Binder Effect On Densification Of Cow Manure As A Solid Biofuel.

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BINDER EFFECT ON DENSIFICATION OF COW MANURE AS A SOLID BIOFUEL

MUHAMMAD NAQIUDDIN BIN SAMARUL FUAD

UNIVERSITI TEKNIKAL MALAYSIA MELAKA

M U H A M M A D N A Q IU D D IN S A M A R U L F U A D B A CH EL O R O F M ECH A N ICA L E N G . (P LA N T A N D M A IN TE N A N C E) ( H O N

S.) 2015 U

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SUPERVISOR DECLARATION

“I hereby declare that I have read this thesis and in my opinion this thesis is sufficient in terms of scope and quality for the award of the degree of

Bachelor of Mechanical Engineering (Plant and Maintenance)”

Signature :... Supervisor : Dr. Nona Merry Merpati Mitan Date : 29 June 2015

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BINDER EFFECT ON DENSIFICATION OF COW MANURE AS A SOLID BIOFUEL

MUHAMMAD NAQIUDDIN BIN SAMARUL FUAD

This thesis is submitted in partial fulfilment of the award of Bachelor of Mechanical Engineering (Plant and Maintenance) with Honours

Faculty of Mechanical Engineering Universiti Teknikal Malaysia Melaka

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DECLARATION

“I hereby declare that the work in this thesis is my own except for summaries and quotations which have been duly acknowledged.”

Signature :...

Author : Muhammad Naqiuddin Bin Samarul Fuad Date : 29 June 2015

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iii

DEDICATION

For my beloved Parents and Siblings

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ACKNOWLEDGEMENT

First of all, deepest thanks God because the Grace, I can complete my Final Year Project (FYP), Binder Effect on Densification of Cow Manure Briquette as a Solid Biofuel. All the challenges and trials in completing this project I faced with courage and patience until the project is completed successfully. All learning in completing this project I will make a guide to the future.

To my supervisor, Dr Nona Merry Merpati Mitan, I cannot express enough thanks and appreciation because her continued cooperation, encouragement, supports and guiding me to complete this project successfully. Thanks for accepting and guided me in completing this project. I’m also want to thanks to technician, En. Mahadir and En. Ismail for accommodating the laboratory facilities and valuable guidance.

I also want to thank both my beloved parents, Hj Samarul Fuad Bin Hj Mamnoor and Robiah Binti Hj Abdullah, because always giving support and encouragement to me. Without them I would not be able to complete this FYP. To my parent, thank you for giving suggestions and opinions and help me in financial.

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ABSTRACT

Nowadays, researchers have shown an increased interest in study another source of energy that can be replaced of fossil fuel. Production of briquette as one of energy alternative source is capable to overcome the shortage of fuel from hydrocarbon natural resources. From the previous study, a cow manure briquette that has been produced is brittle. Therefore, this research was studied about the effect of binder on densification of cow manure briquette as a solid biofuel. The binder applied in this research is starch and calcium hydroxide. The main objective is to identify binder effect on densification of briquette production. Cow manure was collected near Kampung Gangsa at Malacca (U2.293806, S102.261228) as a raw material to produce briquette. It involved six processes namely drying, crushing, milling, carbonization, mix with binders and densification. Sample of cow manure separated into two types which is mix with binders and without binder. The amount of binders ratio was 4% of the weight briquette produced in 100 gram. Cow manure was carbonized at 300ºC. Analysis of calorific value, proximate analysis, compressive test and fourier transform infrared spectroscopy (FTIR) has been conducted. The calorific value for carbonization sample (29.90 MJ/kg to 39.34 MJ/kg) is higher compared to non carbonization sample (23.32 MJ/kg to 24.42 MJkg). Moreover, the proximate analysis shows the value of moisture content for non carbonization sample (10% to 11.33%) is higher compare to carbonization sample (3.33% to 8.33%). Meanwhile, the percent of ash content for cow manure briquette is (21.33% to 30.33%), volatile matter (44.67% to 62.57%) and fixed carbon (4.67% to 21.33%). All this proximate analysis is follow the standard of ASTM of coal and coke. The FTIR results indicate that at 1100 cm-1_{was described a}

carboxylates group and the release of C-O structures from ethers is group of alcohol. A narrow 3900 cm-1_{band attributed to the free stretching O-H vibration. As a result,}

the briquette carbon with starch 1:4 has higher compressive strength 36.34 MPa and briquette carbon with calcium has higher calorific value 39.34 MJ/kg.

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ABSTRAK

Pada masa kini, para penyelidik telah menunjukkan minat yang mendalam terhadap kajian sumber tenaga lain yang boleh menggantikan bahan api fosil. Pengeluaran briket sebagai salah satu tenaga alternatif mampu mengatasi masalah kekurangan bahan api daripada sumber asli hidrokarbon. Daripada kajian yang lepas, briket najis lembu yang dihasilkan adalah rapuh. Oleh itu, kajian ini telah dikaji untuk mengetahui kesan pengikat pada pemadatan najis lembu briket sebagai bahan api bio yang kukuh. Pengikat yang digunakan dalam kajian ini ialah kanji dan kalsium hidroksida. Objektif utama adalah untuk mengenal pasti kesan pengikat terhadap pemadatan briket najis lembu. Najis lembu diperolehi dari Kampung Gangsa di Melaka (U2.293806, S102.261228) sebagai bahan mentah. Ia melalui enam proses iaitu pengeringan, penghancuran, pengisaran, karbonisasi, bercampur dengan pengikat dan pemadatan. Sampel najis lembu akan dibahagikan kepada dua jenis yang bercampur dengan pengikat dan tanpa pengikat. Jumlah nisbah pengikat hanya 4% daripada berat briket yang dihasilkan dalam 100 gram. Najis lembu telah dikarbonisasi pada 300°C. Analisis nilai kalori, analisis proksimat, ujian mampatan dan spektroskopi (FTIR) dijalankan. Nilai kalori untuk sampel karbonisasi adalah lebih tinggi (29.90 MJ/kg hingga 39.34 MJ/kg) berbanding dengan sampel tanpa karbonisasi (23.32 MJ/kg hingga 24.42 MJkg). Selain itu, analisis proksimat menunjukkan nilai kandungan lembapan bagi sampel tanpa karbonisasi adalah lebih tinggi (10% hingga 11.33%) berbanding dengan sampel karbonisasi (3.33% hingga 8.33%). Sementara itu, peratus kandungan abu untuk najis lembu briket adalah (21.33% hingga 30.33%), jirim meruap (44.67% hingga 62.57%) dan karbon tetap (4.67% hingga 21.33%). Semua analisis proksimat ini adalah mengikut piawai ASTM arang batu. Keputusan FTIR menunjukkan bahawa pada 1100 cm-1

digambarkan sekumpulan karboxylat dan pelepasan struktur C-O adalah dari kumpulan alkohol. Pada 3900 cm-1_{menunjukkan getaran bebas regangan OH.}

Kesimpulannya, briket karbon dengan kanji 1:4 mempunyai kekuatan mampatan yang lebih tinggi 36.34 MPa dan briket karbon dengan kalsium mempunyai nilai kalori yang lebih tinggi 39.34 MJ/kg.

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TABLE OF CONTENT

CHAPTER TITLE PAGE

DECLARATION ii

DEDICATION iii

ACKNOWLEDGEMENT iv

ABSTRACT v

ABSTRAK vi

TABLE OF CONTENT vii

LIST OF TABLES x

LIST OF FIGURES xi

LIST OF EQUATION xiii

ABBREVIATION xiv

LIST OF APPENDICES xv

CHAPTER 1 INTRODUCTION

1.1 Background 1

1.2 Problem Statement 3

1.3 Objectives 4

1.4 Scope 4

CHAPTER 2 LITERATURE REVIEW

2.0 Overview 5

2.1 Biomass 6

2.1.1 Biomass Components 7

2.2 Biomass Conversion 9

2.3 Carbonization 10

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2.4.1 Solid Biofuel 13

2.4.2 Liquis Biofuel 15

2.4.3 Gas Biofuel 15

2.5 Cow Manure 16

2.6 Binder Materials 17

2.6.1 Starch 18

2.6.2 Calcium hydroxide 19

2.7 Sample Analysis 20

2.8 Past Studies 20

CHAPTER 3 METHODOLOGY

3.0 Overview 23

3.1 Flow Chart of the Project 24

3.2 Sample Preparation 25

3.2.1 Collecting Raw Material 25

3.2.2 Drying and Chopping Process 25

3.2.3 Crushing Process 26

3.2.4 Milling Process 26

3.2.5 Carbonization Process 27 3.2.6 Sample Mixed with Binder 28

3.2.7 Densification Process 28

3.3 Analysis of Briquette 29

3.3.1 Calorific Value 29

3.3.2 Compressive Test 30

3.3.3 Proximate Analysis 30

3.3.3.1 Moisture Content 31

3.3.3.2 Ash Content 32

3.3.3.3 Volatile Matter 33

3.3.3.4 Fixed Carbon 34

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CHAPTER 4 RESULTS AND ANALYSIS

4.1 Introduction 35

4.2 Moisture Content 36

4.3 Ash Content 37

4.4 Volatile Matter 38

4.5 Fixed Carbon 39

4.6 Calorific Value 40

4.7 Compressive Test 41

4.8 FTIR 42

CHAPTER 5 DISCUSSION

5.1 Proximate Analysis 45

5.2 Calorific Value 48

5.3 Compressive Test 49

5.4 FTIR Characterization 50

CHAPTER 6 CONCLUSION AND RECOMMENDATION

6.0 Conclusion 53

6.1 Recommendation 55

REFERENCES 55

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LIST OF TABLES

NO. TITLE PAGE

2.1 Content of cellulose, hemicellulose and lignin 8

2.2 Major trade form of solid biofuel 14

2.3 Nutrient content in cow manure 16

2.4 Previous study about cow manure 22

3.1 Ratio of starch soluble 28

4.1 Analysis data on the cow manure briquette sample 35 4.2 Analysis data of cow manure briquette for compressive test 41

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LIST OF FIGURES

NO. TITLE PAGE

2.1 Main biomass conversion process 10

2.2 Classification of renewable biofuels 12

2.3 Various technological routes for biofuel production 13 2.4 The chemical structure of straight-chain amylose (α-glucose 1,4) 19 2.5 The chemical structure of the branched chain amylopectin 19 (α-glucose 1,6)

3.1 Flow chart of the project 24

3.2 Fresh cow manure 25

3.3 Drying and chopping process 26

3.4 Crushing machine 26

3.5 Milling machine 27

3.6 Non carbon and carbon sample 27

3.7 Temperature profile during carbonization 27

3.8 Densification mould for produce cow manure briquette and 29 a briquette product

3.9 Universal testing machine (Instron 5583) 30

3.10 Crucible, desiccator and high performance oven 31

3.11 Furnace 32

3.12 Furnace, crucible and desiccator 33

3.13 FTIR Spectrophotometer 34

4.1 Moisture content of sample cow manure briquette 36

4.2 Ash content of sample cow manure briquette 37

4.3 Volatile matter of sample cow manure briquette 38

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NO. TITLE PAGE

4.5 Caloric value 40

4.6 Sample graph of the compressive test for cow manure briquette 42 4.7 FTIR spectra of cow manure briquette for non

carbonization sample 43 4.8 FTIR spectra of cow manure briquette for carbonization sample 44

5.1 Proximate Analysis of cow manure briquette 45

5.2 Comparison of non carbon and carbon of cow manure briquette 46 5.3 Comparison of non carbon and carbon with binder starch

of cow manure briquette 47

5.4 Comparison of non carbon and carbon with binder

calcium hydroxide of cow manure briquette 48

5.5 Comparison of FTIR spectra for non carbonization and

carbonization from cow manure briquette 50 5.6 Comparison of FTIR spectra for starch non carbonization and

carbonization for ratio 1:4, 1:8, 1:12 from

cow manure briquette 51

5.7 Comparison of FTIR spectra for calcium non carbonization and calcium carbonization from cow manure briquette 52

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xiii

LIST OF EQUATIONS

NO. EQUATION PAGE

2.1 Reaction of photosynthesis 11

2.2 Reaction of calcium oxide and water 19

3.1 Calorific value 29

3.2 Percentage of moisture content 31

3.3 Percentage weight loss 32

3.4 Percentage of volatile matter 33

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ABBREVIATIONS

EPA United State Environmental Protection Agencies IEA International Energy Agency

USDA United State Department of Agriculture FTIR Fourier Transform Infrared Spectroscopy NHV Net Heating Value

NC Non Carbon

NCS Non Carbon Starch NCC Non Carbon Calcium

C Carbon

CS Carbon Starch

CC Carbon Calcium

MC Moisture Content VM Volatile Matter

FC Fixed Carbon

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LIST OF APPENDICES

NO. APPENDIX PAGE

1 Gantt chart for Final Year Project (FYP) 1 60

2 Gantt chart for Final Year Project (FYP) 2 60

3 Data of proximate analysis for sample non carbonization 61 4 Data of proximate analysis for sample carbonization 65

5 Calculation of calorific value 71

6 Compressive test 72

7 Standard Test Method for Moisture in the Analysis Sample

of Coal and Coke 77

8 Standard Test Method for Ash in t he Analysis Sample

of Coal and Coke 81

9 Standard Test Method for Volatile Matter in the Analysis Sample

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CHAPTER I

INTRODUCTION

1.1 Background

In era globalization, the world has realized that the source of energy is no longer dependent on fossil fuels only. The increasing demand on energy resources for the next hundred years and the limitation of these resources has led the government to introduce many project based on green technology. One of the green technology projects is sustainable energy production (Gordon et al., 2009). Sustainable energy is the provision of energy that fulfilled the requirements in present generation without prejudice to their needs in the future. Renewable energy is one of the technologies that related to sustainable energy.

For Lalchand (2012), renewable energy refers to energy generated from the waste and it also mean as energy derives from natural resources that are added constantly such as sunlight, wind, rain, waves and geothermal heat.

According to official website of Ministry of Energy, Green Technology and Water, National Renewable Energy Policy 2010 was established to control the entire renewable energy program. Objectives on this plan are to facilitate the growth of the renewable energy industry, to ensure reasonable renewable energy generation costs, to increase renewable energy contribution in the national power generation mix, to enhance awareness on the role and importance of renewable energy and to conserve the environment for future generation (Hashim and Ho, 2011).

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2 Malaysia was formulated a Five Fuel Policy for Power Generation in 2000 as a step to overcome the problems that will occur if government continue to depend on fossil fuels as a main source of primary energy. This five fuel policy is actually continuity from Four Fuel Policy that begins in 1981 which renewable energy was added as a fifth fuel source to become Fifth Fuel Policy (Eighth Malaysia Plan 2001-2005). When natural gas discovered, Malaysia had a Four Fuel Policy which is hydro, natural gas, coal and oil. The policy has changed to a Fifth Fuel Policy, include hydro, natural gas, coal, oil and energy efficiency (Lalchand, 2004).

Renewable energy can reduce the reliance on sources of fossil fuels such as biomass resources from oil palm, wood and rice husks. Mckendry (2002) has defined that biomass is the most common form of renewable energy and it is gaining popular among country that has a lot of waste material or feedstock. Biomass can be categorized into two groups of compounds. The first group is the cell walls which serve as physical supporting structures and the content of the cells in form of proteins, lipids, starches and sugars. The second group is lignocellulosics are mainly composed of cellulose and hemicelluloses held together by lignin (Preston, 2009).

In addition, many biomass feedstocks are easily to found such as woody plants, herbaceous plants or grasses, aquatic plants and manures that are potential to produce a renewable energy resources (Mckendry, 2002). Cow manure is one of an example of the biomass available in Malaysia. The dependence on fossil fuel are able to diminish by modification on biomass resources to become alternative fuel like bioethanol and briquette.

For this study, the densification process was used to producing a cow manure briquette as a solid biofuel. Densification of this materials would contribute to improving their behaviour as a fuel by increasing their homogeneity and allowing a wider range of lignocellulosic materials to be used as fuel (Tabares et al., 2000). This densification process can be completed by mixture between binder and cow manure that will increases the structure strength of the product. Other than that it easier to transport and manage allowing a greater diversity of lignocellulosic materials to be used as fuel (Tabares et al., 2000).

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1.2 Problem statement

Lately, the natural resources in Malaysia become decrease due to the increasing number of population. Based on Department of Statistics Malaysia, the number of population in Malaysia 2010 are 27,565,821 peoples and until May 2015, the number of population in Malaysia increase to 30,458,199 peoples. Therefore, it requires a lot of energy quantities to fulfill the requirements in present generation to carry out daily activities without prejudice to their needs in the future. Nowadays, Malaysia only depends on one source which is fossil fuel as an energy source.

From that problem, government of Malaysia and all people must think and shift toward green renewable energy. Biomass is one of the sources of renewable energy and cow manure was selected because it’s easier to find. Cow manure usually use as fertilizer. Using cow manure as fertilizer can cause water pollution because it can seep into groundwater and flow to the river. Based on article from drinking water impact at United State Environmental Protection Agencies (EPA), in 2011, contamination of cow manure in water can brings negative effect for human health due to the microorganism content such as cryptosporidium. Moreover, if cow manure not managed properly, it can cause disease in human because it contains ammonia, antibiotics, hormones, heavy metal, sediments, pathogens, nutrients and organic matter that can produce danger gas such as methane gas.

Beside that, excess use of farms livestock wastes can overload soil with macronutrients like nitrogen and phosphorous and micronutrients that have been added to animal feed like heavy metals (Burkholder et al., 2007). Aside from that, operations of farms livestock are possibility of lowering air quality in the areas around them and also emit greenhouse gases, and therefore contribute to climate change. Globally, farms livestock operations are responsible for approximately 18% of greenhouse gas production and over 7% of U.S. greenhouse gas emissions (Massey and Ulmer, 2008).

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4 Other than that, the problem that occurred in previous studies is on the structure and quality of cow manure briquette was brittle. This research also shows the result of calorific value is conversely. This is because the carbonization sample has produced a lowest calorific value while it should be highest (Badarulzaman, 2014). One of the solutions for that problem is cow manure briquette are mixed with starch and calcium hydroxide as binder materials before going to the densification process to increase the impact of cohesive quality and structure strength of the product.

1.3 Objectives

The objective of the project is:

1. To obtain briquette from cow manure in presence of binder materials namely starch and calcium hydroxide.

2. To analyse the cow manure briquette product in term of calorific value, proximate analysis compressive test and FTIR.

3. To compare the result of calorific value, proximate analysis and compressive test of cow manure briquette with binder and without binders.

1.4 Scope

This project is about the preparation of cow manure as raw material to produces briquette as a solid biofuel. The main purpose is to study the binder effect on densification of cow manure as a solid biofuel. It includes the process of drying, pulverization, carbonization and densification which is mixture between binder and cow manure. Two types of binders that mix with sample briquette is starch and calcium hydroxide. Furthermore, observation on calorific value, proximate analysis (moisture content, ash content, volatile matter and fixed carbon) and compressive test will perform on cow manure briquette. Load capacity for compressive test is range 60–120 kN with cross head speed at 2 mm/min.

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CHAPTER 2

LITERATURE REVIEW

2.0 Overview

Nowadays, natural resources in our earth become decrease due to increasing the number of population in world. To reduce dependency toward natural resources, there are many alternative way is introduced to generated energy such as biofuel. Biofuels come in many forms which is biogases, liquid fuels and solid biomass. Cow manure is one of an example of the biomass available in Malaysia.

Recently, increasing annually the volume of cow manure generated from feedlot farming, most cow manures are disposed into landfills or applied to the land without treatment (Baba and Nasir, 2012). Usually, the cow manure was used as fertilizer and biogas production. Therefore, the industry of biofuel was introduced as a new solution for overcome the shortage of natural resources and prevent from adverse environmental and health problems. Based on that, research about producing solid biofuel will conduct as well as binder effect on densification of cow manure briquette is observed.

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2.1 Biomass

Biomass can be defined as a term for all organic material that stems from plants that include algae, trees and crops. Mckendry (2002), stated the organic material of plant is happened between the reaction of CO2, water and sunlight at a

natural process. Photosynthesis is a process by which they convert solar energy into chemical energy to produce carbohydrates that form the basis formation of biomass and the carbon fixation by reduction of carbon dioxide (Demirbas, 2009). Equation (2.1) presents the reaction of photosynthesis process.

(2.1) Furthermore, Demirbas (2009) stated that the term biomass refers to non-fossilized and biodegradable organic material originating from plants, animals, and microorganisms derived from biological sources. Example of biomass are waste, wood, alcohol fuel and gas (hydrogen). In addition, the production of fibers and chemicals from plants and animals also belong to the biomass (Piech, 2012). Based on Preston (2009), biomass can be defined as cellulose materials which can be broadly classified as woody and non-woody biomass. Woody biomass is from trees while non-woody biomass is from agricultural residues. Recent studies stated lignocellulosic biomass such as wood contains about 50 % of cellulose, 25 % of hemicellulose and 25 % of lignin from total content of hydrolyzable biopolymers (Feng et al., 2012).

Biomass also has great potential to provide heat and power to industry and to provide feedstocks to make a wide range of chemicals and materials or bioproducts. Ciubota-Rosie (2008) stated that biomass feedstock can be divided into four general categories which are waste, forest product, energy crop and aquatic plant. Manure, crop residues and agriculture product waste are an examples of waste stock. Forest product stock is like wood, trees and sawdust while energy crop is a material such as short rotation woody crop, sugarcane and rice husk. Aquatic plant has an examples of algae, water hyacinth and water weeds.

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To reduce the emission of carbon dioxide, there a lot of biomass source in this world due to it sustainable and renewable source compared to the fossil fuel (Supatata, 2013). Moreover, Parveen et al., (2009) stated that biomass are cleaner burning than fossil fuel, and the short cycle of growing plants and burning fuel made from them does not add CO2 to the atmosphere. As a result, its maybe can be a good

alluring of clean mechanism option for reduce the global warming factor and lowering the green gas house effect.

According to Jamradloedluck (2007), the uses of biomass will discharged less environmental pollution and health risk than the fossil fuel combustion and biomass was considered as neutral because during the combustion it releases the same amount of carbon dioxide . This is because the contains of biomass are less sulphur and nitrogen where it will generate lower emission compared to the fossil fuel (Fernandez et al., 2011). Furhermore, it make the utilization of the biomass is more ecofriendly.

2.1.1 Biomass Components

Biomass contains lignocelluloses and its call lignocellulosic biomass. Lignocellulosic biomass contains cellulose, hemicelluloses and lignin. Hydrogen bonding is use to tightly bound between the carbohydrate polymers and lignin, but also through some covalent bonding (Ahindra, 2008). Recent study from Carriquiry et al., (2010), stated that cellulose and hemicellulose are the main components of lignocellulosic feedstock.

Based on the Parveen et al., (2009), almost 90% of the dry weight of plant materials is stored in the form of cellulose, hemicellulose, and lignin. Table 2.1 shows the content of cellulose, hemicellulose and lignin in common lignocellulosic composition. The presence of lignin in lignocelluloses leads to a protective barrier that prevents plant cell destruction by bacteria and fungi for conversion to fuel. For the conversion of biomass to fuel, the cellulose and hemicellulose must be broken down into their corresponding monomers which are in sugars, so that microorganisms can utilize them.

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1.2 Problem statement

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1.3 Objectives

The objective of the project is:

1. To obtain briquette from cow manure in presence of binder materials namely starch and calcium hydroxide.

2. To analyse the cow manure briquette product in term of calorific value, proximate analysis compressive test and FTIR.

3. To compare the result of calorific value, proximate analysis and compressive test of cow manure briquette with binder and without binders.

1.4 Scope

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CHAPTER 2

LITERATURE REVIEW

2.0 Overview

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6 2.1 Biomass

(2.1)

Furthermore, Demirbas (2009) stated that the term biomass refers to non-fossilized and biodegradable organic material originating from plants, animals, and microorganisms derived from biological sources. Example of biomass are waste, wood, alcohol fuel and gas (hydrogen). In addition, the production of fibers and chemicals from plants and animals also belong to the biomass (Piech, 2012). Based on Preston (2009), biomass can be defined as cellulose materials which can be broadly classified as woody and non-woody biomass. Woody biomass is from trees while non-woody biomass is from agricultural residues. Recent studies stated lignocellulosic biomass such as wood contains about 50 % of cellulose, 25 % of hemicellulose and 25 % of lignin from total content of hydrolyzable biopolymers (Feng et al., 2012).

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alluring of clean mechanism option for reduce the global warming factor and lowering the green gas house effect.

2.1.1 Biomass Components

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