collecting chamber
44
Figures 4.1, 4.2, and 4.3 are adapted from (Chendu and Sichuan, 2009)
Figure 4.1: Cross-section of a digester
The Vc is the volume of the biogas chamber which is the upper part of the digester needed
to collect and store the biogas. The fermentation chamber is the place below the V c where
the liquid mixture of effluent is stored until complete decomposition.
The total volume of cylindrical-shaped biogas digester with a hemispherical head will be:-
V Vc Vgs Vf Vs
(4.3)
Figure 4.2: The geometry of the cylindrical-shaped biogas digester
The parameters in fig 4.2 stand for:
45
 The volume of fermentation chamber=Vf =V3
 Volume of sludge layer = V2 = Vs
 R1 and R2 are the crown radius of the upper and bottom layer of the digester
 S1 and S2 art the surface area of the upper and the lower dome [m2]
respectively
 f1 and f2 are the maximum distance of the upper and lower dome [m]
 H is the height of fermentation chamber [m]
Previously the number of cows required to produce 2.25 m3 of biogas was determined as 6.
Most biogas digesters in operate in the mesophilic temperature range (20℃ < t < 40℃).
For liquid manure undergoing fermentation in this temperature range, the following
approximate retention times apply
 Liquid cow manure 20-30 days
Let HRT = 30 days (for temp. 37℃) taking maximum HRT.
1. Calculating the total discharge
Td  Ddp x N
(4.4)
Td = Total discharge kg/day
Dpd = Discharge per day
kg/day N = Number of Cows
Td = 7 kg x 6=42 kg/day which is total manure available.
Calculating the total solids of fresh discharge (𝑇𝑠𝑓𝑑)
T  T x CT (4.5)
sfd d swt
Where, Tsfd = Ts of fresh discharge kg/day

CTswt = Concentration of TS in fresh discharge by weight kg TS/kg discharge
TS of fresh discharge = 42 kg x 0.18 = 7.56 kg where 0.18 is the TS of fresh manure(Khan,
2009).
2. Calculating the total influent
Tir =
Tsfd (4.6)
Tsf
c
Where,
Tir = Total influent required kg
Tsfc = Ts of favorable concentration %
46
According to (Mattocks, 1984) best biogas production occurs when total solid is ranged
from 7% to 10%. The most favorable TS concentration value is 8% for better biogas
production (Mukumba et al., 2017).
7.56 𝑘𝑔
To make a favorable condition, an 8% concentration of TS
𝑇𝑖𝑟 = = 94.5 𝑘𝑔
8%
3. Calculating water in the input influent (Moisture content or 100-x %)
Wa  Tir  Td
(4.7)
Wa = Daily water addition [kg
/day] Water to be added to make the discharge 8% concentration of TS
𝑊𝑎 =100 kg – 42 kg = 58 kg
4. Calculating the working volume of the digester
 Wvd  Vgs  Vf

T x HRT 

Wv   ir (4.8)
d  slurry 
 
 W
 vd  0.80V
Working volume of the digester, 𝑊𝑣𝑑 = 𝑉𝑔𝑠 + 𝑉𝑓
V V T x HRT
gs f  ir
slurry
kg
94.5 x 30 days
V V day 2835 kg


gs f kg kg
1090 1090
m3 m3
Wvd  2.752m3
The geometry of the bio-digester of the fixed dome type is simple as shown in Fig. 4.3. It
consists of two semi-spherical domes and a cylindrical shape connecting them. Even the
semi-spherical shapes are not identical; all the dimensions can be related to the main
diameter by the relations in Table 4.3.below.
When attempting to estimate the value of each of the geometrical dimension to build the
Bio- Digester, there are a group of assumptions to adopt. The main diameter and the total
volume play a vital role in designing the digester. The following table shows the geometry
relations of both main diameter and total volume.
47
Table 4-3: Assumptions for volume and geometrical dimensions (Mukumba et al., 2017)
For volume For geometrical dimensions

 𝑉𝑐 ≤5% V
1⁄
 D=1.3078 X 𝑉 3
 𝑉𝑠 ≤15% V  𝑉1 = 0.0827𝐷3
 𝑉𝑔𝑠 + 𝑉𝑓 = 80% V  𝑉2 = 0.05011𝐷3
 𝑉𝑔𝑠 = 𝑉𝐻  𝑉3 = 0.3142𝐷3
 𝑉𝑔𝑠 = 0.5 (𝑉𝑔𝑠 +𝑉𝑓 + 𝑉 )  𝑅1 = 0.725𝐷
K Where K = Gas production rate per  𝑅2 = 1.0625𝐷
m3 digester volume per day.  f1 = D/5
For this study K = 0.4 m3/day  f2 = D/8
 S1 = 0.911 D2
 S2 = 0.8345 D2
where D is the diameter of digester
From geometrical assumptions:
𝑉𝑔𝑠 + 𝑉𝑓 = 0.80𝑉
𝑉 = 2.752⁄0.8 = 3.44 𝑚3
Using empirical geometrical relations-following
1
D  1.3078 X V 3
(4.9)
(Putting value 𝑉𝑔𝑠 + 𝑉𝑓 = 2.752 𝑚3) and D = 1.3078 V 1/3 = 1.974 m ≅ 2 m

V  0.3142D3
3 3
V3  0.31422  2.514 (4.10)
m3
Combining Eq. 4.9 and 4.10, Digester height;

4 x0.3142 D3
H (4.11)
3.14D2
4 𝑥 0.3142 (2𝑚)3
= = 0.8 m
3.14(2𝑚)2
5. Calculating the Digester geometrical parameters
By knowing the value of ‘D’ and ’H’ we can find all other geometrical parameters.
Therefore the value of each parameter is calculated by substituting the value of diameter in
the above geometrical relation presented in table 4.5.
48
Now we find from the assumption as we know the value of 'D' and 'H'.
 𝑉1 = 0.0827𝐷3 = 0.662 𝑚3  f1 = D/5 = 0.4 m
 𝑉2 = 0.05011𝐷3 = 0.4 𝑚3  f2 = D/8 = 0.25 m
 𝑅1 = 0.725𝐷 = 1.45 𝑚
𝑚2
 S1 = 0.911 D2 = 3.644
 𝑅2 = 1.0625𝐷 = 2.13𝑚
𝑚2
 S2 = 0.8345 D2 = 3.34
4.3.2 Volume calculation of hydraulic chamber
Figure 4.3: Geometrical dimensions of the hydraulic chamber
Where, h = Distance between ground surface level and dome top m
h3 = Hydraulic chamber height m
H1= Height of gas layer inside V3 m
3.14 xD 2h
V  H 3 (4.12)
H
4
From volumetric assumptions
Vgs  (4.13)
VH
From assumptions, Vgs = 50 % of total daily gas yield

Ydg,total  Tsfd xYdg
(4.14)
Where, Ydg -Volumetric gas yield by TS mass [m3/Kg Tsfd] and Ydg, total - total volumetric
gas yield [m3/Kg Tsfd]
49
Vgs,vol  0.5Wvd Vs  K (4.15)
= 0.5 x (2.752 + (0.15 x 3.44)) x 0.4 = 1.07 m3
50
Again, Vgs = 50% of daily gas yield
Vgs,TS  0.5Ydg ,total xtinc  (4.16)
= 0.5 x TS x gas-producing rate per Kg of TS
The gas yield of cow dung = 0.34 m3/kg TS (Khan, 2005).
= 0.5 x (42 kg x 0.18) x 0.34 m3/kg TS
= 1.285 m3
From A and B let Vgs = 1.285 m3 because 1.12 > 1.07
𝑉𝑐 + 𝑉𝑔𝑠 = (0.05 𝑥 3.44 𝑚3) + 1.285𝑚3 =
1.457 𝑚3
As V1 is known from geometry and diameter D
 D2 x H 
V1  [Vc  Vgs    1
(4.17)

 4 
𝜋𝑥 (2𝑚)2𝑥
0.662 𝑚3 = [{1.457 𝑚3 𝐻1
}−{ }]
4
𝐻1 = 0.0253 m
From the geometry of the hydraulic chamber in the drawing above
h  h3  f1  H1
(4.18)
Where h is the height representing gauge pressure of the biogas (mm) of effluent volume.
Assume pressure inside dome h = 800 mm to 2000 mm H2O above atmospheric. 1
mm H2O = 10 N/m2 or 10 Pascal or 0.1 m Bar of pressure units.
Let h, is fixed @ 800 mm water volume (1 mm = 10 N/ m2)
h  0.8H  h3  f1  (4.19)
H1
h3 = (0.8 x 0.8 m) – (0.4 m + 0.0253 m)

h3 = 0.2147 m
Again from equation 1.28 and 1.29 DH can be derived as:
4VH 4x1.285
DH = = =2.76m (4.20)
3.14h3 3.14x0.2147
51
CHAPTER 5: EXPERIMENTAL SETUP AND TEST
PROCEDURES
5.1 Introduction
This chapter presents the description of the experimental setup and procedures for each
experiment mainly pyrolysis and anaerobic digestion.
5.2 Details of Experiment

The general experimental procedure followed in this work is illustrated as follows using
the flow chart of fig 5.1.
Pyrolysis Experiment Characterization of Characterization of

(Biochar production) Biochar (Surface Fermentation materials
area)
Characterization of Selected
Cow dung Inoculum
Biochar (Proximate)
Anaerobic Digestion Experiment
Methane rich biogas
Figure 5.1: General experimental procedures of the present work
As shown in figure 5.1. first biochar has to be produced with slow pyrolysis method at
different temperature and characterized. Also substrate and inoculum has to be
characterized and finally goes into anaerobic digestion experiment for biogas production.
5.3 Experimental setup and procedures for corn cob pyrolysis

The slow pyrolysis of corn cob was conducted using a muffle furnace. Initially, the
crucible was weighed, and then the corn cob sample was added into the crucible and
covered it with the lid for performing each run. During this process, the desired
temperature was maintained for the desired period to undergo the pyrolysis process.
52
Figure 5.2: Loading of sample to the crucible and then to furnace for CC-BC production
After attaining the required values of the temperature, the particular pyrolysis process was
initiated for the desired time. After achieving the required process time with a stabilized
temperature pyrolysis process was completed and biochar is produced in the crucible. The
experimental process variables used in this study were temperature between 300 ℃ and
600℃, reaction time from 30 to 90 min.
Figure 5.3: Unloading of a sample from furnace and weight of CC-BC
After completion of the process, the furnace was turned off and the cooling unit was started
using a desiccator to drop the temperature of produced biochar up to 25 ℃. After cooling
down, the solid biochar was collected manually from the crucible. However, the gases
produced during pyrolysis were in small quantity and therefore vented out. Finally, it goes
to characterization and is used for the desired application which was an anaerobic digestion
test. A similar procedure was followed for the pyrolysis of all nine samples at different
53
reaction times and temperatures.
54
5.4 Experimental setup and procedures for CC-BC characterization
5.4.1 Iodine number test
The surface area in (mg/g) was determined by following the test method of ASTM D4607-
94 (ASTM D4607-94, 2007) which explains the detailed methodology of iodine adsorption.
Figure 5.4: Iodine number determination for CC-BC
The physicochemical properties of a selected sample of corn cob derived biochar was
determined by following the procedure furnished by ASTMD 1762-84 which was
described in the methodology section.
5.4.2 Moisture content and Total solid
Heat the muffle furnace to 750℃ and place previously ignited porcelain crucibles and
covers in the furnace for 10 min. cool the crucibles in a desiccator for 1 h.
55
Figure 5.5: Adjusting muffle furnace and loading sample for TS of CC-BC450
Weigh the crucibles and add to each approximately 1 g, weighed to the nearest 0.1 mg, of
the ground sample.
Figure 5.6: Weigh of crucible and sample for TS of CC-BC450
Place the samples in the oven at 105℃ for 2 h. Place the dried samples in a desiccator for
1 h and weigh.
56
Figure 5.7: Weight of crucible and sample after drying for TS of CC-BC450
5.4.3 Volatile matter
Heat the muffle furnace to 950℃. Preheat the crucibles used for the moisture
determination, with lids in place and containing the sample, as follows: with the furnace
door open, for 2 min on the outer ledge of the furnace (300℃) and then for 3 min on the
edge of the furnace (500℃). Then move the samples to the rear of the furnace for 6 min
with the muffle door closed. Watch the samples through a small peep-hole in the muffle
door. If sparking occurs, results will be in error. Cool the samples in a desiccator for 1 h
and weigh.
Figure 5.8: Adjusting furnace and loading of sample for VS of CC-BC450
57
Figure 5.9: Weight of crucible and sample after ignition for VS of CC-BC450
5.4.4 Ash content

Place the lids and the uncovered crucible used for the volatile matter determination, and
containing the sample in the muffle furnace at 750℃ for 6 h. Cool the crucibles with lids
in place in a desiccator for 1 h and weigh.
Figure 5.10: Ash content of CC-BC450
5.5 Experimental setup and procedures for substrate characterization

The physicochemical properties of the sample were determined by the following procedure
furnished by APHA 1995.
58
5.5.1 Total solid (TS)
These were the procedures followed for TS determination; A crucible was properly washed
and dried in the laboratory oven at a temperature of 105 ℃ for one hour. The crucible was
stored and cooled in a desiccator until needed. The crucible was re-weighed before use (g).
The laboratory oven was switch on and allowed to reach a temperature of 105 ℃. This
temperature was maintained throughout the experiment.
Figure 5.11: Weight of crucible after cleaning, heating and adjusting oven for TS of CD
10g of freshly collected samples were weighed using an electrical balance (digital weight
measuring device) and placed inside an electric hot air-oven maintained at 105 ℃ using a
crucible. The crucible was allowed to stay in the oven for 24 hours, then taken out, cooled to
room temperature in a desiccator, and weighed.
59
Figure 5.12: Weight and Loading of the crucible with the substrate for TS of CD
5.5.2 Volatile matter

The following procedures were followed in the determination of the volatile solid of the
substrates used. A known mass of residue obtained from the determined of the total solids
is placed in a silica crucible and ignited in a muffle furnace at 550 + 50℃ for 30 minutes.
Then the crucible is taken out of the muffle furnace, partially cooled in air, kept in
desiccators for few minutes, and then weighed.
5.6 Experimental setup and procedures for Anaerobic digestion

The AD experiments were conducted in plastic bottles of 1 liters capacity used as a
digester at mesophilic temperature (37℃±1℃) with a working volume of 0.8L. The
control and digesters amended with corn cob derived biochar at four different
concentrations (4, 6, 8, and 10 g/L of media) were investigated. Each experimental
condition was conducted in duplicate, with all digesters placed in a water bath. Five
samples, one without biochar and four with the addition of biochar were prepared with
inoculum by mixing the cow manure and biochar. To set the TS value to 8%, water was
added to the prepared samples. The experimental sets were labeled as ADM0, ADM1,
ADM1.5, ADM2, and ADM2.5.
60
Table 5-1: Experimental conditions used for anaerobic batch experiments
Labels Ingredients
Test 1 Test 2
ADM0 Inoculum + substrate Inoculum + substrate
ADM1 ISB (4 g/800L of media) ISB (4 g/ 800L of media)
ADM1.5 ISB (6 g/ 800L of media) ISB (6 g/ 800L of media)
ADM2 ISB (8 g/ 800L of media) ISB (8 g/ 800L of media)
ADM2.5 ISB (10 g/ 800L of media) ISB (10 g/ 800L of media)
The experiment was done using a total of 10 aforementioned capacity plastic bottles placed
in a water bath at 37℃. The plastic digester's effective volume was fully immersed in the
bath and equipped with a stretchable tube having a roller as a valve which is directly
connected to the urine bag and then to the reversed graduated cylinder for biogas
measurement. Biogas formed was measured by the liquid displacement method. The valve
was used to control the flow of gas for composition analysis.
Figure 5.13: The experimental set up of batch anaerobic digestion
5.7 Measuring yield and quality of biogas

The gas production was measured by water displacement method whereas the quality,
which is the content of methane from the biogas, is estimated by the displacement of
61
sodium
62
hydroxide solution. The gas produced in the plastic bottle was captured in the airbag and
allowed to pass to a graduated cylinder filled with water. When a gas bubble entered the
graduated cylinder with water, the gas replaced the water, which was then forced out of the
graduated cylinder. The displaced water indicates the total volume of biogas produced.
Note that a small amount of gas coming out of the digester which is stored in the airbag
also allowed passing through a 5% NaOH solution in another inverted graduated cylinder..
The CO2 and H2S from the biogas would be retained in the solution whereas the methane
would displace its equivalent volume of NaOH. Collecting the displaced solution and
measuring its volume using a measuring cylinder would give the volume of methane from
the produced biogas
Figure 5.14: Measurement of biogas using the water displacement method
63
CHAPTER 6: RESULT AND DISCUSSION
6.1 Introduction
This section describes the results obtained during the laboratory scale experiment of
anaerobic digestion of cow dung. The characteristics of biochar and substrates used in the
study, biogas production, CH4 production without and with biochar addition are presented.
The experiments were conducted in a 1 L reactor with different concentrations of biochar
to achieve the objectives of the thesis.
6.2 Characteristics of CC-BC at Different Operating conditions

The important physical characteristics of biochar is specific surface area (SSA). These
characteristics are affected by different feedstock and operating conditions of pyrolysis
(Masebinu et al., 2019). The surface area of CC-BC produced at different pyrolysis
temperatures and reaction time was determined using the iodine number test method
(ASTM D4607-94, 2007) as shown in fig. 6.1.
80
75
CC-BC350
Iodine Number(mg/g)
70
CC-BC450
CC-BC550
65
60
55
50
30 40 50 60 70 80 90
Holding time(min)
Figure 6.1: Effect of temperature and time on SSA of CC-BC

Pyrolysis temperature strongly affects the surface area of biochar. CC-BC550 had the
highest surface area (78.14 mg/g) than CC-BC450(75.58mg/g) and CC-BC350
(52.58mg/g). This result indicates that the surface area of the biochar was directly
64
correlated with pyrolysis
65
temperature. But according to (Masebinu et al., 2019) the higher the pyrolytic temperature,
˃450℃, the more suitable the biochar is for the adsorption of organic contaminants,
because of the improved surface area, the increased distribution of micropores, and the
higher level of hydrophobicity.
However, due to the loss of oxygen-containing and hydrogen-containing functional groups

at temperatures above 450℃, the capacity to adsorb organic contaminants will be impacted
negatively. Conversely, biochar produced at lower temperatures, less than 450℃, is
suitable for the adsorption of inorganic and nonpolar organic contaminants. CO 2 being a
nonpolar compound can be adsorbed into the sorption sites of biochar and retained in the
appropriately sized pores (Masebinu et al., 2019). Considering the aforemention reasons
CC-BC450 was selected for the study and sent to further characterization.
Moisture content, yield, ash, volatile matter, and resident matter contents of selected CC-
BC at pyrolysis temperatures of 450℃ for 60min. The result of proximate analysis (MC,
AC and VM) of the corn cob derived biochar according to ASTM D1762-84 has shown in
Table 6.1. Table 6-1: CC-BC characterizations produced at 450℃ and 60 minutes
Parameter Mass of Mass of Temperature Residence Result
crucible, g sample, g ,℃ time, min in (%)
TS 40.1 w1  1 105 1440 96.5

Moisture 40.1 w1  1 105 1440 3.5
VM 40.1 w2  0.965 950 11 32.22
Ash 40.1 w3  0.654 750 3600 5.07
6.3 Characteristics of the substrates used

The fresh cow dung were analyzed with respect to total solids and volatile solid content,
moisture content and pH. The characteristics of CD a single substrate and inoculum were
determined and the results are shown in Table 6.3 below. When the CD and inoculum were
characterized, the mean value of the total solid and volatile solid for CD were 16% and
84.5
% and for inoculum were 17.3 % and 83% respectively.
66
Table 6-2: Intial characteristics of the substrate
Materials Types of analysis
TS (%) VS (%) MC (%) pH
Cow dung 16 84.5 84 7.12
Inoculum 17.3 83 83.7 6.89
Total solids concentration is one of the most important waste characteristics. As indicated
in Table 8, fresh cow dung has a TS of 16 in percentage. But according to (Mukumba et al.,
2017) and (Mattocks, 1984), 8% of TS is favorable for AD. As a result, some amounts of
water have to be added to prepare a wet organic feed mixture with 8% total organic solids
for biogas production in the anaerobic fermentation process.
The pH is regarded as the key indicator of operational stability. The initial pH of input
substrate and inoculum before seed into digester was 7.12 and 6.89 respectively. So this
result was in agreement with a pH range of input mixture in the digester between 6.80 and
7.60, which is suitable for anaerobic microorganisms. The VS is an important factor in
determining the BMP of a particular type of biomass, as the VS is broken down to produce
biogas. According to (Deublein and A. Steinhauser, 2011), the amount of VS in the manure
determines the biogas yield from the AD process to produce methane gas.
The value of VS indicates that fresh cow manure contains high organic matter which
explains energy content for biogas production. The results of the proximate analysis of feed
material showed that the moisture content of the cow dung was 84%. This result is
comparable with the study done by (Zhang et al., 2007) who carried out the study on cattle
manure and found that the optimum moisture content was 74 to 90%. Therefore, the result
is more likely similar to this researcher.
6.4 Lab-scale biogas production
Ten number of lab-scale anaerobic digesters were developed and utilized for the digestion
of cow dung as a single substrate in this study. The AD experiments were conducted for
approximately 33 days to examine biogas production from cow dung with various
concentration of biochar using digesters labeled as ADM 0, ADM1, ADM1.5, ADM2, and
ADM2.5, where M represents the temperature and the number after M represents the
concentration of CC-BC450 (g/800L of digester) divided by four which was shown in the
experimental setup. The production of biogas started on 14th days for all digesters.
67
6.4.1 Measurement of Biogas production
The production of biogas was observed and volumes of the biogas collected were recorded
during the experiment period of 33 days. Biogas production was measured until biogas
production was reduced. The daily biogas production rates from the digestions of the CD
without the addition of biochar in ADM0 and with the addition of biochar in ADM1,
ADM1.5, ADM2, and ADM2.5 are shown in Fig. 6.1. It was observed that biogas production
started on the 14th day in all the digesters, and increased for consecutive days. After that, it
reached its peak point. The peak values of daily biogas production rates were found to be
93, 83, 72, 68, and 57 mL/day after 29, 23, 27, 25 and 29 days of digestion from ADM 1,
ADM1.5, ADM2, and ADM2.5 respectively.
ADM0(Control)
100 ADM1 (4g/800ml)
ADM1.5
(6g/800ml) ADM2
Daily biogas production (mL)
80 (8g/800ml)
ADM2.5
60
40
20
0
0 5 10 15 20 25 30
Retention time (Days)
Figure 6.2: Daily biogas production of cow dung
The digester ADM0 followed by ADM1 produced biogas at higher rate per digester volume
than the other three digestion tests during periods of the experiment, this maximum rate
indicates that CD can be used as a single substrate for the production of energy but still
needs additives to enhance energy quality.
As shown in fig 6.2, in the first 14th day of experimnt, biogas production was not formed
yet and tend to decrease at the end period of experiment. This is predicted due to the biogas
68
production rate in batch condition is directly corresponds to specific growth rate of
69
methanogenic bacteria in the digester. In the range of 13 to 30 days observation, biogas
production is significantly increase due to exponential growth of microorganisms.
6.5 Effect of CC-BC450 on Biogas and Methane Production

The current study was conducted to examine the beneficial effect of biochar on methane
production. The results show that the biochar addition significantly increased methane
production.
6.5.1 Identification of biochar concentration for highest biogas production

The time course of cumulative biogas production for the digestion of CD for different
experimental conditions is shown in Fig. 6.2.
ADM0(Control)
160
ADM1 (4g/800ml)
0
ADM1.5
Cumulative biogas pproduction (mL)
(6g/800ml) ADM2
(8g/800ml)
120
0
100
0
800
600
400
200
0 5 10 15 20 25 30
Figure 6.3: Cumulative biogas production
This experiment indicates that there was higher biogas production for ADM 0 (1491.1 mL),
(1244 mL) for ADM1, (1062 mL) for ADM1.5, (755.5 mL) for ADM2 and for ADM1.5
(728.5
mL) per volume of the digester respectively. Cumulative biogas production decreased with
the increase of biochar concentration. Biogas production of all biochar-amended digesters
was significantly lower than that of ADM0. This is due to trace elements of biogas such as
carbon dioxide and hydrogen sulfide were adsorbed into adsorption site of CC-BC450, and
this result is consistent with (Shen et al., 2015).
70
6.5.2 Identification of biochar concentration for highest CH4 production
Fig. 6.4 shows the daily methane production of each group of experiments. all digester
showed a gradual increase of daily methane production and eventual decrease afterward.
The rest of the digesters with the addition of CC-BC450 (ADM 1, ADM1.5, ADM2, and
ADM2.5) showed high daily methane production than those of the ADM0. There was
methane production from the ADM1 with the second-lowest peak methane production and
there were small peaks of methane production in the late stage of AD. This performance
may be explained by the presence of toxic organic compounds in CD, causing a decrease of
the microbes’ activity and the inhibition of cow dung anaerobic digestion.
60 ADM0
ADM1 (4g/800ml)
ADM1.5 (6g/800ml)
Daily methane production (mL)
50 ADM2 (8g/800ml)
ADM2.5
(10g/800ml)
40
30
20
10
0
0 5 10 15 20 25 30
Figure 6.4: The time course of methane production rate for the tested conditions
The increased methane yields in the late stage were the result of recovered microbial
activity and decomposition and utilization of organic compounds in CD due to the
presence of CC-BC450.
The digesters with CC-BC450 addition attained high peaks of daily methane production
than ADM0 and declined slowly afterward, indicating that the addition of CC-BC450
mitigates the inhibitory effect of CD on the AD system. The addition of CC-BC450 can
reduce the microbial adaptation period and lead to a more rapid onset of the growth phase
(Mumme et al., 2014).
71
ADM0
700 ADM1 (4g/800ml)
Cumulative methane production (mL)

ADM1.5
600 (6g/800ml) ADM2
(8g/800ml)
500 ADM2.5
400
300
200
100
0
0 5 10 15 20 25 30
Figure 6.5: Cumulative methane production with various concentration of biochar
Fig.6.4 shows the cumulative methane production obtained in each group of experiments.
In the first 13 days, there were no difference in methane production was observed between
all digesters. All digesters showed uniform and similar trends, exhibiting a slow increase
during the first 20 days and then a rapid increase after the 20th day.
The cumulative methane production of the ADM2.5 exceeded that of the ADM1.5 on the
23rd day and exceeded that of the ADM1 on the 21st day. For ADM1, ADM1.5, ADM2, and
ADM2.5, the cumulative methane production at the last stage was much higher than that of
the control reactor, indicating that these four biochar samples can rapidly alleviate the
toxicity of CD and accelerate the degradation of organics so that AD can start quickly.
Simultaneously, in the presence of CC-BC450, all digesters showed a slight improvement
in accumulative methane production. This indicated that CC-BC450 addition could
accelerate CD digestion in the whole anaerobic process and result in higher methane
production.
72
1600 Max. biogas production
1491.1
(mL) Max.methane
1400 production(mL)
Max. biogas and CH production (mL)
1244
1200
1062
1000
800 755.5 728.5

4
647
600 540
486
444
392.5
400
200
0
ADM0 ADM1 ADM1.5 ADM2 ADM2.5
Reactors
Figure 6.6: Maximum biogas and CH4 vs CC-BC450 concentrations
CH4 (%) and CH4 increament per reactor
83.43
74.12
Methane
45.76
35.69 39.33
26.31 27.31
0 11.5 19.23

Digesters
Methane (%) Methane Increament (%)
Figure 6.7: Percentage of methane by volume and its increament per digesters
73
6.6 Analysis of the cumulative CH4 with the Modified Gompertz Model
The results of methane gas produced in each run were plotted against time and were fitted
using the modified Gompertz model to determine the highest methane production (mL) as
shown from Fig.6.5. to Fig. 6.10.
ADM0 Experimental value

400
Cumulative methane production
ADM0 Predicted value
300
200
100
(mL)
0
0 5 10 15 20 25 30
Figure 6.8: Methane production (mL) without CC-BC450 to CD in an 800 mL of a 1 L lab-

scale bioreactor in batch fermentation.
500
ADM1 Exerimental
value ADM1
400
300
200
100
(mL)
0
0 5 10 15 20 25 30
Figure 6.9: Methane production (mL) with a dosage of 4g CC-BC450 to CD in an 800 mL

of a 1 L lab-scale bioreactor in batch fermentation.
74
500 ADM1.5 Experimental

value ADM1.5 Predicted
400
300
200
100
0
0 5 10 15 20 25 30
Figure 6.10. Methane production (mL) with a dosage of 6g CC-BC450 to CD in an 800

mL of a 1 L lab-scale bioreactor in batch fermentation.
70
0 ADM Experimental
2
60 ADM Predicted
2
0
50
0
40
0
30
0
20
0
10 0 5 10 15 20 25 30
Figure 6.11: Methane production (mL) with a dosage of 8g CC-BC450 to CD in an 800 mL

of a 1 L lab-scale bioreactor in batch fermentation.
75
600
ADM 2.5 Experimental

500 ADM 2.5 Predicted
400
300
200
100
0
0 5 10 15 20 25 30
Figure 6.12. Methane production (mL) with a dosage of 10g CC-BC450 to CD in an 800
mL of a 1 L lab-scale bioreactor in batch fermentation.
700
ADM0 Experimental
600 ADM0 Predicted
ADM1 Experimental
ADM1 Predicted
500 ADM1.5 Experimental
ADM1.5 Predicted
ADM2 Experimental
400
ADM2 Predicted
ADM2.5 Experimental
300 ADM2.5 Predicted
200
100
(mL)
0
0 5 10 15 20 25 30
Figure 6.13: Comparison of methane production (mL) at a different dosage of CC-BC450

to CD in an 800 mL of a 1 L lab-scale bioreactor in batch fermentation.
76
The results obtained from the modified Gompertz equation is given in Table 6.3. The
highest methane production was found in run ADM2.5 that representing the dosage of
8g/800mL, which corresponding to the Gompertz constants of P = 592.82 ml, Rm = 56.517
mL/day, and L=18.527 days. Meanwhile, the trends of methane production obtained were
comparable among other runs that contained CC-BC450 at different concentrations.
Table 6-3: Modified Gompertz equation parameter values for CH4 production (per 800 ml
working volume)
AD P (mL) Rmax (mL/day) L(day) R2
ADM0 363.09 35.348 18. 42 0.993
ADM1 422.94 43.050 18.348 0.994
ADM1.5 462.22 46.501 17.65 0.994
ADM2 592.82 56.517 17.53 0.990
ADM2.5 507.57 53.062 17.527 0.997
The experimental data of cumulative methane production was also fitted using the
Gompertz model and the fitted curves were presented. The R2 of all of the fittings ranged
from 0.993 to 0.997, suggesting a good fitting between experimental data and the modeling
results, thus the feasibility of using the Gompertz model for the calculation of λ, P, and
Rmax. As shown in Table 6.3, the Rmax of the digesters with biochar additions were higher
than that of the control. However, the Rmax increased as the biochar addition increased from
0 to 8 g/800 mL biochar and then decreased as the biochar addition was further increased
to 10 g/800 mL. The P of all digesters amended with biochar was higher than that of the
control, whereas, the digesters with higher biochar additions (10g/800mL) showed lower P.
The highest P was achieved for the culture with an 8 g/800 mL biochar addition. By adding
CC-BC450, λ of ADM1 decreased from 18.42 days to 18.348 days; λ of ADM 1.5, decreased
from 18.42 days to 17.65 days; λ of ADM 2 decreased from 18.42 days to 17.53 days, and λ
of ADM2.5 decreased from 18.42 days to 18.527 days, respectively. Similarly, Luo et al.
(2015) reported that addition of fruitwood derived biochar (10 g/L) shortened the λ by
16.5%, 11.4%, 30.3% and 21.6% during AD of 2 g/ L, 4 g/L, 6 g/L and 8 g/L of glucose,
respectively. Additionally, the experimental data from (Jang et al., 2018) indicated that By
adding M-BC, λ of P1 and P10 decreased from 10.81 d to 10.48 d and 9.26 d; λ of M1 and
M10 decreased from 2.08 d to 1.87 d and 1.52 d; λ of T1 and T10 decreased from 3.94 d to
3.58 d and 2.98 d, respectively.
77
6.7 Evaluation against literature data
The results from the present study are compared with the literature data. Similar studies
report the beneficial effects of biochar on CH4 production (Table 6.4). The present work
suggested strong evidence of the increment of CH4 production with the addition of biochar,
in good agreement with other studies in the literature using various wastes as the feedstock.
The results of the current study are within the range of the findings of other studies. At the
appropriate dosage of biochar, the CH4 production increased by 2-44% compared to the
control, depending on the types and addition ratio of biochar, the feedstock of AD, and
operating conditions as reported by (Mumme et al., 2014a), (Xu et al., 2015),(Lü et al.,
2016), (Fagbohungbe et al., 2016), (Lü et al., 2016), (Jang et al., 2018) and (G. Wang et al.,
2018) respectively.
Table 6-4: A comparison of the current experimental results with the literature data on the
batch lab-scale methane production with the addition of different types of biochar
Feedstock Feedstock of Biochar Operating condition Methane yield

of AD biochar addition (Type, Temperature, compared to
(g/L) and pH) control (%)
AD Sludge Paper sludge 20 Batch, 42℃, and 32
and WH N.A
DM Diary manure 1-10 Batch, 35℃ and 7.7 5-24.5
Food waste Fruit woods 2-10 Batch,35℃ and 7 39-44
FW and AS Sawdust 2-15 Batch, 35℃ and 2-4
N.A
Glucose Fruit woods 10 Batch, 35℃ and 7 11.5
This study Corn cob 4-10 Batch, 37℃ and 39.33
7.12
78
CHAPTER 7: CONCLUSION AND RECOMMENDATIONS
7.1 Introduction
The outcomes of this study have contributed useful experimental data on the effect of
utilizing biochar in AD to enhance CH 4 production in lab-scale AD. This chapter tells the
key conclusion and recommendations as follows.
7.2 Conclusions
While much work has been done in modifying the biochar for adsorption of desired organic
or inorganic compounds, very less is known on its application in anaerobic digestion, and
the overall quality of the biogas. In this study the effect of biochar addition on the CH 4
production in laboratory scale AD of cow dung under the same initial pH and mesophilic
conditions has been studied.
Physicochemical analysis of corn cob biochar showed positive results for using CCBC450
in AD to improve biogas quality when compared with the control sample. The results of
this study show that the reprocessing of crop residues such as corn cob into biochar and its
application to AD was beneficial in many ways. Due to its physicochemical properties,
biochar derived from corn cob, has been shown to improve biogas quality. The application
of AC to AD also has similar advantage but direct disposal of AC with effluent would
cause additional concerns for environmental pollution and safety (Luo et al., 2015). Thus,
the use of biochar instead of AC has the potential to reduce the extent of environmental
issues.
The most important finding from this research was that the CC-BC450 added to reactor
has significant effect to cummulative methane production and methane production rate.
The effect of biochar addition on CH4 production in AD was observed and increased the
maximum CH4 production by 11.59-39.33%. The optimum biochar addition was found to
be 8g/800 (mL). Under the optimum condition, the P and Rmax were 592.82 mL and
56.517 mL/day. It is found that the quality of biogas produced mostly depends on the
concentration of biochar added based on their surface area value and, the best performance
of methane production was obtained at CC-BC concentration of 8g/800 (mL).
From the result obtained, cow dung which can be found in abundance everywhere in
Ethiopia, are a very good feedstock for biogas production, and utilizing CC-BC can also
increase the quality of gas production. In conclusion, based on the results derived from this
79
study, as well as previous studies, biochar should be considered as an alternative solution
for
80
increasing energy quality from biogas and environmental problems, also it has been
demonstrated as an eco-friendly system.
7.3 Recommendations
The previous literature and the present study demonstrated the possibility of
increasing the quality of biogas using biochar amended digeste as well as AD stabilityr.
The overall objectives of the present study have been achieved. However, various new
gaps have also been identified during the evaluation of the findings of the current study due
to the lack of information regarding the surface properties of the biochar samples, and how
they can influence fundamental biochemical processes. Based on this thesis work, the
following recommendations are suggested for future research which is related to biogas
production using biochar.
 The biochar used in the study, however, was only limited to one type of biochar,
which was the CC biochar, prepared at 450C. Considering the different
characteristics which may be possessed by different types of biochar prepared
under different operating conditions, their effects and mechanisms in AD may be
different. There could be some biochars that may not show the same or similar
beneficial effects as CC-BC450 studied in the present work does and it would be
scientifically interesting and practically useful to clearly define the key
characteristics of biochar and relate them to the biochar effects in enhancing CH4
production in AD operations. Therefore, further studies using different types of
biochar in AD are recommended.
 This work was done on the study of effect of CC-BC450 under a fixed set of
operating conditions, further studies has to be done to examine the effect of CC-BC
addition under various operating conditions.
 Also, the characteristics of CC-BC is limited to surface area and proximate which
was clearly clear understood that, how pyrolysis temperature influences factors as
surface area, and from this analysis, the potential uses of the biochar as an additive
for AD processes. However, in future work further characterization has to be done
to clearly define the characteristics of any biochar applied for study including
scanning electron microscopy (SEM) and elemental analysis should be performed
to determine the exact composition and morphology of CC-BC biochar samples.
 The results of the present study show the potential benefit of using CC biochar in
anaerobic digestion in laboratory scale on batch basis, but more research is required
to fully understand how lab-scale results can be translated to commercial scale
systems.
81
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APPENDICES
Appendix A: Biochar Production Data Sheet

Sample Mass of Mass of Temperature, Residence time Mass of Mass of biochar
crucible, CB °C (min.) crucible + produced(yield), g
g sample, g sample, g
1 114.2 43 350 30 129.4 15.2
2 118.3 42 350 60 133.3 15
2 115.5 45.5 350 90 130.2 14.7
4 114.2 42.1 450 30 125.9 11.7
5 115.5 44.8 450 60 126.9 11.4
6 58.6 20 450 90 64.1 5.5
7 58.6 20 550 30 63.7 5.1
8 56.1 20 550 60 61.3 5.2
9 57 20 550 90 62 5
Appendix B: Biochar Sample Characterization, Surface Area Data Sheet
Aim P(mL) R(N) S(mL) in triplicate N1(N) I(mL) S(mL) in triplicate N2(N)
Solution 1 2 3
standard 25 1 2 3 0.1361 15. 15. 15. 0.084
ization 0.1 18.1 18.9 18.1 7 25 6 4 4 2
Note: N1= (P*R)/S and N2=(S*N1)/I
90
Appendix C: Biochar Sample Characterization, Proximate Data Sheet
Biochar characterization produced at 450℃ and 60 minutes
METHOD: APHA 1995
The material used: locally available corn cob
Mass of Mass of Temperature, Residence Result
crucible, sample, g ℃ time, min
Parameter (%)
g
Total solid 40.1 w1  1 105 1440 96.5
Moisture 40.1 w1  1 105 1440 3.5
volatile matter 40.1 w2  0.965 950 11 32.22
Ash 40.1 w3  0.654 750 3600 5.07

w4  0.0149
Appendix E: Cow dung sample characterization before and after digestion

Substrate characterization experiment
METHOD: APHA 1995
The material used: Fresh cow dung
Result
Parameter A B C Temperature, ℃ Residence time, min %
Total solid 58.7 68.7 60.3 105 1440 16
Moisture 58.7 68.7 60.3 105 1440 84
volatile matter 58.7 60.3 58.95 600 30 84.5
pH 7.12
91
Appendix F: Anaerobic digestion experiment results
A. Biogas production rate (mL/day)
Daily biogas production (mL/day)
Retention ADM1 ADM1.5 ADM2 ADM2.5

ADM0
Time
Control 4g/800ml 6g/800ml 8g/800ml 10g/800ml
1 0 0 0 0 0
2 0 0 0 0 0
3 0 0 0 0 0
4 0 0 0 0 0
5 0 0 0 0 0
6 0 0 0 0 0
7 0 0 0 0 0
8 0 0 0 0 0
9 0 0 0 0 0
10 0 0 0 0 0
11 0 0 0 0 0
12 0 0 0 0 0
13 0 0 0 0 0
14 26 24 18 16 12
15 43 42 37 21 15.5
16 49 48 45 21 18
17 55 54 50 24 19
18 60 59 48 29 22.5
19 62 58 59 32 23
20 74 69 63 34 31
21 79 74 59 45 34.5
22 83.5 74 61 47 38
23 88 83 63 50 43
24 93 79 69 64 51
25 97 76 70 68 54.5
26 87 73 68 64 51
27 89 71 72 45 53
28 88 71 57 43 53.5
29 93 77 58 39 57
30 91 63 47 37 50
31 88.5 66 52 31 44
32 73 49 37 26.5 32
33 72.1 34 29 19 26
92
B. Cumulative biogas production (mL)
Cumulative biogas production(mL)
Retention ADM0 ADM1 ADM1.5 ADM2 ADM2.5

Time Control 4g/800ml 6g/800ml 8g/800ml 10g/800ml
1 0 0 0 0 0
2 0 0 0 0 0
3 0 0 0 0 0
4 0 0 0 0 0
5 0 0 0 0 0
6 0 0 0 0 0
7 0 0 0 0 0
8 0 0 0 0 0
9 0 0 0 0 0
10 0 0 0 0 0
11 0 0 0 0 0
12 0 0 0 0 0
13 0 0 0 0 0
14 26 24 18 16 12
15 69 66 55 37 27.5
16 118 114 100 58 45.5
17 173 168 150 82 64.5
18 233 227 198 111 87
19 295 285 257 143 110
20 369 354 320 177 141
21 448 428 379 222 175.5
22 531.5 502 440 269 213.5
23 619.5 585 503 319 256.5
24 712.5 664 572 383 307.5
25 809.5 740 642 451 362
26 896.5 813 710 515 413
27 985.5 884 782 560 466
28 1073.5 955 839 603 519.5
29 1166.5 1032 897 642 576.5
30 1257.5 1095 944 679 626.5
31 1346 1161 996 710 670.5
32 1419 1210 1033 736.5 702.5
33 1491.1 1244 1062 755.5 728.5
93
E. CH4 Production rate, mL/day
Daily CH4 Production, mL/day
Retentio ADM0 ADM1 ADM1.5 ADM2

n ADM2.5
Control 4g/800ml 6g/800ml 8g/800ml 10g/800ml
Time
1 0 0 0 0 0
2 0 0 0 0 0
3 0 0 0 0 0
4 0 0 0 0 0
5 0 0 0 0 0
6 0 0 0 0 0
7 0 0 0 0 0
8 0 0 0 0 0
9 0 0 0 0 0
10 0 0 0 0 0
11 0 0 0 0 0
12 0 0 0 0 0
13 0 0 0 0 0
14 6 7 7 3 1.5
15 7 10 9 6 3.5
16 8.5 10.5 9.5 10 5
17 9.5 12 15 20 6
18 11.5 15 21.5 24 20
19 13 16 26 25 21.5
20 15 25 29 31.5 26
21 20 31 34.5 34 34
22 27 33 36 36.5 43
23 33 36 39 42 51
24 35 38 40 47 53
25 30 42 39.5 51 45
26 30 42 43 49 42
27 31 30 36.5 48.5 40
28 29.5 29.5 32 49 37
29 20 33 27 54 25
30 19.5 16 15.5 40 24.5
31 17 9 13 36 22
32 16 7 8 25.5 21
33 14 2 5 15 19
94
F. Cumulative CH4 Production (mL)
Cumulative CH4 Production, mL/day
1 0 0 0 0 0
2 0 0 0 0 0
3 0 0 0 0 0
4 0 0 0 0 0
5 0 0 0 0 0
6 0 0 0 0 0
7 0 0 0 0 0
8 0 0 0 0 0
9 0 0 0 0 0
10 0 0 0 0 0
11 0 0 0 0 0
12 0 0 0 0 0
13 0 0 0 0 0
14 6 7 7 3 1.5
15 13 17 16 9 5
16 21.5 27.5 25.5 19 10
17 31 39.5 40.5 39 16
18 42.5 54.5 62 63 36
19 55.5 70.5 88 88 57.5
20 70.5 95.5 117 119.5 83.5
21 90.5 126.5 151.5 153.5 117.5
22 117.5 159.5 187.5 190 160.5
23 150.5 195.5 226.5 232 211.5
24 185.5 233.5 266.5 279 264.5
25 215.5 275.5 306 330 309.5
26 245.5 317.5 349 379 351.5
27 276.5 347.5 385.5 427.5 391.5
28 306 377 417.5 476.5 428.5
29 326 410 444.5 530.5 453.5
30 345.5 426 460 570.5 478
31 362.5 435 473 606.5 500
32 378.5 442 481 632 521
33 392.5 444 486 647 540
95
G. Predicted values of commulative methane production

1 0 0 0 0 0
2 0 0 0 0 0
3 0 0 0 0 0
4 0 0 0 0 0
5 0 0 0 0 0
6 0 0 0 0 0
7 0 0 0 0 0
8 0 0 0 0 0
9 0 0 0 0 0
10 0 0 0 0 0
11 0 0 0 0 0
12 0 0 0 0 0
13 0.02 0.01 0.05 0.03 0
14 0.16 0.13 0.43 0.22 0.03
15 0.86 0.91 2.16 1.21 0.27
16 3.22 3.91 7.47 4.57 1.62
17 9.06 11.96 19.44 13.01 6.33
18 20.39 28.07 40.63 29.72 17.95
19 38.54 53.87 71.72 56.99 39.87
20 63.52 88.65 111.17 95.24 73.44
21 94.02 129.68 155.84 142.78 117.23
22 127.89 173.41 202.22 196.51 167.7
23 162.82 216.51 247.19 252.79 220.59
24 196.78 256.52 288.58 308.34 272.1
25 228.32 291.99 325.17 360.63 319.52
26 256.57 322.36 356.52 408.05 361.35
27 281.16 347.68 382.73 449.81 397.03
28 302.1 368.34 404.25 485.73 426.71
29 319.62 384.95 421.67 516.08 450.92
30 334.07 398.14 435.61 541.34 470.39
31 345.87 408.52 446.67 562.13 485.85
32 355.42 416.64 455.38 579.09 498.04
33 363.09 422.94 462.22 592.82 507.57
96
H. Cumulative biogas production and CH4 (%) and CH4 increament

Digesters Control 8g/
4g/800ml  6g/800ml 10g/
800ml 800m
Biogas (mL) 1491.1 1244 1062 775.5 728.5
Methane (%) 26.31 35.69 45.76 83.43 74.12
Others NA NA NA NA NA
Percentage of methane increament
Methane (mL) 392.5 444 486 647 540
Increament CH4 (%) 0 11.5 19.23 39.33 27.31
Appendix E: Experimental setups, Materials and Equipments
A. Experimental setups
A. 1: Digesters placed in water bath A.2: WDM with inverted graduated cylinders
A.3: Filtration using sand paper A.4: Pouring 5% HCl to the sample
97
A.5: Yellow light observed during titration A.6: Methane measurement
B. Materials
B.1: Corn cob B.2: Corn cob derived biochar
B.3: Chemicals B.4: Prepared solutions
98
B.4: Cow dung slurry B.5: Intestinal residue
C. Equipment’s
C.1: Muffle furnace C.2: Universal hot air oven
C.3: Constant temperature water bath C.4: PHS-1701 pH meter
99
C.5: Desiccator C.6: Digital weight balance
C.7: Weight balance C.8: Electric agitator
C.9: Streachable tube C.10: Syringe
10
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EXPERIMENTAL INVESTIGATION OF UPGRADING BIOGAS PRODUCTION

USING CORN COB DERIVED BIOCHAR

EXPERIMENTAL INVESTIGATION OF UPGRADING BIOGAS PRODUCTION

A THESIS SUBMITTED TO THE DEPARTMENT OF MECHANICAL ENGINEERING

IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF

Dawit Hailu Takore

Dr. Dawit Gudeta

Dawit Hailu Takore

Advisor Signature Date

External Examiner Signature Date

Internal Examiner Signature Date

Chair Person Signature Date

Head of Department Signature Date

School Dean Signature Date

Post Graduate Dean Signature Date

APPROVAL OF BOARD OF EXAMINERS........................................................................ii

1.1 Background of the Study..............................................................................................1

1.2 Problem Statement........................................................................................................3

1.3 The Objective of the Study...........................................................................................4

1.4 Scope of the Study........................................................................................................4

1.5 Limitations of the Study...............................................................................................4

1.6 Significance of the Study..............................................................................................5

1.7 Research Focus.............................................................................................................5

CHAPTER 2: LITERATURE REVIEW................................................................................6

2.2.1 Biogas composition...............................................................................................6

2.2.3 Sources and potential feedstock’s for biogas production......................................8

2.3 Anaerobic Digestion.....................................................................................................9

2.3.1 The biochemical process of anaerobic digestion...................................................9

2.3.2 The biochemistry of the anaerobic digestion process..........................................10

2.4 Impact of Process Parameters on Biogas Production.................................................12

2.4.1 Effect of pH value................................................................................................12

2.4.2 Effect of temperature...........................................................................................13

2.4.3 Effect of total Solid..............................................................................................14

2.4.4 Hydraulic retention time......................................................................................14

2.4.6 Summary of factors affecting the anaerobic digestion process...........................15

2.5 Challenges in Anaerobic Digestion............................................................................15

2.6 A Conventional Approach for Alleviating the Challenges with AD..........................15

2.7 Biogas upgrading.......................................................................................................16

2.7.1 Challenges in small-scale biogas upgrading........................................................16

2.7.2 Upgrading biogas within AD (An approach used in this study)..........................17

2.8 Effect of Biochar on the Anaerobic Digestion System...............................................20

2.8.1 Biochar as ammonium adsorbents.......................................................................21

2.8.2 Biochar concentration in AD...............................................................................22

CHAPTER 3: MATERIALS AND METHODS..................................................................27

3.3 Equipment and measuring instruments.......................................................................29

3.4 Preparation of Raw materials......................................................................................29

3.4.1 Preparation of CC-BC.........................................................................................29

3.4.2 Pyrolysis of corn cob...........................................................................................30

3.4.3 Characterization of CC-BC.................................................................................30

3.4.4 Preparation and characterization of cow dung and inoculum..............................31

3.4.5 Inoculum preparation...........................................................................................32

3.4.6 Media preparation................................................................................................33

3.5 Lab-scale Biogas Production Experiment...................................................................34

3.6 The Modified Gompertz Model..................................................................................34

CHAPTER 4: SIZING DIGESTER......................................................................................35

4.2 Customers Energy Demand for Cooking....................................................................35

4.2.1 Amount of biogas required..................................................................................35

4.2.2 Cow dung and number of cow requirement.........................................................36

4.3 Sizing of Anaerobic Digester......................................................................................37

CHAPTER 5: EXPERIMENTAL SETUP AND TEST PROCEDURES............................44