ACKNOWLEDGEMENT

First of all, I need to thank almighty God for the great protecting of me in health and helping me to do everything on time. Great thanks to my advisors Dr. Alemayehu Kiflu. and Ato Ashenafi Hailu. for the progressive advising, providing materials, and equipments and supporting me in all my work that make me to complete the thesis successfully. Great thanks to Ethiopian petroleum enterprise (EPE) for helping me with quick experiment result with no killing of my time specially centre head of petroleum quality testing, Ato Manaye Balcha. I wish to thank all my classmates that the cooperative advising of one another, working things together. Lastly, thanks to chemical department of Bahir Dar University, for the enough computers providing to get internet service and writing on it and allowing to me lab to my experimental test.

TABLE OF CONTENTS
Contents pages

ACKNOWLEDGEMENT ............................................................................................................. i TABLE OF CONTENTS .............................................................................................................ii Index of Tables ..........................................................................................................................v Index of Figures .......................................................................................................................vi Nomenclatures ........................................................................................................................vii ABSTRACT............................................................................................................ viii CHAPTER 1 ............................................................................................................. 1 1 INTRODUCTION ................................................................................................. 1 1.1 1.2 Problem Statement .....................................................................................................5 Objectives of the study ................................................................................................6

1.2.1 General objective .......................................................................................................6 1.2.2 Specific objectives......................................................................................................6 1.3 1.4 Methodology ...............................................................................................................7 Background .................................................................................................................8 Ethanol stove development ....................................................................................8 Impacts of Household Energy Patterns ................................................................ 11 Clean cooking fuel, ethanol and benefits............................................................. 15

1.4.1 1.4.2 1.4.3

CHAPTER 2 ........................................................................................................... 19 2 PROPERTY OF ETHANOL-WATER MIXTURE ....................................................... 19 2.1 2.2 2.3 Property of ethanol ...................................................................................................19 Ethanol- water mixture .............................................................................................21 Determination of ethanolwater mixture property ..................................................23 Boiling point pressure and temperature ............................................................... 23 Fraction distillation of an azeotrope of ethanol-water mixture ............................... 25 Enthalpy of mixing .............................................................................................. 26

2.3.1 2.3.2 2.3.3 2.4 2.5 2.6

Partial molar volume .................................................................................................29 The maximum flame temperature ............................................................................30 Flammablity of ethanol-water mixture fuel..............................................................34

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2.7 2.8 3

Activity coefficient of ethanol-water mixture fuel ...................................................36 Flash-point of ethanol- water mixture analytical estimation ..................................38

CHAPTER 3 ........................................................................................................... 40 ETHANOL-WATER MIXTURE AS COOKING FUEL IN ETHIOPIA ............................ 40 3.1 3.2 3.3 Potential and quality of ethanol production in Ethiopia .........................................40 Ethiopia Policy toward using of ethanol as cooking fuel .......................................41 Optimal flammable ethanol-water mixture ..............................................................42 Flame height measurement set-up...................................................................... 42 Flash-point measurement set-up ........................................................................ 44 Data analyzing .................................................................................................... 45 Experimental Result and discussion ................................................................... 46

3.3.1 3.3.2 3.3.3 3.3.4

CHAPTER 4 ........................................................................................................... 50 4 DESIGN OF ETHANOL-WATER MIXTURE STOVE ................................................ 50 4.1 4.2 4.3 4.4 The stove Parts specifications .................................................................................50 Burner holes diameter ..............................................................................................53 Vertical height of flame .............................................................................................57 Heat losses through stove .......................................................................................58 Radiation from flame ........................................................................................... 58 Convection from flame .........................................................................................69

4.4.1 4.4.2 4.5 5

Air-to- fuel ratio .........................................................................................................61

CHAPTER 5 ........................................................................................................... 63 MANUFACTURING PROCESS AND COST ESTIMATION ....................................... 63 5.1 Efficiency of the stove ..................................................................................................63 5.2 Material and Cost estimation .......................................................................................65 5.3 Parts and Manufacturing Process ...............................................................................67 5.4 Operation and Working Principle of the Stove ...........................................................68 CHAPTER 6 ........................................................................................................... 69 6 CONCLUSION AND RECOMMENDATION ............................................................ 69 6.1 Conclusion ....................................................................................................................69 6.2 Recommendation.........................................................................................................70

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7 8

REFERENCE ..................................................................................................... 71 ANNEXIES ........................................................................................................ 74

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Index of Tables
Table 2-1: Physical property of ethanol and water ........................................................... 24 Table 2-2: Antoine constants of ethanol and water ........................................................... 25 Table 2-3: Maximum flame temperature and % volume of ethanol ................................... 35 Table 3-1: Ethanol production capacity of Ethiopia (1000 liters) ....................................... 40 Table 3-2: The measured mean flame height of ethanol-water mixture ............................ 46 Table 3-3: Property summary of 60 % ethanol-water mixture ............................................49 Table 4-1: Thermal property of liquid hydrocarbon fuels .................................................. 55 Table 5-1: Cost and specification of materials of stove .................................................... 65

Index of Figures
Figure 1-1: Two burner CleanCook ethanol stove .............................................................. 9 Figure 1-2: Low concentration ethanol stove ...................................................................10 Figure 1-3: Ethanol stove for both cooking and lighting .....................................................11 Figure 1-4: Rural house wife from fire wood collection ......................................................14 Figure 2-1: Ideal case partial pressure of ethanol, water and ethanol-water mixture .........24 Figure 2-2: Mixing enthalpy of ethanol-water mixture ....................................................... 28 Figure 2-3: The calculated volume change OF 10 mL sample...........................................30 Figure 2-4: Combustion model of controlled system ..........................................................31 Figure 2-5: Activity coefficient of ethanol-water mixture by UNIFAC ................................. 38 Figure 3-1: Flame height measure set-up ........................................................................ 44 Figure 3-2: Flash-point measure set-up ............................................................................45 Figure 3-3: Flash-point and ambient temperature relation ................................................ 47 Figure 3-4: Flash-point data of ethanol-water mixture ...................................................... 48 Figure 4-1: Parts of the stove ........................................................................................... 51 Figure 4-2: Top surface area of canister or burner ........................................................... 53 Figure 4-3: Librated heat energy and single burner hole burner ....................................... 56 Figure 4-4: Vertical height of hottest zone flame .............................................................. 57

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Nomenclatures
a AFR Cl Activity Air-to-fuel ratio Confidence level Specific heat capacity at constant pressure Burner hole diameter Flex-fuel vehicles Lower flammability limit Flame height Liquid petroleum gas fuel Pressure Heat energy Temperature Upper flammability limit Mole fraction of ethanol in water mixture at liquid state Mole fraction of ethanol in water mixture at vapor state Absorpibity Radiation Boltzmann constant (5.67X10 -8 w/k4m2) Emissivity of flame Activity coefficient

FFV LFL

LPG P Q T UFL x

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ABSTRACT
Ethiopia is the third largest user of traditional cooking fuels and this leading to environmental, ecological, economic, and healthy impacts. To improve the quality of life and to avoid these negative effects, clean and renewable alternatives fuels are selective for cooking. The availability of clean cooking and lighting fuels which are renewable and can be produce locally will be the first and an important step in raising the quality of life in the case of cooking. Liquid or gaseous fuels are far superior to solid fuels for cooking because of their clean combustion and existing supply chain convenience and high energy content. Again, liquid fuels are most suitable since they have much higher energy density than gaseous fuel like biogas or LPG and easy handling. Among all the liquid fuels that can be produced locally and in a renewable manner, ethanol is one and the best alternative. Thus, it is an excellent substitute for kerosene and burns better than kerosene without any particulate output or unpleasant smell of combustion and its renewability. Ethanol used for cooking in most areas with different concentration of water in order to reduce its flammability hazard. Therefore, the optimal flammable ethanol-water mixture is between inflammable water and flammability hazard of ethanol. This study is going to come-up with the optimal flammable clean cooking ethanol-water mixture stove for house hold cooking purpose of Ethiopia in both experimental and analytical investigation. Maximum temperature of flame of mixture is calculated using combustion energy balance and vertical flame height and flash-point is measured. In both determinations, 60% (v/v) ethanol-water mixture is selected as the optimal flammable solution for the household cooking. It get as flash-point 23.7 oC and vertical flame height is 5.41 Cm. Increasing the flash-point of ethanol is to make it safe for house hold cooking purpose. Key words: Clean fuels, Ethanol, Flammability hazard, ethanol-water mixture

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CHAPTER 1 1 INTRODUCTION
Food to be cooked to make it favorable and the right absorption of our body, heat energy used to cook beside with killing or inactivating the potential of harmful organisms including bacteria or virus and to change the flavor of food with food ingredients. There are many methods of cooking, and among which have been known are; baking, roasting, frying, grilling, barbecuing, boiling, steaming, and braising. All methods of cooking needs heat energy and that may get from burning of firewood, biofuels, LPG and other fossil fuels as energy source. Cooking is an activity unique to humans and some scientists believe that the advent of it played an important role in human evolution and development. Most anthropologists believe historically that cooking fires first developed around 250,000 years ago before starting of cook. The development of agriculture, commerce and transportation between civilizations in different regions offers the development of cooking with many different new ingredients. New inventions and technologies such as pottery for holding and boiling water, improved cooking techniques with the life change revolution develop through time. Some modern cooking stoves apply advanced scientific techniques to food preparation and saving of energy in safer manner within a little cooking time. Therefore, the system of cooking, cooking stove, and cooking fuel is still in developing through time to time with advance of the life standards. Therefore, the progress development of cooking stoves is mainly based on saving of energy, with no or little smoking, stove functionality in different cooking fuels, and cooking time and like. To achieve all these goals, design and development of different cooking stove accordingly its available fuel still not satisfied. Using of traditional fuels for cooking has negative effects on environmental, economic and healthy impacts. That is, the ample use of firewood and charcoal leads to deforestation, leading to ecological imbalance, and increased use of agricultural residues and animal dung deprives the land of essential nutrients that are necessary for soil fertility. Similarly, uncontrolled use of traditional cooking fuels is destruction of ample of cooking fuels and wastage of time.

Furthermore, smoke from the use of fuel wood, animal dung, and agricultural residue for cooking contributes to acute respiratory infections. This latter problem, i.e., indoor air pollution is worse in poor countries where households houses are not equipped with separate living with cooking places and selected air conditioning system. Therefore, for the development of clean cooking fuel these steps are followed: Changing cooking habits is not an easy task; users have to be convinced that there are better methods than the traditional way. Improved stoves and clean stoves have to be efficient, clean-burning and convenient; they have to look modern and must still be affordable. Experiences of many different household energy initiatives have shown that a commercial approach is the most successful and sustainable way of promoting improved cooking technologies. Finally the availability of both fuel and stove to be prepared for the individual household users. Ethiopia is the third largest user in the world of traditional fuels for household energy use; this is in comparison to 90 % of Sub-Saharan Africa and approximately 60 % of the African continent [1]. As reported by the Ethiopian Rural Energy Development and Promotion Center (EREDPC 1998), in 1996, the most recent year statistics on the energy sector shows, 77 % of total final energy consumption consisted of firewood and charcoal while another 15.5 % consisted of agricultural residues, and only roughly 7 % was met by modern energy sources such as petroleum and electricity. Accordingly EREDPCA report, over 90 % of Ethiopia population using fire wood, agricultural residues, charcoal and animal dung but all such fuels produce high emissions of carbon monoxide, hydrocarbons and particulate matter during cooking. Hydrocarbon emissions are highest from the burning of dung for fuel, while particulate emissions are highest from agricultural residues. Women and children suffer most from indoor air pollution because they are traditionally and culturally responsible for cooking and other household activities that involve spending hours near the cooking fire and exposed to smoke. Young children are particularly

susceptible to disease, which accounts for their predominance in the statistics for premature deaths due to the use of biomass for cooking. The effects of exposure to indoor air pollution depend on type of fuel and stove efficiency, how pollution is dispersed and how much of their time household members spend in indoors. The type of fuel used and individuals participation in food preparation have consistently been the most important indicators of indoor pollution. As well as being much more dependent on biomass, poor households rely on low-quality cooking equipment and live in poorly ventilated housing, exacerbating the negative health impact, as there is incomplete combustion and nondissipation of smoke in the area. The overall impacts in using traditional biofuel in cooking process are in detail found in section 1.4.2. Ethiopian demand for clean cook energy sources is expected to grow faster than for any other energy source; biomass fuels will continue to dominate total energy consumption and the effects for which is to live without any harmful consequences. The energy and environment policies of Ethiopia supports the initiatives and introduction of clean cook fuels, the drafts of biofuel strategy is also prepared. This is the critical measure for the improvement of economy and healthy of residents. The availability of clean cooking and lighting fuels, which are renewable and can be grown locally, will be the first and an important step in raising the quality of life of rural population. No modern society uses solid fuel like coal or wood for cooking. Liquid or gaseous fuels are far superior to solid fuels for cooking because of their clean combustion and existing supply chain convenience and high energy content. Again, liquid fuels most suitable since they have much higher energy density than gaseous fuel like biogas or LPG and easy handling. Among all the liquid fuels, which can be produced locally and in a renewable manner, ethanol is one and the best. Thus, it is an excellent substitute for kerosene and burns better than kerosene without any particulate output or unpleasant smell of combustion and its renewability. Hence, the use of ethanol fuel for cooking and lighting for rural areas should be encouraged to sustain all environmental, economic, and healthy impacts of cooking.

This study is going to develop clean cooking ethanol stove for household in optimum flammable in water mixture for cooking. After testing of different ethanol-water percentage of mixture in flammability and having of enough energy for cooking, the best solution is selected and therefore, the stove designed for the selected concentration of ethanol-water mixture.

1.1

Problem Statement

In Ethiopia, together with under developed areas of Africa, the use of traditional fuels and fossil fuels for cooking is facing housewife and cooking bodies in different diseases due to poor indoor air quality and deforestation problem of the area which further leads to ecological imbalance. Using of fossil fuels for cooking in urban area leads to energy crises and assisting of global warming problem. Ample using of wood for cooking and charcoal production makes most area desert and destroyed forests and forest habitants. Identification of this problem from different area is leading to think idea toward to use clean and renewable fuels for cooking. Among the clean and renewable fuels, liquid fuels are superior in their high energy density and easy handling. Ethanol is a good alternative except its pure case flammability hazard. For different design models of the stove, cooking energy of flammability of ethanol with water solution, but optimal percentage is still not determined. For the economy of the fuel and sufficient energy content, the best percentage of ethanol-water mixture for cooking is not known quantitatively. Thus, the use of ethanol for cooking is not in progress. The production of ethanol in Ethiopia is not using in our country, it export but the other cooking fuels import from other country and others consumes electricity. The current production and future development of ethanol production is not motivated if the ethanol market not encouraged linearly with the production rate. If the ethanol stove is designed, and manufactured, and distributed in our country, both the economic and indoor air quality problems, deforestation and ecological imbalance value confidently to be improved and the same time agricultural based country agro-business encouraged.

1.2 Objectives of the study

1.2.1 General objective This study is conducted to experimental and analytical determination of flammability best ethanol-water mixture for safety of cooking and its stove development in Ethiopia. 1.2.2 Specific objectives The object of this project is to conduct a paper of design ethanol stove to use ethanol as cooking fuel in our country. To be achieved this through which; Experimentally flame height of different percentages of ethanol-water mixture and flash-point measured to determine optimal concentration in flammability and flame property to be observed Result discussion of tests of measurements for comparison of different concentration of ethanol-water mixture. Design the stove for cooking in the best flammable percentage of ethanol-water mixture Assembly and detail drawings of the stove parts , and operation principle of stove Determine the unit cost (Investment cost), payback period, life cycle cost, life cycle saving comparing with kerosene and other ethanol cooking stoves by fuel cost and stoves fabrication cost

1.3

Methodology

The methodologies incorporated to achieve the specified objectives of the study are the followings: Data collected for the quality of ethanol production in major sugar factories of Ethiopia. Reviewing of books, internet sites, journals, and magazines that can be source of the study and increases the idea of research. Experimental carried in different percentage of ethanol-water mixture; and the values of flame height and flash-point measured, and observation of flame property. Based on the experimental flame data flame height, flash-point comparison, analytical calculation of energy, and flame property observation the best flammable ethanolwater mixture to be selected. For the selected best concentration of ethanol-water mixture stove designed; the fuel storage, and burner combustion area, and flame turbulence area of combustion to be sized. Assembled and detail drawing of the stove for detailed description of the stove of the design to be included. Economic evaluation and comparison with other stoves to be conducted.

1.4

Background

1.4.1 Ethanol stove development Now a day, number of design and models of ethanol stoves are designed and in use most area of the world. Since, ethanol having of high flammability, pure ethanol cant use in domestic purpose. Ethanol is clean and non toxic fuel that can use in wide range of applications, either as additives of automotives fuel, and domestic cooking purpose. The only hazard associated with ethanol is its high flammability in pure form. It has wide range of flammability, the upper flammability limit (UFL) 19 % and lower flammability limit (LFL) 3.3 % in volume ratio to air content [2]. When the content of water increases in a solution of ethanol and water mixture, the combustion stochiometric air requirement is increase and hence the flammability to be reduced. Thus, mixing it with water is one alternative technique to use ethanol for cooking by reducing its hazardous flammability. One of the ethanol stove designed before is, CleanCook of Gia project ethanol stove, which is designed and manufactured in Swedish company as shown figure 1-1. It works in the concentration of 95 % ethanol, and 4.5 % water less of 0.5 % of other additives in volume ratio [3]. It introduced to Ethiopia during the protracted conflict of Somalia, for disrupted people of refunge camp. The CleanCook stove is modeled on the Origo stove, which was invented in 1979 by Bengt Ebbeson and developed for the European and North American leisure market. Its model has both single and double burner. The CleanCook is currently manufactured in Slovakia, but the possibility of local production by Makobu Enterprises PLC of Ethiopia is underway. This local production is in its early stages in Addis Ababa, with a starting goal of 18,000 stoves to be produced yearly.

Figure 1-1: Two burners CleanCook ethanol stove (95 % v/v ethanol-water mixture) [3] Gaia Association collected indoor air pollution data under CEIHD (Center for Entrepreneurship in International Healthy and Development) guidance homes in Addis Ababa and refugee camps through Ethiopia. Gaia Association is an Ethiopian NGO formed to further the aims of Project Gaia research studies, which has as its purpose to demonstrate the use of alcohol fuels for household and refugee use in Ethiopia. The association seeks to replace existing traditional fuels such as firewood, kerosene, charcoal, and dung that have been shown to be harmful to human health. A study was conducted in a total of 9 households in Addis Ababa and consisted of indoor air quality monitoring for 48 hours both before and after the introduction of the CleanCook stove. Monitoring equipment was again positioned in kitchens in accordance with the standard placement protocols given by CEIHD. They also stated as using of two extra additives for the change need of colorless ethanol-water mixture to colorful and bittering to avoid the inhalation problem of peoples during cooking. The average particulate matter concentration in the kitchens was reduced after the households began using the CleanCook stove (from 640 g/m3 to 230 g /m3), a very significant improvement in indoor air quality. The households moved closer to the WHO interim target (75 g/m3) for PM2.5 and the Air Quality Guideline (25 g/m3) in the after phase. The average CO

kitchen concentration in charcoal and kerosene stove case was 28.5 mg/m3 and dropped to 6.7 mg/m3 with the CleanCook stove, below the WHO guideline of 10 mg/m3 (Annex A) [4]. The other model of ethanol stove designed, manufactured, and distributed to consumers is lowconcentration ethanol stove in rural areas of India, as shown in figure 1-2. It works in weight ratio of 50 % ethanol-water concentration and uses hand pump to pressurize the fuel from the separate fuel tank to the burner canister [5]. It is an ethanol stove running on 50 % ethanol-water mixture has been developed at Nimbkar Agricultural Research Institute (NARI) the first time makes and the idea of its development is very novel. Field tests conducted on the stove show that it is safe to use and very suitable for a typical rural household and average CO concentration near the stove is found as 9 ppm. In addition, the cost of using the ethanol stove is comparable to those of the conventional liquid fuel alternatives. It is the lowest ethanol in water content and thus it called as low-concentration ethanol stove. Nimbkar Agricultural Research Institute (NARI) was the first to propose and develop a stove running on 50 % ethanol-water mixture to solve the cooking fuel crisis. This mixture is selected for which it can easily be distilled very efficiently in a rudimentary rural distillation unit. It burns very cleanly without any smoke or smell and has clear yellowish than blue of pure ethanol.

Figure 1-2: Low concentration ethanol stove (50 % w/w ethanol-water mixture) [5] Nimbkar Agricultural Research Institute (NARI) also developed Ethanol stove for both cooking and lighting area where having deficiency of alternative lighting source. The clear white

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yellowish color flame used in cooking gives light for the area near stove present as shown figure 1-3 below. It is usually a low grade between 45-60 % (w/w) ethanol-water concentrations [6].

Figure 1-3: Ethanol stove for both cooking and lighting (45-60 % w/w ethanol-water mixture) [6] Many small projects also conducted by the base of ethanol flammability for cooking, lighting and other applications. Different models are also available in internet, YouTube video of ethanol fire rating and applications. The main attention of this study to come-up with best concentration of ethanol-water mixture based on safe flammability for household cooking purpose. Finding of safe flammable ethanolwater concentration is the most economical in comparison of fuel consumption and stove design consideration in feasibility. Ethanol and water molecular similarity and due to weak hydrogen bond makes them complete miscible. Using of pure ethanol for household cooking is dangerous due to its high flammability of alcoholic property. So, the optimal value of ethanol-water mixture for cooking is between the inflammability of water and high flammability of ethanol. 1.4.2 Impacts of Household Energy Patterns Naturally, dry air is a mixture of 78 % nitrogen, 21 % oxygen, 0.03 % carbon dioxide as well as argon and other trace concentrations. Air is said to be polluted when one or more of

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contaminants present in sufficient amount for such duration as to affect the physical well being of people, animal, vegetation, or materials. Traditional biomass such as fuelwood, agricultural waste and animal dung, to meet the people daily energy needs of cooking used in most areas of the world. This accounts over 3 billion peoples in the world, and 575 million people (76 %) in sub-Sahara Africa. Since Ethiopia is the third largest user in the world of traditional fuels for household energy use, which is accounted over 90 % dependency of traditional biomass for cooking [7]. Even if traditional fuels were harvested sustainably, it would not be carbon neutral due to its incomplete combustion in the idealized fuel cycle in which all the carbon is converted to carbon dioxide and is not a realistic model. Due to its incomplete combustion, carbon is released in other forms and including methane (CH4), nitrous oxide (N2O), carbon monoxide (CO) and nonmethane hydrocarbons and sulfur compound. These compounds are referred to as products of incomplete combustion and have a much greater potential impact on climate change. Therefore, the category of fuel in cooking which can produce little or no such impure compounds we called clean cook fuels and their importance and advantage is shown in detail in the next section. Cooking with wood fires is also unsustainable and contributes to rapid deforestation in the developing world. Where wood is already limited and taking of long time to replacement, its collection leads to desertification. In Africa, collection of wood for cooking and charcoal production is the primary reason for the disappearance of the forests. Further, the burning of hydrocarbon fuels, coal, charcoal, and even dung contributes to the accumulation of greenhouse gases. Smoky cooking fires and stoves contribute to the soot that is estimated to cause approximately 16 % of global warming. Black carbon particles in the atmosphere are considered one of the most dangerous pollutants after carbon dioxide. The World Health Organization estimates that 1.5 million premature deaths per year are directly attributable to indoor air pollution from the use of solid fuels. That is more than 4,000 deaths per day, more than half of them children under five years of age. This means that indoor air pollution associated with biomass use is directly responsible for more deaths than malaria, almost as many as tuberculosis and almost half as many as HIV/AIDS.

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In Ethiopia, about 200 hectare forest cover is lost annually because of people need to cut trees for firewood. With that about two billion square meters of soil is lost annually due to erosion consequently farm yield potential is reduced by 2 % every year [8]. This is fatal for such a poor under poverty level agriculture based country that is still not able to cover its own daily hand to mouth food demand. In addition, beside environmental and agricultural consequences, the energy of household has further economical and healthy impacts. Though fossil fuels account only for 5% of the primary energy consume in Ethiopia, they costs nearly 50 % of the export earnings of this developing country. Moreover, the world market prices are rising with the economic and progress with standard of life for the future expectation is make more fear. Beginning with health, it estimated indoor air pollution of cooking results in 1.6 million deaths worldwide each year, and among 24 % of which occur in Africa. Therefore, the primary cause of this indoor air pollution is household fuel use, particularly from traditional fuels burned in highly inefficient traditional stoves. Since, Ethiopia is in position as the third largest user in the worlds of traditional fuel with the habit of burning fuel wood in the traditional three stone fire place whose efficiency is just 5 to 10 % compared to 70 to 80 % of an electric stove. It is clear that, in Ethiopia most population resides in rural area where only wood and agricultural residue to be used for cooking, using traditional mud cooking pots, and inefficient open cooking condition needs lots of energy. Thus, for the need of high cooking energy and long cooking time need results the high emission particulate concentration and these influences the life of cooking mothers frequently. In the way of energy use patterns affect different members of the household to varying degrees are not limited to health. The major task division acquiring sufficient energy in Ethiopia to meet in family basic needs of food and shelter culturally delegated to the women of the household than men depending on access to energy and biomass. Rural housewife and children of Ethiopia travel up to 12 kilometers from their home to collect cooking fuels. They are also force to collect inferior fuels in the form of bushes, twigs, roots, and crop residues and all of which translate into longer preparation and cooking times; the same is true for urban women, who also operate under extremely harsh conditions and, like their rural counterparts, have to walk long distances on

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harsh terrain, often barefoot, and with heavy loads. Border guards at checkpoints will sometimes harass these women, demanding bribe money to allow them to bring in fuel. Traditional healers in the urban centers of Addis Ababa and Delanta often treat women for severe abdominal pains attributed to carrying these heavy loads over long distances. Once collected, additional time must be spent by women preparing the fuels for use not only in cooking, but also in the supply of water, space heating, and for use in household processing industries, often crucial as income and employment generating sources.

Figure 1-4: Rural housewife from fire wood collection These impacts are not felt equally all members of the household. The WHO (2004) estimates that just over half of worldwide deaths in children under the age of five are caused by indoor air pollution, while the proportion of the total global burden of disease in children of the same age caused by indoor air pollution is a staggering 80 %. In regards to Ethiopia, those same reasons offered above as to why Ethiopians likely share in the count of worldwide deaths from indoor air pollution similarly apply here. Furthermore, as the majority of household energy demand in Ethiopia is due to cooking, with approximately 50 % of Ethiopias primary energy consumption used to bake injera, women also share an unequal burden of death and disease from indoor air pollution as they are the primary cook; studies have shown that emissions are not equally dispersed about a room, but rather are highest at the source of combustion, decreasing as movement away from the energy source occurs.

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1.4.3 Clean cooking fuel, ethanol and benefits A sustainable energy production and consumption is a basic need for under developed countries for sustainable development and energy access for daily the basic needs. It is a very important precondition for education, health, economic progress as well as for a reliable food supply. Energy is also strongly related to the local, national and global environment. The lossing of forests, farm lands, and wild life by desertification and whole eco-systems imbalance and also the dramatic impacts of climate change are all consequences of non-sustainable traditional energy generation and consumption. Some of the clean and renewable fuels for cooking are gaseous fuels like biogas, solid fuels like charcoal, and liquid fuels like biodiesel and ethanol. However, due to their high energy density, easy transportability and storage the liquid fuels are superior to other renewable alternatives. The selection and demand of household energy is mainly depends on not to harm cooking mothers, availability in that area, and suitable to handle. Liquid fuels are considered to be a good alternative in easy handling rather than solid and gaseous fuels for house hold purposes. Among all the liquid fuels which can be produced locally and in a renewable manner, ethanol is one of the best biofuel. It is an excellent substitute for kerosene and burns better than kerosene without any particulate or unpleasant smell and its renewability and local production make ethanol better. In fact, its combustion is almost as clean as that of LPG. Hence, the use of ethanol fuel for cooking and lighting for rural areas needs to be encouraged for developing rural areas. Combustion of a liquid fuel in an oxidizing atmosphere actually happens in the gas phase. Therefore, a liquid will normally catch fire only above a certain temperature: its flash point. The flash point of a liquid fuel is the lowest temperature at which it can form an ignitable vapor composition for easy mixing with air. Several countries in Africa are currently distilling ethanol at significant scales, including Ethiopia, Kenya, Malawi and Zimbabwe. The ethanol produced is mainly used as an additive in transportation fuels. Ethanol is produced by fermenting the sugars containing various types of biomass feedstock. It can also be produced from starches if they are first converted into simpler sugars. The resulting mixture is then distilled to yield a high concentration or pure ethanol in

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minimizing of water content of fermentation solution. There are a wide range of crops that can be used as feedstock or inputs of ethanol production, including sugarcane, cassava, sweet sorghum, maize and wheat. The ideal feedstock for the production of ethanol is dependent on regional climate and soil conditions, the crops annual cycles, and available technology. Alcohol fermentation is done by yeast and some kinds of bacteria. These microorganisms convert sugars in to ethyl alcohol and carbon dioxide. Alcoholic fermentation begins after glucose enters the cell. The glucose is broken down into pyruvic acid. This pyruvic acid is then converted to CO2, ethanol, and energy for the cell. The yeast secretes enzymes that digest the sugar (C6H12O6), yielding several products including lactic acid, hydrogen, carbon

dioxide (CO2), and ethanol (C2H5OH) with water contents. Thus water content is further separated from ethanol by continuous distillation and carbon dioxide to be push out through chimney. The chemical equation of the dissociation summarized in equation 1-1, the fermentation of glucose, whose chemical formula is C6H12O6. One mole of glucose is converted into two moles of ethanol and two moles of carbon dioxide: C6H12O6 2C2H5OH + 2CO2 (1-1)

While ethanol is still in development as a cooking fuel in many African countries, Project Gaia has taken the lead in Ethiopia to make it commercially available to urban households. A large number of stakeholders have contributed to the effort. With respect to ethanol production, Ethiopias position among other sub-Saharan African nations is unique: since 2008 eight million liters of ethanol are produced from waste product molasses at the Fincha Sugar Factory each year, and none of this ethanol currently has a market. Because of this great potential, Domestic AB introduced the ethanol-compatible CleanCook Stove and conducted a pilot study among 850 Addis Ababa households and emission rate is estimated. The study confirmed the stoves popularity among users, who cited a number of benefits.

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Therefore, ethanol is the most favorable clean cooking fuel among other clean cooking fuels. That is based on its easily handling and transportation, low emission rate and having of capacity to produce. This is the idea for this study to select ethanol for cooking and develop ethanol stove.

Reduced deforestation
The loss of the worlds forests is a pressing environmental issue: the global forest area is decreasing by 0.2 % per year. The rate of deforestation is greatest in Africa, where the area of forested land decreases by about 0.6 % per year. In case of Ethiopia over 200 hectare cover forest is losing annually due to using of traditional cooking with traditional fuels [9]. Researchers have pointed to numerous causes for this high rate of loss, including agricultural expansion, firewood collection, charcoal production, timber harvesting, and development of infrastructure. Despite the difficulties inherent in measuring the extent to which these factors contribute to deforestation, a number of studies have attempted to do so. The findings of these studies vary depending on their regional focus. Despite regional differences there is a clear link between wood fuel extraction and deforestation: a statistical analysis that includes data from 40 African nations reports a strong correlation between the rate of deforestation and the rate of wood fuel production. A transition to clean cooking fuels has the potential to reduce the rate of sub-Saharan deforestation as households would depend less on wood fuel for energy.

Climate change mitigation

The predominance of wood fuel in household cooking is related to global climate change through two primary mechanisms. First, to the extent that biomass for wood fuel is being harvested at an unsustainable rate (i.e. the rate of extraction exceeds the rate of replenishment since it takes long time for replacement) the capacity of the biosphere to remove carbon dioxide from the atmosphere is reduced. Secondly, because of the combustion of wood fuel in household cooking is incomplete as I have stated before, some of the carbon in the wood fuel is released in forms other than carbon dioxide, which may have a greater effect on surround climate. Because of deforestation, the amount of carbon that can be stored in the biosphere is continually decreasing, which results in a net increase of carbon dioxide in the atmosphere since reduction of carbon dioxide absorbing plantation. In the most ideal biomass fuel cycle, one in which combustion is

17

completed so that all the carbon is converted to carbon dioxide. When the sustainability condition is not met, the rate at which carbon dioxide is emitted exceeds the ability of the forests to remove it from the atmosphere, resulting in increased atmospheric concentrations of carbon dioxide and similarly other pollutants.

Reduction of indoor air pollution

The wood fuel, agricultural residue, and animal dung that most of Africas households use for cooking are major sources of indoor air pollution. The inefficient and incomplete combustion of these fuels release a number of hazardous pollutants, including carbon monoxide, sulfur and nitrogen oxides and particulate matter and soot accumulation. In many households, poor ventilation exacerbates the effects of these pollutants and women children are often exposed to them at significant levels for between three, and seven hours each day accordingly cooking time. Such prolonged exposure to indoor air pollution has been implicated in the increased incidence of a number of respiratory, and eye diseases in developing nations. Therefore, in using of clean cooking fuel completely avoids indoor air pollution.

Safety issues for clean liquid and gaseous fuels for cooking in the scope of sustainable development
Several fuel types have been used for cooking throughout the world, ranging from solid fuels to liquid to gas. Gaseous fuels are considered cleaner because of their inherent characteristics of low pollutant formation and emissions during handling and during cooking. Nevertheless, from the viewpoint of sustainable development, other safety properties are important to know, such as flammability limits, autoignition temperature, specific gravity, vapour pressure, toxicity and flash point. The value of these properties of ethanol-water mixture is tabulated in appendix at end page of the paper.

18

CHAPTER 2 2 PROPERTY OF ETHANOL-WATER MIXTURE 2.1 Property of Ethanol

Ethanol under ordinary condition is a volatile, flammable, clear, colorless liquid. Its odour is pleasant, familiar, and characteristic, as is its taste when it is suitably dilute with water. Ethanols miscibility with water contrasts with that of longer-chain alcohols (five or more carbon atoms), whose water miscibility decreases sharply as the number of carbons increases. The physical and chemical properties of ethanol are primarily dependent upon the hydroxyl group. This group imparts polarity to the molecule and also gives rise to intermolecular hydrogen bonding. In the liquid state, hydrogen bonds are formed by the attraction of the hydroxyl hydrogen of one molecule and the hydroxyl oxygen of a second molecule. It is completely miscible with water and organic solvents and due to its high hydroscopic readily absorbs water from air and this is due to having of weak hydrogen bonding. Ethanol has widespread use as a solvent of substances intended for human contact or consumption, including scents, flavorings, colorings, and medicines. In chemistry, it is both an essential solvent and a feedstock for the synthesis of other products. It has a long history as a fuel for heat Combustion. Ethanol has a boiling point 78.5 oC and specific density of 0.793 at 20 oC. Complete combustion of ethanol forms carbon dioxide and water in pure case at STP: C2H5OH + 3 O2 2 CO2 + 3H2O (l) (2-1)

Flash point is a unique property of a liquid fuel is to know the relative hazard of fuels and used to classify the liquid fuels whether flammable or combustible. Flash point is a lowest possible temperature at which a fuel has enough flammable vapour to ignite by the surrounding air. For pure ethanol flash point is 13.4 oC and the highest flash-point is at a mixture of 5 % v/v ethanolwater mixture and which is 62 oC thus the safety of ethanol for household application in open air is increase with increase of water content. Any liquid with a flashpoint less than 37.8 C is considered as flammable liquid. Any liquid with a flashpoint between 37.8 C 92 C is

19

considered to be combustible liquid [10]. Therefore, ethanol-water solution is considered as flammable for the ethanol percentage greater than 20 and less than of it is classified as combustible liquid (Annex B). Comparing the flammability limit for the fire hazard maintenance of ethanol with others hydrocarbon fuels like kerosene, gasoline and diesel, ethanol has the highest value of lower flammability limit (LFL). Accidental fires often occur because flammable vapor increases from a fuel at low level flammability producing the minimum concentration of ignitable vapour at which ignition will occur. The higher the value for the LFL, the less likely a fire hazard will result. Thus, a high value for LFL is considered to be safer than a low LFL value. Ethanol has a LFL value of 3.3 % in air at room temperature and methanol a value of 6.0 %. These values are significantly greater than for kerosene at 1.7 % and gasoline at 1.4 %. Depending upon the nature or composition of the kerosene, its LFL can sometimes be lower up to 0.7 %. The LFL of diesel is 0.6 % [11]. Ethanol is the most flammable alcoholic fuel. A method for maintaining a flammable solvent is a treating with a nonflammable environment involves maintaining of flammable solvent, nonflammable vapor blanket in combustion provided by non flammable solvent, such that vapor from the flammable and nonflammable solvent form a non flammable gaseous mixture in the blanket. Such method is used in removal of both oil-based polar contaminants to control the flammability potential of an alcohol solvent. Since, it is miscible in water using water to maintain its flammability is best way. For the mixture of ethanol and water, the water molecules in the mixture vaporize along the length of the flame during combustion, it restricts the speed and length of the flame but it has no contribution of the combustion. In addition to the maintaining the flammability of ethanol, it improves the consumption of the fuel. For the case of household cooking, mixing ethanol with water is a mechanism in order to reduce its flammability since it is flammability in volume ratio up to ethanol 20 %. The oxygen-balance or an expression used to indicate the degree to which an explosive can be oxidized of ethanol is -208.7 %, which is far from other cooking fuels such as methane (CH4), is -4 %, gasoline (C8H18) is -3.5 %, and kerosene (C10H22) is -3.5 %. But, when the percentage of

20

water increased and the percentage of ethanol reduced in mixture case the oxygen-balance negatively reduced and this is the percentage reduction of explosiveness. The oxygen-balance of explosive molecule of zero is that all carbon atoms of the fuel convert to carbon dioxide, all hydrogen atoms of the fuel is converted to water, all sulfur of the fuel to sulfur dioxide, and all metals to metal oxides with no excess and is called zero oxygen-balance. The negative oxygenbalance means the compound contains less oxygen than need and in reverse case having of excess oxygen than the need one. Ethanol is one of clean fuels that used in the house hold energy consumption for cooking. Even if the energy content of ethanol is lower than gasoline, it is high flammable than gasoline and thus impossible using of ethanol- gasoline mixture in open air whether cooking or other purpose. However, their blend is commonly used for engines of vehicles in a closed carburetor. Now days flex-fuel vehicles (FFV) with some engine modification are more developing through the world. This accommodates the application ethanol in wider range as fuel for vehicles.

2.2

Ethanol- water mixture

Solution may be binary or tertiary and so on accordingly the number of substances to be contributed in mixture. In a solution, substance present in a large quantity is called solvent and the other to be solute in the arbitrary convention at known temperature and pressure. For the binary solution formed by ethanol and water, nomenclature of solvent and solute reverse depending on the relative amount one two. If the mixture is formed equal amount of two quantities, the nomenclature of solvent and solute left in the wish of experimentalists. Solution is physical bonding of molecules of two or more either solid or liquid soluble quantities mixing in one space of they occupy. The solubility of mixture depends on either of molecular interaction force (attraction or repulsion) and/or thermodynamic functions. Ethanol and water are completely miscible in to each other in all proportion. The explanation for this is given by the fact that water-ethanol attraction force is stronger than that of water-water and ethanol-ethanol interaction. That is the interaction force between water and ethanol are predominantly dipole-dipole and hydrogen bonding. In thermodynamic relation of mixture, any dissolution processes the free energy change

21

must be negative that is the process must be exoergonic. This implies that the free energy of solution must be less than the free energy of solute and solvent. All values of ethanol-water mixture the mixture enthalpy is negative as shown section 2.3.3, and the small mixing temperature and entropy, the free Gibbs energy of is always negative. Therefore, the right dissolution of two mixtures, to get negative free energy of solution, there must be either higher negative or exothermic mixing or there to be higher positive randomness of solution. The other principle for solubility is like dissolves like principle and usually based on phase similarity. This usually indicates that similar materials with similar property dissolved one by another. Since, the molecules of ethanol are much smaller than water molecules in the solution of ethanolwater mixture, so when the two liquids are mixed together the ethanol falls between the spaces left by the water thus reduction of volume than the sum volume of two quantities. It's similar to what happens when you mix a liter of sand and a liter of rocks. You get less than two liters total volume because the sand fell between the rocks, right? Intermolecular forces (hydrogen bonding, London dispersion forces, and dipole-dipole forces) also play their part in miscibility, but that's another story. The great similarity of the two molecules and hydroscopic attractive property of ethanol, ethanol and water are complete miscible to each other solutions thus the water molecules (H2O) and ethanol molecule (CH3CH2OH) are interchangeable arrangement in the solution. The molecules are in sense "dumb" and can't distinguish one from the other since both are colorless and there to be no possible limit for concentration of water in ethanol or ethanol in water. The boiling point temperature of pure ethanol is 78.5 oC and the boiling point temperature of water is 100 oC, thus the boiling point temperature of ethanol-water mixture is between 78.5 oC and 100 oC. But from the experimental determination the boiling point temperature decrease linearly up to ethanol-water mixture of 95.6 % in volume ratio (at 78.2 oC), then increase again linearly to the boiling point temperature of pure ethanol. This is the unique property of ethanol in

22

water solution. Since ethanol and water forms non-ideal mixture, the vapour pressure of vapour composition is large positive deviation from Raoult's Law between liquid compositions during boiling of ethanol water mixture. The occurrence of week hydrogen bonding is responsible for large deviations in the random distribution of molecules that commonly used equations of state and liquid solution models are not able to describe.

2.3

Determination of ethanolwater mixture ideal property

The property of ethanol-water mixture is different from property of pure ethanol or pure water. Boiling point, density, flammability, flash point and freezing point changed accordingly the mole fraction of both quantities in the solution. To come-up with the correct numerical value of property of the mixture some correlations may used or in other case the experimental data values used. Knowing of both physical and chemical property of substance is the initial step to put the material as important and selective for the specific applications. The properties may be either in ideal or non-ideal property. 2.3.1 Boiling point pressure and temperature The boiling point temperature is an important property for the ready combustion and continuous burning property of the fuel. Considering the ethanol-water mixture as ideal in its vapour pressure, total solution pressure is the sum of molar partial pressure of ethanol and water. The partial molar pressure of ethanol and water and it is a linear relation with vapor pressure in pure case of each. The relation is stated as the equations shown below ;

Pwater = Powaterxwater Pethanol = Poethanolxethanol

Therefore, the total pressure of mixture ethanol and water is to be the sum of partial molar pressure of both components.

Pmixture = Pwater+ Pethanol

23

Relation of Saturation Pressure of mixture and ethanol mole fraction

7

Saturation pressure kPa

6 5 4 3 2 1 0 0 0.1 0.2 0.3 P ethanol 0.4 0.5 P water 0.6 0.7 P mix 0.8 0.9 1

Figure 2-1: Ideal case partial pressure of ethanol, water and ethanol-water mixture

Table 2-1: Physical Properties of ethanol and water Value Liquid density Vapour density @ 95 oC Molecular weight Liquid Heat Capacity Heat of Vaporization Vapour Pressure @ 90oC Units g/mL g/mL g/mol J/gK J/g torr Ethanol 0.789 0.0015 46.0634 2.845 855 1187 Water 1.000 0.001 18.0152 4.184 2260 525

Antoine formula for the relation of temperature and saturation pressure ln (Psat) = A - B/ (T+C): Psat (kPa) T (oC) where: A, B, and C are Antoine constants and listed in table below. (2-2)

24

Table 2-2: Antoine constants of water and ethanol Species of solution Ethanol Water A 16.6758 16.2620 B 3,674.49 3,799.89 C 226.45 226.35

The actual partial pressure relation of ethanol and water mixture is determined by using of Antoine relation of temperature and pressure. Experimental data of ethanol and water mole fraction in both liquid and vapour case up to the azeotropic point (95.6 %) of ethanol, the relation of mole fraction and boiling point temperature developed [Annex C]. 2.3.2 Fraction distillation of an azeotrope of ethanol-water mixture Deviation of partial molar quantities of solution comparing with pure case of individual, solution may classify as either ideal or non-ideal solution. Ideal solution, there is no change of partial molar quantities (volume, internal energy and/or other quantities) of mixture and is completely satisfy the Raoults Law with zero deviation in both liquid and vapour composition state in both pressure and temperature. In other case Non-ideal solution is there is quite positive or negative change of partial molar quantities (volume, internal energy and/or other quantities) of mixture compared with pure state. Changes of partial molar quantities of liquid and vapor composition during boiling and is not satisfied with Raoults Law of solution. The relation of vapour and liquid concentration with the boiling point temperature varies. It deals that at certain point temperature the composition of liquid phase and vapour escaped from the liquid surface except the azeotropic point. But at the azeotropic mixture of ethanol-water solution, the concentration of liquid and vapour escape from the liquid surface is identical (i.e. x 1 = y1 = x2 = y2) and hence by method of fractional distillation is impossible to separate in to the individual mixture component.. That is we called liquid-vapour equilibrium (LVE) property of ethanol-water solution. The minimum boiling point temperature (78.2 oC) ethanol-water mixture attained at the concentration 95.6% by mass ratio. Fractional distillation used to reduce the water content after

25

fermentation process produces 95.6 % concentrated ethanol by mass which is an azeotrope mixture having boiling point of 78.2 C . If the solution with the azeotropic composition is heated then vaporization takes place in such a manner that the relative amount of two components are identical in the vapour and liquid phase. Similarly, the freezing point temperature of ethanol-water mixture is between the freezing point temperature of ethanol (-114.3oC) and the freezing point temperature of water (0 oC). Mixing ethanol and water to make it safe for household use the ratio above 50 % ethanol usually the freezing temperature below -32 oC and since there is very far of freezing point temperature than usual ambient condition, no usual freezing problem of mixture. However, the density of mixture varies with temperature, for all case its variation is only within the density of ethanol and water [12]. At the azeotropic concentration, the mole fraction of liquid and vapour in each quantity is equal. That means for example, the liquid and vapour mole fraction of ethanol or water is equal in ethanol-water mixture. The azeotropic concentration of binary liquid solution of solute is determined by using the equation 2.5 below.
ln ln
P az P 1sat P az P 2sat

1 x 1az

=1+

(2-3)

Where: o P1sat is saturation pressure of solute o P2sat is saturation pressure of solvent o Paz is pressure of mixture at azeotropic point 2.3.3 Enthalpy of mixing Enthalpy of solution or enthalpy of mixture for a binary solution is measured using a suitable calorimeter. Here it is not possible to determine the absolute value of total enthalpy of solution or

26

the mean molar enthalpy rather we have to use the thermodynamic relation to calculate the change in partial molar enthalpy. The enthalpy change accompanying the formation of (n 1 + n2) mole mixture is calculated as follows; H mix = n1H1, m + n2H2, m For a liquid-liquid solution of enthalpy of mixture per mole is: H (n1+ n2) mix = x1H1, m + x2H2, m = x1H1, m + (1- x1) H2, m H (n1+ n2) mix = x1(H1, m - H2, m) + H2, m Where: Hm = , mean mole enthalpy The Enthalpy of Solution is the heat change which takes place when one mole of a solute is completely dissolved in a solvent to form a solution of concentration measured under certain conditions. Enthalpy of Solution can be measured experimentally. It can also be calculated; it is the sum of two imaginary steps: the reverse of the lattice enthalpy plus the sum of the hydration enthalpies of the ions. The mixing process of ethanol and water is exothermic process and energy released to form alternative bonding between ethanol and water. The relation of mixture enthalpy and mole fraction of ethanol and water shows that increasing mixture enthalpy up to 15 % ethanol in mixture and the decrease linearly. Therefore the maximum energy release (-780 J/mol) occurs at 15 % ethanol in water mixture. Since ethanol-water mixture is non-ideal solution, the calculated value of equation 2-5 cannot match with the real data of mixture enthalpy. The excess Gibbs energy is as the correction factor between the experimental and analytical values. The real experimental data of mixture enthalpy of ethanol-water mixture at STP is plotted in figure 2-2 below [13]. When two miscible liquids
H

(2-4)

(2-5)

27

are mixed, a positive or negative heat effect occurs, which is caused by the interactions between the molecules. This heat effect is dependent on the mixing ratio. The integral mixing enthalpy and the differential molar mixing enthalpy can be determined by calorimetric measurements of the heat of reaction.

% mole fraction of ethanol-water mixture

0 -100 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95 0.97

Mixiture enthalpy J/mol

-200 -300 -400 -500 -600 -700 -800 -900

Figure 2-2: Mixing enthalpy of ethanol-water mixture [12] The temperature change when known amounts of water and ethanol mixed was determined; this is the enthalpy change in an isothermal and isobaric environment. Agreeable data was found by analytically and compared to similar experiments. Since waters structure and unique properties affect many aspects of a solution, the solutions enthalpys decreased at a certain time due to ethanols non-electrolyte nature. All the values of ethanol-water mixture enthalpy are negative and which shows that Gibbs free energy to be negative for all temperature values and this indicates the miscibility of ethanol and water.

28

2.4

Partial molar volume

If you add 50 mL of water to 50 mL of water you get 100 mL of water. Similarly, if you add 50 mL of ethanol (alcohol) to 50 mL of ethanol you get 100 mL of ethanol. But, if you mix 50 mL of water and 50 mL of ethanol you get approximately 96 mL of liquid, not 100 mL why? First, the molecules of ethanol are much smaller than water and thus they filled with the space left between water molecules just as mixing of fine sand and larger stone. In the other case, the intermolecular force of ethanol-ethanol or water-water is less than that of ethanol-water or waterethanol. Mixing of known concentration is prepared by mixing calculated quantities of the two substances and the density of each mixture is accurately measured. From Eulers theorem of homogeneous mixture is related as; V = n1(n1 ) + n2(n2 ) is volume of mixture = n1V1, m + n2V1, m
V V

Vm =

V n1+n2

w 1+w2 12(n1+n2)

is the mean molar volume

V = n1+n2 = (X1M1+X2M2 )(X1V1, m + X2V2, m) Where: M- is the molar mass w-is the mass of the components

w1+w2

(2-6)

Therefore, by using of the simplified formula based on only known quantities, in equation 2-6 above, the volume of mixture is calculated and for the sum volume of two quantities there is little depression of volume. Thus, change of volume of sum volume of two quantities and mixture volume with the mole fraction of ethanol in the ethanol-water mixture relation shown in figure 23 below.

29

Volume change with ethanol mole fraction

0

Excess volume (mL)

2.5

-0.2 -0.4 -0.6 -0.8 -1

-1.2
-1.4

Figure 2-3: The calculated volume change of 10 mL sample The maximum flame temperature

When fuel burns definite amount of products are formed and a definite quantity of heat is librated by breaking down of molecules of the fuel. This quantity of heat may be utilized to rise a temperature of the products of combustion sufficiently to produce a flame. This temperature is called maximum flame temperature or calorific intensity. In the case, experiment is performed at a constant pressure of combustion then heat librated is denoted by (Hc) and maximum temperature attained is the flame temperature or usually called adiabatic flame temperature. The measurement of adiabatic is the combustion is absolutely adiabatic with no loss of heat. The fuel maximum flame temperature calculated by considering simple steady-state thermal energy balance can be constructed around a constant-pressure combustion system by using first law of thermodynamics. However, measuring and construction of adiabatic chamber to get maximum flame temperature is so difficult practically

0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95

30

Figure 2-4: Combustion model of controlled system The energy balance about the combustion of fuel in controlled system can be written as: CV + HR = Qc + Hc + HP Where: CV- calorific value of fuel HR-sensible heat of reactants Qc heat loss through the combustion chamber Hc useful heat or heat of total reaction or enthalpy of combustion HP Heat loss of flue gas (2-7)

HR, the sensible heat in the air and fuel (ref. @ 25 oC) is very small since it is in equilibrium with the environment and often neglected. The case heat loss from the outside of the plant, QC is may be conduction, and convection loss through the combustion chamber and loss due to flue gas is to be zero for the adiabatic assumption case. So, by using heat of reaction or useful output heat by heat of combustion, we can determine the maximum flame temperature using equation (2-7) by rewriting of equation 2-8.

31

 = = Where:

2 1

(2-8)

o T1 is the initial reference temperature o Tf is maximum flame temperature o is sum of heat capacities of all species present in system after reaction complete Based on the property, initial temperature and composition of the fuel, the maximum flame temperature to be determined accordingly equation (2-8). For the reaction of pure ethanol (equation 2-1) is modified for mole balance and then in mass relation is as follows; C2H5OH + 3(O2 + 3.76 N2) 2CO2 + 3H2O + (3x3.76) N2 From this relation of balanced equation, again the mass balance is: 1 Kg C2H5OH +2.087 Kg O2 + 6.86 Kg N2 1.91 Kg CO2 + 1.17 Kg H2O + 6.86 Kg N2 The procedure of calculating the adiabatic flame temperature of fuel by straightforward method is; 1) Evaluate the initial energy values of the fuel (CV and HR); But for this calculation, assuming the initial temperature change of reactants is zero i.e. HR=0. 2) Guess the value of Tf and use this value to find the specific heat of combustion products at the average between that value and the reference temperature i.e. [(Tf + 25)/2] oC 3) Solve by using equation (2-7). 4) Compare the new value of Tf with the original estimated and if there substantial difference, use the new value to re-evaluate the specific heat, looping back to equation (2-7) until satisfactory convergence is achieved. This is for the

32

calculation accuracy for that the specific heat of flue gases is change with temperature difference. From the relation of equation (2-8) the right side is the high calorific value of ethanol at a standard temperature and pressure (298.15 K and 1atm) is 29,700 KJ/Kg and the left side is summation of heat capacities of all species present in combustion of ethanol. Simplified relation for maximum flame temperature is; Tf = T1 + CV mCpm

For initial guess of Tf =700 oC, thus the specific heat Cp of products is; CO2 = 1.230 KJ/Kg oC H2O = 2.264 KJ/Kg oC N2O = 1.159 KJ/Kg oC

= 1.911.230 + 1.17 2.264 + 6.861.159 = 12.949 Tf =2591.8 K = 2318.65 oC And the mean temperature of the flue gases to be [(2318.65 + 25)/2] oC =1155.32 oC and the specific heat at that temperature is; CO2 = 1.316 KJ/Kg oC H2O = 2.564 KJ/Kg oC N2O = 1.237 KJ/Kg oC

= 1.91 1.316 + 1.17 2.564 + 6.86 1.237 = 14.009 Tf = 2419.7 K = 2146.6 oC there is no more difference come in further iteration. Therefore the adiabatic flame temperature of ethanol is 2146.6 oC. This value is more accurate and close to measured value or data, than the theoretical data it is best in my opinion.

33

2.6

Flammability of ethanol-water mixture fuel

In the chemical reaction of ethanol in air one mole of ethanol react with three moles of air, two moles of carbon dioxide and three moles of steam produced as equation (2-1) stated above. The stochiometric air quantity is the minimum amount of air needed for the complete conversion of fuel to its product gases. But for most cases to achieve satisfactory complete combustion, some quantity of excess air is used. However, the excess air used for combustion may get as product in the product side that reduces the combustion heat and further reduces flame temperature. Ethanol is very flammable with very low flash-point (~15 ) and has been used in Brazil and South Africa as cooking fuel. However generally it is used (85 % v/v) and higher concentration and is a dangerous fuel and many fire deaths have been reported in its use at those concentrations. For the mixing of incombustible water to ethanol the water at the reactant side is converted to steam and as flue gas at the product side together with the product of ethanol combustion steam. Flash-point is clearly decreased with increasing water content in the mixture and this makes volatile ethanol safe for cooking. Therefore, when the content of water in the mixture increase, the quantity of flue gas increase thus the quantity of heat librated is reduced also the temperature of flame is again reduced. To determine the stochiometric air of the mixture of ethanol and water for example, 50 % ethanol-water solution fuel, since there is 50 % (v/v) ethanol in ethanol-water mixture and 21 % oxygen in air in the balanced equation of C2H5OH + 3O2 2CO2 + 3H2O: 1/0.50 = 2.0 Volumes of ethanol-water mixture requires 3/0.21 = 14.285 volumes of air, Or, one volume of ethanol-water mixture requires 14.285/2.0 = 7.1428 volumes of air or in percentage relation (1/(1+7.1428) = 0.1228 =12.28 %). This is ethanol-water mixture in air (stochiometric air requirement of ethanol mixture). Every fuel has its upper and lower flammability limit. The upper flammability limit (UFL) is the highest percentage limit of fuel in combustion air that is still flaming and the lowest flammability limit (LFL) is the lowest percentage of fuel in air that the flaming end. The similar calculation of above, flammability of pure ethanol is 6.54 % and shown the flammability of 50 % ethanol-water mixture is 12.28 %. That means the flammability is reduced by half. Ethanol will burn over wide

34

range of flammability from the lower flammability level (LFL) of 3.3 % to the upper flammability level (UFL) is 19 % ethanol in air [14]. The flame temperature of different percentage ethanol-water mixture is depends on the percentage increase of Stochiometric Volume of air for unit volume mixture of fuel and Stochiometric volume percentage of air in constant pressure combustion process. Having of solution with the water content, the temperature is reduced due to in the reduction of generated heat to evaporate water content of mixture and increase of volume percentage of stochiometric air. For that, the relation of maximum flame temperature for the volume percentage ethanolwater mixture is product of Volume % fuel, Volume % air, Peak Temperature (oC), and Peak Pressure (atm) [15]. The peak temperature is the maximum temperature of ethanol-water solution in pure case which calculated in previous section. The calculated values of maximum flame temperature of ethanol-water mixture are summarized in table 2-3 below. Table 2-3: Maximum flame temperature and % of ethanol-water mixture Percentage of ethanol-water mixture (% v/v ratio) 50% 60% 70% 80% 90% 95.0% 100% 7.1428 8.571 9.9995 11.428 12.856 13.570 14.285 87.72 89.55 90.90 91.95 92.78 93.136 100 941.49 1153.37 1365.88 1579.04 1792.45 1899.29 2146.6 Stochiometric Volume of air for unit volume mixture Stochiometric volume % of air Maximum flame temperature (oC)

35

2.7

Activity coefficient ethanol-water mixture

In chemical thermodynamics, activity (symbol a) is a measure of the effective concentration of a species in a mixture, and meaning that the species chemical potential depends on the activity of a non-ideal solution in the same way that it would depend on concentration for an ideal solution. By convention, activity is treated as a dimensionless quantity, although its actual value depends on customary choices of standard state for the species. The activity of pure substances in condensed phases (solid or liquids) is normally taken as unity. A solute in dilute solution is more usual to express the composition of the solution of the solute which shows ideal behavior (also referred to as "infinite-dilution" behaviour). Activity depends on temperature, pressure, and composition of the mixture among other things [16]. The difference between activity and other measures of composition arises because molecules in non-ideal gases or solutions interact with each other, either to attract or to repel each other. Activities should be used to define equilibrium constants but, in practice, concentrations are often used instead. The same is often true of equations for reaction rates. However, there are circumstances where the activity and the concentration are significantly different and, as such, it is not valid to approximate with concentrations where activities are required. The chemical potential of ith component in a liquid non-ideal solution is i = o + RTlnai Where: o o -is chemical potential of ith component in pure case of solution or it is standard value at temperature T, o R -Is gas constant, R=8.31J/K mol o ai -activity of ith component o RT*lnai is excess Gibbs energy (excess chemical potential) (2-9)

36

We can find the activity of a component of a non-ideal solution from measurements of the vapor pressure of that component in the vapor in equilibrium with the solution. We know that the chemical potential of a component must be the same in the vapor as in the liquid.

il = og i = ol + RT lnai = og + RT ln( i )
Po P

(2-10)

Therefore, ai = Where:

pi po

o is actual vapor pressure and o is the vapor pressure of the pure liquid The ratio of activity to mole fraction of i component in a solution is called activity coefficient: = ai/xi and for ideal solution = 1 (that means the activity each element contributes as equal as mole fraction) and for non-ideal solution may be either greater than one (positive deviation) or less than one (negative deviation). Sometimes it is convenient to write the activity as the product of an ideal part times a non ideality correction part. For example, in a non-ideal solution we might write,

= x
In the case of a non-ideal solution i 1 as xi 1 when the solution going to the ideal approximation. That, and from which we can conclude that for a non-ideal solution, i = Pi actual vapor pressure = xi Pi Raoult s law vapor pressure

Activity coefficient is a fundamental thermodynamic quantity which measures the solution nonideality and is as a correction factor to the Raoults law, governs dilute range fluid-phase

37

equilibrium. Predicting of the activity coefficient of ethanol-water solution by using UNIFAC model based on the above relation at temperature of 298 oK is plotted in figure 2-5 below. From the graph below, the activity coefficient of ethanol and water is equal at the mole fraction of x=0.4 accordingly the UNIFAC model prediction. Above the mole fraction of ethanol (x=0.4) the activity coefficient of ethanol is less than that of water is a dilution range of ethanol-water mixture. The UNIFAC model -mole fraction of ethanol relation

9 8

Activity coefficient

6
5 4 3 2 1 0 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

ethanol water

Figure 2.5: Activity coefficient of ethanol-water mixture by UNIFAC [17] 2.8 Flash point of ethanol-water mixture Analytical estimation

The flash-point of a given liquid is the experimentally determined temperature adjusted to standard sea-level atmospheric pressure of 760 mmHg (0.1 MPa) at which substance emits sufficient vapour to form combustible mixture with air. Mathematically, flash-point is the temperature at which the vapour pressure is equivalent to the lover flammability limit in the air.

= ()/

38

Where: Psat(Tfl) is vapour pressure at the flash-point temperature (KPa) P is ambient pressure (KPa)

The flash-point of binary solution is determined by the formula developed by Liaw et.el [18]
x i i P sat i 1P sat (Tfl )i

=1

(2-11)

Where: xi is mole fraction of components of mixture i is activity co-efficiency of components of mixture The above equation is re-witted for the binary mixtures of ethanol and water mixture is as:

xe e Psat e Psat (Tfl)e

xw w Psat w Psat (Tfl)w

=1

A binary aqueous mixture contains water and flammable ethanol, water is non-flammable component and therefore has no flash-point (Tfl). The prediction is equation is reduced from the original Liaw model for the saturation pressure ethanol is:

Psat e =

P sat (Tfl )e xe e

(2-12)

The saturation pressure of with the mole fraction of ethanol in water solution is estimated by using the Antoines relation of section 2.3.1. Therefore, from the relation of equation 2-12, the saturation pressure of ethanol in the water solution at flash-point linearly related by the ethanol mole fraction and activity coefficient.

39

CHAPTER 3 3 ETHANOL-WATER MIXTURE AS COOKING FUEL IN ETHIOPIA 3.1 Potential and quality of ethanol production in Ethiopia
In Ethiopia, Over eight million liters of ethanol is being blend with petrol at the Sululta mixing depot adding that efforts being made to enhance blending are vital to promote the culture of using blended petrol. This blending has saved since 2008 over $10 million of total spends around $ 1.1 billion annually to import fuel for its consumption by blending nearly 13 million liters of ethanol with over 245.2 million liters of benzene. Sugar factories in our country produce ethanol and private investors are also encouraged to engage in the production, which is vital to ensure the countrys energy security [The Ministry of Mines and Energy, 2009]. The main ethanol source in Ethiopia is a co-production of sugar in majorly sugar factories by fermentation of molasses. The quantity of production capacity is high enough for the use of ethanol for cooking As well as blending of it for vehicles fuel. At the beginning of 2009, for the five year plan of Ethiopia water and energy minister, with the production of sugar factories and private factories the country will able to produce over 180 million liters of ethanol in each year [19]. The main area of ethanol production in Ethiopia and its production capacity is listed in table 3-1 below. Table 3-1: Ethanol production capacity of Ethiopia (1000 liters) [19] Ethanol co- 2006/7 2007/8 2008/9 2009/10 2010/11 2011/12

product of sugar Fincha Wonji/shoa Metehara Tendaho Total 8,000 20,245 23,296 58,105 8,000 8,000 12,245 17,000 17,809 18,600 20,836 17,676 47,508 104,620 18,600 25,153 21,301 64,051 129,106 18,600 25,153 24,480 60,616 128,849

40

As table 3-1 above shows, Ethiopia has the capacity to produce more than 120 million liters of ethanol production in each year since 2010. There also increasing of ethanol production thus it is a co product of sugar. Therefore, ethanol usage must be motivated in Ethiopia and ethanol using stove development and optimizing its high flammability to the safe range by mixing with non-flammable liquid is inevitable and award research to go with state product. The production quality ethanol Fincha is 99.7% ethanol and others are 94.6 % ethanol. The low viscosity, absence of tendency of gumming and formation of soot in ethanol makes it a more attractive possibility for cooking. Ethanol can be produced locally from a variety of materials that can be classified as sugar-containing (e.g., sugar cane and sweet sorghum), starchcontaining (e.g.; maize and grain sorghum), and cellulose-containing (e.g.; wood and crop residues). In Ethiopia, ethanol can be produced inexpensively from sugar cane and molasses at different sugar factories as shown table 3-1. Thus, the low cost and abundant availability of raw materials for the production of ethanol will make it very competitive with the other fuels used for cooking.

3.2 Ethiopia Policy toward using of ethanol as cooking fuel

Ethanol to be used as a cooking fuel in rural household, the policy to be addressed is;
1. The government of Ethiopia allows ethanol to be used as a cooking and automotive fuel

blending with gasoline according to information from the Ethiopia energy ministry, since 2008, the nation has saved over $10 million by blending nearly 13 million liter of ethanol with over 245.2 million liters of gasoline. Besides solving the energy crisis, the production and use of ethanol in rural areas will provide major stimulus to the rural economy.
2. Presently the production and sale of ethanol is controlled by a very rigid exercise regime

primarily because of issues regarding the drinking of this ethanol. However, there is enough chemistry known to mankind to make ethanol non-potable and unpalatable. Use of such chemicals will completely prevent drinking ethanol meant for use as fuel. If the government does decide on making such ethanol available as a cooking and lighting fuel in rural areas then it should exempt this ethanol from all excise duties. This will reduce its

41

cost and make it a viable alternative to LPG and kerosene for household purpose. Besides its use for cooking and lighting, it can also be used in internal combustion engines for producing decentralized electricity. Thus, all the present subsidies given in rural areas for cooking fuels (kerosene and LPG) and electricity should be lumped together and made available for ethanol use in rural areas of Ethiopia. The energy and environment policy initiates the production and consumption of biofuels such as biodiesel from jatropha plant and ethanol from molasses co-production of sugar and the strategies are prepared. It is clear and more interesting the using of biofuels for the agricultural based Ethiopia economy.

3.3 Optimal flammable ethanol-water mixture

Flammability is easily flaming or volatility of the liquid fuel. The volatility of liquid fuel is maintained by treating the fuel in mixing with the other non-volatile liquid. However, there is always an optimal concentration in flammability between volatility and non-volatility of mixture fuel. The development of flammability optimal ethanol in water solution is a critical and first indeed to use ethanol for cooking safer manner than pure ethanol. To do so and come-up with the best concentration, testing in the different percentages of ethanol-water mixture is taken until the best concentration value will be selected. The experiment is taken in a percentage of ethanol at 50, 60, 70, 80, 90, and 95 % of ethanol in water mixture from the 100 mL sample. When the content of ethanol is increasing, the color and property of the flame observed during the flame height measure. To care the fuel during cooking, the flash-point measured relate with the ambient temperature of major cities of Ethiopia. Finally, the calculated, the site data, and measured values graph are made for comparison. 3.3.1 Flame height measurement set-up To select the best concentration of the mixture the measured flame height and property of flame observed. Then, the optimal percentages of mixture in considering the calculated temperature of the flame that satisfy the cooking activity energy requirement and which is better than the pure case.

42

The procedures listed here are beside with the construction of measuring canister and the consecutive activities of each test carried out. The test canister construction is in the base of flammability favorable for ethanol-mixture and for easy caching of fire by it. The sequential procedures of all processes are as follows; 1. The single wick lit with ethanol mixture from the bottom of cylindrical can through the burner hole to the burner is prepared in similar manner for each six samples of testing as shown in figure 3.1 below 2. Careful measured volume ratio ethanol-water mixture is prepared for each testing samples 3. The fuel poured to the canister absorbed with the flame testing wick 4. The top of the canister burner small holes to evaporate the ethanol-water mixture ready to burn 5. Fire through the burner hole diameter observed 6. The flame height measured and data recorded for each test

Flame height is measured by careful observation of the clear blue colored ethanol-water mixture flame is measured by parallel aligning of the unit numbered ruler along the height of flame of single wick. Bussmann .el al. introduced a theory for open air with the aim that an insight in to the process that are involved with open fires, will lead at least to first guesses on the ruler governing the dimensioning of combustion [20 21]. To avoid the wind blowing of flame problem, the time and the experiment area to should be atmospherically stable in wind speed. The time and condition of experiment is carried in a closed door usually at night 3: 30 to 5: 00 and burner hole diameter is 6 mm2. The ambient temperature is measure my hand glass mercury thermo meter is usually 24 3 oC. I have used light switch off room for the clear observation of white-blue flame. The average measured value and standard deviation of measurement is listed in next section table 3-2.

43

Figure 3-1: Flame height measure set-up 3.3.2 Flash-point measurement set-up There are two methods of the measurement of flash-point value of liquid. These are closed-cup test and the open-cup device test. The open-cup flash-point value is typically a few degrees greater than closed-cup flash-point value and thus it is for heavy non-volatile fuels like asphalt grease. The closed-cup test is used for the small flash-point valued of the volatile fuels. The flash-point of liquid mixture depends on the composition of a mixture and type of chemical involved. For the ethanol-water mixture the value of flash-point increase when the amount of water increase.

44

The flash-point is measured in the Petroleum quality testing lab of Ethiopia petroleum corporation (EPE) by the well calibrated closed-cup device IP-170 (closed-cup) and well experienced operators. The ambient condition of measurement is at 21 oC and corresponding atmospheric pressure 583 mmHg (Addis Ababa) thus the observed measure value is corrected to the sea level normal atmospheric condition (760 mmHg).

Figure 3-2: Closed-cup IP-170 flash-point measuring device 3.3.3 Data analyzing The mean flame height and flash-point of each sample of mixture is summarized in table 3-2 below. For the relation of each measure the standard deviation is done for each samples of ethanol-water mixture. The maximum uncertainty at 95 % confidence level is 0.62 for the flame height by Z-test and 0.34 for the flash-point by T-test. The values are little greater than the significance level of and shows that the external affection of the measurement.

45

Table 3-2: The measured mean flame height and flash-point of ethanol-water mixture Ethanol-water mixture sample (% v/v ratio) Mean flame height (cm) Standard deviation Uncertainty @ 95 % Cl Flash-point ( C) Standard deviation Uncertainty @ 95 % Cl
o

50 5.0 0.79 0.28

60

70

80 7.55 1.63 0.58

90 9.00 1.74 0.62

95 9.29 1.80 0.6

5.40 6.20 0.56 0.97 0.2 0.34

24.45 23.7 22.01 20.28 18.64 16.4 0.51 0.5 0.54 0.55 0.34 0.5 0.34 0.55 0.34

0.316 0.34 0.34

3.3.4 Experimental Result discussion The datas are observed and measure is to come with optimal concentration ethanol-water mixture for cooking. The color of flame is from the blue to the yellowish-blue color when the content of water increased in the mixture and which little difficult to observe in ordinal light. The length of flame has been increasing with the percentage concentration of ethanol increase as data shown in table 3-2. At 50 % ethanol-water mixture the flame is weak and it may need some complex mechanism of stove design for the requirement of favorable cooking and some time fire catching problem if the wick is not lit more by the fuel. In the pure case, it catches the fire in a distance makes some sound of catching fire suddenly. This is the flammability hazardous of ethanol. It is clear that some content of water added the flammability is reduced in the same time temperature of flame is reduce by expending energy to evaporate the added amount of water. Based on the datas of flame height, flash-point, maximum flame temperature, over all property of flame, and flammability limit of ethanol-water mixture of different concentration 60 % (v/v) is selected as best flammable concentration of ethanol for cooking based on the best study knowledge of me. However, the measured data of table 3-2, all the flash-point data are still less than the medium flammability hazard limit (38 oC).

46

The 60 % (v/v) ethanol-water mixture flash-point is 23.7 oC which is increased from 15 oC (100 % ethanol) is around the average annual temperature of most regional cities of Ethiopia. The relation of flash-point values of experimentally measured, site data in figure 3.4 below. The maximum monthly temperature (Annex E) of major cities of Ethiopia to compare with the flashpoint tabled at the end of this document. The measured flash-point of 60 % (v/v) ethanol-water mixture and the maximum monthly ambient temperature of Bahir dar and Addis is shown the figure 3-3 below.
35

Maxi. monthly temperature ( oC)

30 25 20

15
10 5 0

Jan

Febr March April May June Jully Aug Sept AA

Oct Nomb Dece Bahir Dar

Flash-point of 60 % ethanol-water mixture

Figure 3-3: Flash-point and ambient temperature relation

47

Ethanol solution & flash-point relation

30 25

Flssh-point (oC)

20 15 10 5 0

50%

60%

70%

80%

90% Site data

95%

100%

Experimental result

Figure 3-4: Datas of flash-point and % ethanol-water mixture The flash-point of ethanol-water mixture is to be above 38 oC (the medium flammability hazard limit) at the concentration of above 85 % water but this is not flammable. The flash-point of flammable liquid is increased one by mixing it with inflammable liquid like water or tetrachloromethane and/or in other case blending of high flash-point liquid. flammable ethanol energy for cooking, it needs to enhance the flash-point. To use the The other

recommendable way of increasing flash-point of volatile alcoholic solvent ethanol is again blending it with volatile high flash-point solvents, Alph-terpeneol whose flash-point is 95 oC. For the organic solvent selected from the group ketones, alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, ethers and esters wherein said first solvent has a flash point less than 140 F (60
o

C) and a second organic solvent comprising a terpene alcohol or terpeneol in an amount of at

least about 5 volume percent of the total solvent system makes the mixtures flash-point above 140 F (60 oC) accordingly the test of ASTM D-93. The additive alpha-terpeneol invented to decrease the flammability of normally flammable alcohols and other solvents in America and patented (7273839) on September 25, 2007. The

48

additive is Alpha-Terpineol (C10H18O), which will increase the flash point of flammable alcohols or other solvents by blending it into the flammable solvent or alcohol. Solvents such as acetone, methanol, ethylacetate, ethanol and xylene to name a few, increases flash points up to 50 C to 60 C, by addition of 12-14% terpineol in weight ratio which meet Federal and state Volatile Organic Compound regulations. The availability and cost problem of terpene alcohol, using of only 10 % terpene alcohol, 30 % water, and 60 % ethanol in volume relation is to be best cooking fuel in the case of flash-point. This makes the solution flash-point above 50 oC which is witnessed by the flash point of 86 % ethanol and 14 % Alph-terpeneol is 63.6 oC in weight relation (Annex F). The alcohol alpha-terpeneol is slightly soluble in water and completely soluble in all alcohols and other organic solvents. Therefore, it can take in to the ethanol-water mixture with no miscibility doughty. Table 3-3: Property summary of 60 % (v/v) ethanol-water mixture Parameters Boiling point temp. & pre. Mixing enthalpy Mixture volume change (10 mL) Flammability Stochiometric volume of air for unit volume of fuel Flame height (Measured) Flash-point (Measured) Maximum flame temperature (calculated) Cm
o o

Units KPa and oC J/mol mL

Values 4.42 KPa and 88.5 oC -650 J/mol -1.13 mL

10.45 % 8.571

5.40 Cm 23.7 1153.37 oC

C C

49

CHAPTER 4 4 DESIGN OF ETHANOL-WATER MIXTURE STOVE 4.1 The stove Parts specifications

The main parts of the stove and introduction of them and with geometrical compactness for the portable simple stove is based on the combustion heat release and flammability property the fuel use in the stove which it designed for. For the high flammability and energy of ethanol and for safety and favorability for cookers, ethanol stove should include the following parts of the stove. The burner: Is the heart of the stove where the vaporized fuel and air combine and combusted. The type of burner suitable for this light ethanol-water mixture fuel to be vaporizer type and the mechanism of initial vaporization for the ready combustion by the atmospheric air is simply matching or firing on the liquid mixture. This is the preheating step is required to cold-start the stove (as is required by the presently-used kerosene stoves). The canister is packed with special refractory toilet soft paper fiber which can adsorbs ethanol-water mixture on the surface of it. When the ethanol lits over the fiber, the ethanol evaporates and mix with air to burn readily. The resultant clean flame burns with a yellowish-orange color and has a temperature of around 950 C to 1200 C. This low temperature and color is due to the presence of water vapor in the combustion zone and along the length of the flame. The advantage of the vaporized type burner is that vaporized fuel closer to its flash point and acts like a gas, making it easy to mix with air. The size and number of burner hole where combustion takes place is determined accordingly the energy of the fuel release in the next section. The turbulence jacket: The area that provides the turbulence required for complete combustion of the ethanol vapor. The flame can be regulated easily by the flame-regulating bar which designed and integrated with the canister of stove. The main indeed of turbulence jacket is contribution to the reduction of heat due to the blowing wind and it makes the entrance of air to the burner at the base and this make blow of air along the length of the flame rather the open fire flame.

50

Stand of the stove: Is the structural part of the stove which supports the main parts of the stove and it give good height for the cookers suitable during cooking if necessary. Flame regulator: It is the most important parts of the stove which provide the control of the energy of the flame and to shut-down the burner when cooking finished avoiding the further loss of fuel by evaporation. Fuel storage: Is the additional fuel holder and it arranged diffusion provision of fuel to the fiver packed canister. The parts of the stove include: 1. Cooking pan sit 2. Flame guide cylinder 3. Turbulence cover 4. Burner 5. Fuel storage

Figure 4-1: Parts of the stove

51

The other stove models such as kerosene stove, clean cook stove of ethanol, low concentration ethanol stove, and others have their own stove parts. For simple operation, fabrication simplicity, and function smoothness with different types of stoves parts included in different models of the stoves. The design of stove is based to provide the heat energy that is enough to cook any food types. The burner is the area where combustion of ethanol solution in the air takes place. The burner heat transferring vaporizes the ethanol mixture in side of the canister continuously to make it ready for combustion. For the ready of continuous combustion of liquid fuels, they first must be vaporized. Then, the vapour through the burner hole easily burn by the atmospheric air through the small hole pierced turbulence cylinder. The greater amount of air than the stochiometric air needed for the complete combustion, the number height of turbulence cylinder which guides the flame jacket is estimated accordingly and the observed flame height. The design and geometry compactness and parts determination of cooking stove is based on the property and flame propagation of the working fluid. At the burner holes of stove, the flames must be held and mixed together and uniformly distributed through the length of turbulence cylinder especially at the hottest zone of flame. For ethanol alcohols the flame propagation velocity at its maximum flame temperature is 1m/s and propagated horizontal length of preheated flame is different accordingly the diffusion passage of the stove [22]. The diameter of the burner holes circle is flexible to the usual use cooking pan capacity of the base are of it. Since the usual cooking pans base diameter are less 140 mm, let take the burners hole circle diameter 100 mm for this specific design.

52

Burner hole

Figure 4-2: Top surface area of canister or burner

The diameter of the burner hole is related with the amount of heat librated by the stove. Then, the number of holes to be determined accordingly the size of the burner circles diameter and heat energy librated. The number and diameter of the burner holes to be determined by the ethanol propagation property to get uniform mixed flame before reaching the upper burner area of pot sit that should be at complete combustion or the hottest zone of flame.

4.2

Burner holes diameter

The heat energy librated during combustion of ethanol-water mixture is the sum of heat energy needed to evaporate the contents of water and the loss of energy to the cooking surround. The amount of energy need to evaporate water in the solution is to diminish the unsafe flammability of ethanol. In the other case the amount of energy lost to the surrounding is minimized for the seeking of high efficiency require of the stove. Therefore, for the final flame temperature of 1153.37 oC, the heat librated for evaporation of 40% water of 60% (v/v) ethanol-water solution; taking the unit gram for each water and ethanol.

53

The amount of heat released per unit gram mass of ethanol is directly related with the molar heat of combustion of ethanol. Thus, the molar heat of combustion of ethanol H = 1360kJ/mol and mole of ethanol of unit mass. Qe = mfhf = 29.61 KJ/g =23.36 KJ/mL For the unit liter of mixture, only 60 % is ethanol and the energy is also to be 60 % of the calculated value and which is equal to 14.02 KJ/mL The heat energy loss for the evaporation of water in the solution is calculated by using maximum flame temperature Tf and the minimum ambient case water temperature Ta. For the 60 % (v/v) ethanol-water mixture Tf = 1153.37 oC (table 2-5) and normal water temperature Ta = 28 oC and specific heat of water Cp = 4.18 J/K g (table 2.1). That is the amount of heat added to evaporate water content by combustion of ethanol that increases the temperature of steam to maximum flame temperature of unit mass. Qw = mwCp (100 oC - Ta) + mwHf + mwCp (Tf - 100 oC) Since, all the water converted to vapor is directly to super steam, in all case mass is constant and the latent heat of vaporization of water Hf = 2.260 KJ/g. Therefore, the above equation is reduced for the unit mass of steam is; Qw = Cp (Tf - Ta) + Hf =6.964 KJ/g =6.964 KJ/mL Similarly for remain 40 % water of unit volume of fuel is also 40 % of the calculated value and which is equal to 2.7844 KJ/mL.
54

The heat energy only delivered to the flue gases to rise temperature of flame of the mixture is energy difference of energy produced by combustion of ethanol and energy lost to vaporize the water content of the mixture. Q = Qe Qw =14.02 KJ/mL - 2.784 KJ/mL =11.23 KJ/ mL
This energy is the amount of energy librated by the breaking the molecules of ethanol in unit seconds. Usually the consumption of ethanol in new ethanol stove is 1 mL/10 se above calculation is 1.123 KW [23]. The diameter of burner hole and the heat energy librated by burning of specific fuel is related by the formula; and thus the energy of the

Q = hc (1 - e-kb*db) Ab Where: Q is heat energy (KW) Mass burning rate of fuel in unit area of burner (kg/m2-s) Kb material property (m-1) Ap Area of total burner holes where flaming (m2) dp diameter of burner hole (m) Table 4-1: Thermal property of liquid hydrocarbon fuels [23] Mass Fuel type Burning Heat of Density (kg/m3) %

(4-1)

Rate (kg/m2- Combustion sec) ethanol Hc (kJ/kg)

Empirical Constant kb (m-1)

water

Methanol Ethanol Butane

0.017 0.015 0.078

20,000 29,700 45,700

796 794 573

100 100 2.7

55

By using the relation of heat energy and flame flow hole (equation 4-1) the relation is shown by figure 4-3 below. It shows that the heat energy is exponentially increase with increasing of flame flow burner hole diameter. From this relation it is simple to determine the size of burner accordingly the energy requirement of certain application.

Figure 4-3: Librated heat energy and single burner hole burner From the relation heat energy librating and the burners hole diameter (from figure 4-3) and considering the energy requirement of all foods in cooking, the heat energy is 1.123 KW is the energy through the total area of burners. Therefore, the diameter in a single case is 0.054 m, and area is 0.00196 m2 along the selected circumference of 100 mm diameter of burner holes circle (figure 4-1). But this diameter is only one hole is used for the whole system to get the required amount of heat energy. This area is divided in to the small holes of burner for the required geometry and flame control mechanism. The burner holes are equally spaced at the top of canister and spaced between inner and outer flame guiders of turbulence area just as house kerosene stove. Therefore, the number and diameter of burner holes are n = 10, and db =5 mm.

56

4.3

Vertical height of flame

Heskestad proposed the following equation for determining the mean flame height, L, for turbulent diffusion flames (but not jet flames) based on McCaffreys (2002) work: Lf = 0.235Q2/5-1.02db (4-2)

Where: Q is the lower heating value heat generated by the flame (KW) db is single burner hole diameter (m)

Figure 4-4: Vertical height of hottest zone of flame

The heat equally distribute to the number of flame flowing burner holes is (n = 10) is 1.123 KW/60 = 0.0187 KW and thus the hottest zone flame length of ethanol, by substituting the values is; Lf = 0.235(0.0187 KW) 0.4-1.020.005m = 4.271 cm From this relation of flame, the height of flame guider jacket of the stove to be some little blow the hottest zone of the flame and which is Lt = 4.0 cm and the turbulence cover is little above the turbulence cylinders and which is exactly at the height of hottest zone flame length.

57

4.4

Heat losses through stove

Fire of flame releases hot gases and in most case hot particles called soot from the surface of flame. The hot gases and smokes flow upward from the fire and is called plume. The surrounding air entrained or mixed in to the upward flowing plume and it makes; reduce flame temperature reduces plume velocity increases total mass of plume dilutes the plume Therefore, the losses when the flame spreading over the pot sit area includes radiation loss of the flame and convection loss due to the horizontal flowing surround air. There may be the conduction losses through the sides of stove, but it highly minimized by the presence of turbulence cover and turbulence cylinders that guide the upward flowing of flame with the iterance of air from all direction equally. 4.4.1 Radiation from flame Every matter in the universe can absorbs or scatters radiation heat whose temperature is above absolute zero temperature or 0 K. The gases like H2O, CO2, NH3, O3, SO2, NO, hydrocarbons, and alcohols are called participating media of radiation, since they at each point in their volume can absorb and scatter the incident radiation while emitting their own [24]. Flame is a hot flue gases diffusion of heat to open air. The radiation transfer of flame is depends on the emissivity, the temperature, and dimensions of the flames. The total emissivity of flame is superposition of the contribution from soot particles and the flue gases formed by combustion. The total emissivity of flame is the total sum of emissivity of flue gas and soot and subtracting of the product emissivity of both flue gases and soot. Ethanol produces a very little or no soot and has a coefficient of absorption 0.37/flame thickness [25]. Emissivity will tend to rise to maximum of about 0.4 as flame thickness increases since radiation occurs in only parts of the spectrum.

58

 = 1 e-t Qr = ATf4 the radiation heat loss from the flame in unit time Where: Absorpibity t thickness of flame Q radiative heat in unit time A area fuelbed surface emissivity of flame

The radiation heat loss from the flame of open air per unit area of fuel-bed per unit time is Qr = T4 = 0.45.6710-81153.374 =39.95 KW/m2 The consumption of ethanol in unit area in unit second is 0.015 Kg/m2-se (table 4-1) and thus the radiation heat loss from flame is; Qr = 40.134 KW/15g/se = 2.67 KJ/g 4.4.2 Convection from flame The heat loss from flame by convection is may be due to the blow of wind between cooking pan and cooking stove. Even if the cooking is in a closed door and there is no wind, there is a convective heat loss from the hot solid metal surface to the cold surrounding. The convection heat loss is directly related to the convective heat transfer coefficient, and area of the loss concerns. The heat transfer coefficient h of flame depends on the velocity of flame and which is also related with the speed of surrounding air and the dimension and shape of burner and wind speed. However, main convective heat loss from the cooking stove is due to wind speed.
59

Qc = hAT convective heat loss fuel-bed area of flame Where: h-convective heat transfer coefficient A-is the area of loss occur T-change of temperature

The heat transfer coefficient h due to wind speed is calculated as [26]; h = 5.7 + 3.8V, V-is wind speed, take the minimum value 1m/s, the speed of flame h = 9.5 W/m2 oC Qc = 9.5 W/m2 oC (1153.37 oC - 28 oC) = 0.712 KJ/g The heat energy of combustion of ethanol-water mixture (section 4.2) 11.23 KJ/ mL is for the ethanol is equal to 15.45 KJ/g. The final useful energy of the stove is determined subtracting all energy losses from the fuel and through the stove. Qu= Q Qr Qc the useful energy of the system = 15.45 KJ/g - 2.67 KJ/g - 0.712 KJ/g = 12.068 KJ/g Since there is no food particle whose specific heat is greater than the calculated value of useful heat energy of the stove, it is readily satisfactory cooking stove for all food particles.

60

4.5

Air-to- fuel ratio

The stochiometric air-to-fuel ratio of different percentage of ethanol-water mixture is stated at section 2.3.5.1 in this text. However, the combustion reaction is not usually based on the real required amount of air of the fuel. The right requirement of air for right complete combustion of the provided fuel is always with some excess air. But if the combustion is too rich, has too much fuel, then it will burn badly and incompletely, result carbon monoxide (which is poisonous) and soot (carbon particles) and further unexpected consumption of fuel. Again if the combustion is too lean, it gets not enough energy and the flame to be a disturbed flame. Burners are usually run slightly lean, with a small excess of air, to avoid the danger of the flame becoming rich. This is the stochiometric volume require for this specific combustion process of the stove. However, for the combustion quality and economy of fuel energy, there is certain economic value of excess air need for the combustion. For the calculated volume mole fraction of air-fuel ratio, it to be converted to the mass fraction. 8.571 mole of air = 8.571 mol29 g/mol = 248.559 g 1 mol of ethanol = 46 g AFR=248.559 g 46 g = 5.4 Excess air is usually expressed by the percentage and usually for liquid fuels the economic excess air is around 10-20 % [27 28]. Thus, let take excess air 18% and the combustion of the one gram of ethanol-water mixture 118 % of stochiometric air fuel ratio. 1.18 %5.4 = 6.372 g

Since the density of air is 1.29 g/L of air needed and the volume of this air is =6.372 g/1.29 g/L =4.94 L Similarly, one gram of 60 % ( v/v) ethanol mixture of with water has density, =1 g/ 0.872 g/litr =1.146 litr =1.14610-3 m3
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Thus, the air interning hole should be 4.94 10-3 m3 /1.14610-3 m3= 4.33 5. This means that for similar diameter 10 burner holes needs 50 holes of air flow through the external turbulence cylinder. For easy manufacturing and the finely diffusion requirement of air to the flame nearby turbulence cylinder, 1.5 mm diameter of air interflow hole is good and thus the total air entrance hole number is 167. The diameter and height of the external turbulence cylinder accordingly the geometry and the values determined of the stove is 10 cm and 4 cm respectively. The geometry of the air flow holes may be either diagonal or parallel to each other. The equally distributing from the bottom of flame guider air to be distributed equally in all circumference of the layer of the flame, equalspacing of holes diagonally is better. The detail and assembled drawing of the expected ethanolwater mixture stove is shown at the end section of this paper (Annex G).

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CHAPTER 5 5 MANUFACTURING PROCESS AND COST ESTIMATION 5.1 Efficiency of the stove
The overall stove efficiency can be determined in water boiling test because water is the highest calorific valued, dividing the amount of heat absorbed by the boil water in the pot during the test to calorific value of the fuel used in a test run. Input energy can be calculated by multiplication of the mass of ethanol with the energy density of the fuel by measuring the flow and pressure of fuel Chemical Energy (Input) and which is Mass of ethanol times Energy density of ethanol. Overall efficiency () = (output energy / input energy)x100 % Overall efficiency () of a stove depends upon different parameters and test conditions such as ambient temperature, pressure, specific heat capacity of vessel taken for test, size of vessel, bottom and overall shape of vessel, weight of vessel and the amount of specimen (water) taken. Thus difference test efficiency can produce different result for same stoves. As the input energy is accounted by the calorific value of the fuel (ethanol for this purpose) and the calorific value may vary from digester to digester and day to day. Overall efficiency is calculated by dividing output energy by input energy. In this process the heat gained by vessel in which water is boiled should be accounted. Hence. Heat gained by vessel = Mv * Cv * (Tb - Ti) Joule Heat gained by water in HPP = Mw * Cw * (Tb - T,) Joule Heat gained by water in LPP = (Mstesm *Lwboil) Joule Energy of fuel = (Mfule * Hfuel ) Joules

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So the overall efficiency of the stove can calculated as: Mstesm Lwboil + Mw Cw Tb T, + Mv Cv (Tb Ti Mfule Hfuel )

= Where: -

Mv mass of vessel Cv specific heat of vessel Mw mass of water

In many ethanol-water mixture stove models such as clean cook and low concentration ethanol stove has the measured efficiency is between 43-65 %, the test is carried out in different area and in different conditions, and the overall efficiency may changed by: The material of cooking stove The amount of cooking water Ambient temperature of the test and like

For the calculated value of this specified design of 60 % (v/v) ethanol-water mixture stove is in analytically by dividing the output useful energy to the input calorific content of ethanol. The effectiveness includes the loss of energy due to evaporation of water content in the mixture and other radiation and convective losses from the combustion of ethanol in this specific determination. Therefore, the efficiency of the stove is calculated as; e = =

Qu Qe
12 .068 KJ / g 17 .6652 KJ / g

= 68.3 %

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5.2 Material and cost estimation

A material of major parts of the stove to be steel since the fuel contains water and steel selected to avoid corrosion problem. For its high melting point which is above 1400 oC mild steel is selected for the parts of the stove. The main Parts of the stove include: Body canister Fuel holder Flame guide or turbulence jacket Turbulence jacket cove Flame control arrangement Table 5-1: Cost and specification of materials of stove Parts of stove Fuel holder Material Heat treated mild steel Fiver packed canister Flame guider cylinder Heat treated mild steel Heat treated mild steel Specification 27.64cm 3 cm 12 cm 5 cm 10 cm 4 cm 30 55 Cost (Birr) 95.2 Remark Welded and painted Rolled seamed Small holes on surface Pot sit and support Aluminum bar 3(2 mm2 mm5 mm) 10 For rivet to turbulence cylinder cover the and

The total cost the portable 60 % (v/v) ethanol-water mixture as detail summary of table 5-1 of above is 190.2 birr. The manufacturing cost of whole stove may need only one day for single labour in all thing prepared work shop. Therefore, the per-diem of single labor is never greater than 100 birr everywhere in Ethiopia and thus the total production cost is 290.2 birr. This is twice of the cost of now a days market household kerosene stove. The stove design is expected
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for the life time of 15 years because the life of steel which can be over 100 years in the protected environment; to show how much it recover the expense by the low cost, country product, renewable ethanol fuel. Since the portable stoves used for the small application, there may be average 0.l L per single stove of fuel used each day and the cost of ethanol is lower than onethird of the cost of kerosene comparing the production cost of ethanol with no import tax expense [29]. The current cost of kerosene in Bahir dar city is 13 birr/L and for the 15 years in that average household consumption, it equals to 7,117.5 birr and for the same consumption average daily cooking of ethanol-water mixture costs. For the designed 15 year life of ethanol the total cost in the one-third of kerosene is 2,372.5 birr. It is only 33.34 % cost of kerosene which is surprising. For the 60 % ethanol-water mixture only 60 % is ethanol and 40 % water is non-cost part of the fuel which only accounts 20 % of 15 year kerosene cost. The advantage of using renewable ethanol for cooking is not only cost, but household air quality to keep the cookers in health. The life-cycle cost of the stove is the sum of maintenance and operation cost and fabrication cost of the stove. However, for the portable stoves, the maintenance and operation cost are zero and thus the life-cycle cost is only the fabrication cost of stove (195.2 Birr). The money saving by using ethanol for cooking compared with ordinary kerosene stove as shown is 80 % life-cycle fuel cost of kerosene stove (5,694 birr). Again comparing with the kerosene stove, the recovery time for the excess stove cost by fuel cost saving is within only half year from the life of stove.

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5.3 Parts Manufacturing Process

Manufacturing process of ethanol stove development is mainly by rolling of sheet mild steel for the stove body and then welding, seaming, boring, and drilling of preheat holes of the stove to come with the finished ethanol stove for the requirement of smooth function. Mild steel can take high temperatures of softening point, and is not brittle, easily welded and is very strong, so can be used for many components like total canister parts, fuel storage cylinder, turbulence cylinders, and turbulence cover. The detail of the parts of the stove and their manufacturing processes is described here. The other parts of further extend like the stand of stove, no matter if it be aluminum or cast iron. 1. Fuel cylinder: is a fuel holding cylinder, and it may be either cubic or cylindrical. It processed by the punching of sheet metal either cubic or cylindrical presser for the required size of fuel requirement for daily consumption. For the development of

mechanical stress through sharp corners, a cylindrical shape is select as better. The cover of fuel holding cylinder hole is bored ether cutting or successive drilling in outer diameter of canister to insert the canister in to it. 2. Stove canister: it is the heart of the stove where burner found. The open at bottom end canister packed with soft mineral fiver to absorb the fuel from the fuel cylinder. The lower end is bored equidirection for the entrance the fuel. Therefore, to get this shape, the sheet metal to be rolled in the canister diameter and then held by seaming and welding for the strength. The upper closed burner hole drilled end is the combustion area of the stove. The burner holes of the canister are formed by the drilling of it. 3. Turbulence cylinders: Turbulence cylinders are manufactured by rolling in the required diameter and seamed and then final random welding for the strength. The small air hole through the surface of cylinder is drilled for the spontaneous diffusion of air for complete combustion of ethanol mixture. 4. Turbulence cylinders cover: it is the accessory part f the stove which allows the base entrance of the air and provides a cooking pot sitting similarly of kerosene stove. It also processed by punching and bored at top just as the house use kerosene stove.

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5.4

Operation and Working Principle of the Stove

The parts of stove are for the suitable function and easy operation of the stove for any level cooking body. The working principle is as stated through the design section, the canister packed with soft toilet paper to absorb the ethanol-water mixture. The fuel should be lit over the soft toilet paper and stay the same level by assisting the absorptance of fuel from the fuel from the integrated fuel tank as shown figure (from Annex E). The upper flame 10 small holed surface is the combusted flame of mixture is flaming through the burner holes. For the continuous flaming complete combustion air requirement, the air enters through the very small holes on the surface of outer turbulence cylinder. The function of inner turbulence cylinder is only to guiding the flame and is called flame guider. The cover of turbulence cylinder is to lead the entrance of air from the base of combustion area and reduces the heat through the turbulence cylinder beside with providing of the cooking pot support. The operation principle of the stove is here described verify for the safety and fuel handling care during cooking. Even if the fuel used for this stove is 40 % water, the flash-point is still lower than the lower hazardous flash-point value of fuels. Therefore, after the fuel poured to the fuel tank of the stove, any droplets on any part surface of stove should be swept dryly. In addition of caring or controlling the droplets of fuel from surface of the stove, the extra fuel also managed in the insulating jar, or spring closing safety can to keep in close always keeping it from the heated material whose temperature above the flash-point of the mixture. Therefore, after the ethanolwater mixture lit over the soft toilet paper, the fire matched to the burner holes to flame through it. Similarly as the home kerosene stove, the holed outer canister attached to the burner little time kept for the flame stable. Then, the canister cover put to the position and cooking started.

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CHAPTER 6 6 CONCLUSIONS AND RECOMMENDATION 6.1 Conclusion

The development of optimal flammable ethanol-water mixture and design of stove for house hold cooking is a best science of environmental friend fuel use and snatching the house women from using of traditional cooking stove and fuel and its negative effects. Although there is no wide use ethanol stove in Ethiopia, ethanol is more favorable for the cookers and environmental health and safety of the cooking process. Ethiopia has enough ethanol production capacity, but is still no known best concentration of ethanol-water mixture in flammability and no well developed flexibility of design and models of ethanol stove except the clean cook stove of GIA association and there is no producing company in Ethiopia. The experiment carried to determine the actual flame height, and flash-point measured for flame property observation, and fire catching property of each samples (50, 60, 70, 80, 90, and 95% (v/v) of the 100 mL sample ethanol-water mixture). Accordingly, the mean flame height value, flash-point around the atmospheric temperature for more safety, and maximum flame temperature for enough energy content for cooking is determined. Based on all these criterion of flammability, 60 % (v/v) ethanol-water mixture is get as the best in flammability and energy require of cooking accordingly the energy require of boiling of water which is maximum specific heat than all food types. Its maximum flame temperature is calculated as 1153.37 oC and flashpoint measured is 23.7 oC the mean flame height is 5.40 cm. It is the lowest possible

concentration of ethanol-water mixture for the best cooking fuel consumption and cooking house hold safety. The energy of ethanol-water mixture is determined by subtracting of the amount of energy utilized to evaporate water content by energy released by combustion of ethanol. The design of stove both radiation and convection heat losses from flame are calculated and further reduced to get useful energy to the cooking pan. The calculated useful energy is from the combustion of unit gram mass of ethanol is 12.068 KJ/g. Therefore, the efficiency of stove calculated in general meaning by the ratio of the final useful energy of the stove to input ethanol combustion energy of

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the stove. Thus the efficiency of the stove is determined and is equal to 68.31 % which is the best efficient than the design and models of ethanol stoves present before.

6.2 Recommendation
In implementing an environmentally friend ethanol stove, the production and distribute company may plays a major role for the rapid distribution and use of the optimal flammable ethanol stove. So, it is best if the small companies start production of stove since it is not so complex and cost effective. One thing I want to recommend is that not in the case of Ethiopia thus the ethanol production process using of cellulose as input material is better; not to short edibility of the area. But in the case of Ethiopia, the main source of ethanol is the co-product of sugar in sugar factories; molasses it may not effect on the cost of food availability. I have used the maximum flame by the calculation by limitation high scaled temperature measure instrument. But I recommend that it well if the maximum flame temperature is experimentally determined accordingly the real environment. The flash-point is still below the safe value. The flash-point of volatile solvent is increased by treating the solvent with the non-flammable liquids like water, tetrachloromethane etc. and/or blending with other high flash-point flammable solvents like terpenolic alcohols. For the further enhancement of flash-point of ethanol-water mixture blending with alpha-terpeneol at least 5 % (v/v) to make above flammability hazardeous limit. For cooking energy requirement, fuel

economy and lower flammability hazard 60 % ethanol, 10 % alpha-terpeneol and 30 % water recommendable. Finally, anybody who is interested to continue this study, I would like to motivate to make base and recommend that one should improving the efficiency of stove in experimental based with manufacture optimal flammable stove. Production smooth is the most require indeed coming up with the best function of the stove and its efficiency. Moreover, there should be different ways to improve the efficiency of the stove which comprises the higher quantity of heat gain and at the same time safety of cooking.

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7 REFERENCE
[1] Alemu Mekonnen and Gunnar Khlin, Determinants of Household Fuel Choice in Major Cities in Ethiopia August 2008. [2] Flannery-Allen, Julie, "Vital, Ethanol brings an energy revolution to households in the developing world". Retrieved 30 May 2010. [3] Christopher Walsh, World Bank Enables Thousands of Africans to Access Modern Energy Washington April 2008. [4] Grima Gezaheign W/Selassie, Evaluating the Efficiency of Local Liquor Distillation Stove by Measuring the Indoor air Emission AAU December 2008. [5] Anil K.Rajvanshi, S.M. Patil and B. Mendonca, Low-concentration ethanol stove for rural area in India Nimbkar Agricultural Research Institute (NARI) , March 2007. [6] Anil K.Rajvanshi, Ethanol lantern cum stove for rural areas of India Nimbkar Agricultural Research Institute (NARI) June 2009. [7] World Energy Outlook, Energy for Cooking in Developing Countries. 2006 pp 424 425. PDF found at http://www.2.gtz/dokumente [8] Stefan Heimann, Renewable Energy in Ethiopia, 13 Months of Sunshine for a sustainable Development Berlin 2009. [9] Nicolai Schlag and Fiona Zuzarte, Market Barriers to Clean Cooking Fuels in SubSaharan Africa: A Review of Literature Stockholm environment institute, April 2008 [10] P. R. Rastogi, and R. R. misra, Introduction to chemical thermodynamics Fourth edition, April 2005. [11] Harry stokes, Gia project, Alcohol fuels (ethanol and methanol): safety pp 2, January 2005. [12] Franklin Chen, Bartenders Conndrum: partial molar volume in ethanol-water mixtures Wisconsin university. PDF at found at http://www.uwgb . [13] Eduardo Perez, Yolanda Sanchez-Vicente, Albertina Cabanas, Concepcion Pando, Juan A.R. Renuncio, Excess molar enthalpies for mixtures of supercritical carbon dioxide and water + ethanol solutions 23 March 2005. PDF found at http://www.sciencedirect.com

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[14] Harry stokes, Commercialization of a new stove and fuel system for household energy in Ethiopia using ethanol from sugar cane residue and methanol from natural gas October 30, 2004. [15] Web-site: The flame temperature of volume of mixture http://www.me.utexas.edu [16] Vladimr Dohnal, Dana Fenclov and Pavel Vrbka, Temperature Dependences of Limiting Activity Coefficients, Henrys Law Constants, and Alkanols in Water. Critical Compilation, Correlation, and Recommended Data April 2005. [17] Chih-yung Huang, Pey-yu Chung, I-Min Tseng2 and Liang-sun Lee, Measurements and Correlations of Liquid-liquid-Equilibria of the Mixtures Consisting of Ethanol, Water, Pentane, Hexane, and Cyclohexane [18] M. Hristova, D. Damgaliev, D. Popova,estimation of Water-Alcohol Mixture Flashpoint Journal of the University of Chemical Technology and Metallurgy, January 2010. [19] Meskir Tesfaye Asfaw, Bio-fuels in Ethiopia. Presented on Eastern and Southern Africa Regional Workshop on Bio-fuels. Nairobi, Kenya, June 29, 2007. [20] N.A.Verhoeven, Kerosene Stove and single wick fuel burning Eindhoven University of technology, February 1989. [21] Cahill, P., Evaluation of fire Test Methods for Aircraft Thermal Acoustical Insulation DOT/FAA/AR-97/58, September 1997. [22] Audouin, L., Kolb, G., Torero, J.L., Most, J.M., Average Centreline Temperatures of a Buoyant Pool Fire Obtained by Image Processing of Video Recordings, Fire Safety Journal Volume 24, pp 167-187, September 1995. [23] Butler, B. W. and J. D. Cohen, Firefighter safety zones: a theoretical model based on radiative heating. International Journal of Wildland Fire 8: 73-77, 1998 [24] Amare G/Egziabher, James Murren and Cheryl OBrien, An Ethanol-fueled Household Energy Initiative in the Shimelba Refugee Camp, Tigray, Ethiopia: A Joint Study by the UNHCR and the Gaia Association 20 January 2006. [25] Adrian Bejan, Heat Transfer John Wiley & Sons, Inc. 1993. [26] D. Rasbash, G. Rama Chandran, B. Kandola, Evaluation of fire safety June 1990. PDF found at http://www.wileyurope.com [27] G.D.RAI, solar Energy utilization 5th Edition, KHANNA, NEW DELHI, 2001.

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[28] Baltasar, J. et al., Flue Gas Recirculation in a Gas-fired Laboratory Furnace, Fuel, Vol. 76, pp. 919-929 1997. PDF found at http://texasiof.ces.utexas.edu [29] Harry Stokes, Commercialization of a New Stove and Fuel System for Household Energy in Ethiopia Using Ethanol from Sugar Cane Residues and Methanol from Natural Gas. Presented to the Ethiopian Society of Chemical Engineers (ESChE), October 30, 2004. PDF found at http://bioenergylists.org

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8 ANNEXIES Annex A:
WHO Exposure guide line Indoor air pollution is original air pollution problem and it still exists (WHO/UNEP, 1990). The inefficient burning of solid fuels on an open fire traditional stoves creates a dangerous cocktails of hundreds of pollutants: carbon monoxide, soot, dust and particulates, nitrogen oxide, sulphur oxides, formaldehydes, hydrocarbons and many other health-damaging chemicals. In developing countrys households, daily average of pollutant level emitted indoor often exceed WHO guide lines and accepted level. Health affecting limit according to WHO exposure guide line [Usinger, 1996] product Carbon monoxide Concentration 100 mg/m3 60 mg/m3 30 mg/m3 10 mg/m3 Formaldyde Lead Nitrogen dioxide 100 g/m 1 g/m3 400 g/m3 150 g/m3 Ozone 200 g/m3 120 g/m3
3

Time limit 15 min 30 min 1 hr 8 hr 30 min 1 year 1 hr 24 hr 1 hr 8 hr

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Annex B:
Flash point of ethanol-water mixture The flash point of a volatile liquid is the lowest temperature at which it can vaporize to form an ignitable mixture in air i.e. is value of temperature having enough flammable vapour to ignite. Flash point is often used as a descriptive characteristic of liquid fuels and it is also used to help characterize the fire hazard of liquids. Flash point is measured in two basic flash point measurements; open cup and closed cup. In the open cup device the sample is contained in the open cup which is heated at the intervals a flame is brought over the surface. Closed cup devices are also equipped to hold the sample in closed cup. It used to measure normally give the lower values for the flash point than open cup typically (5-10 oC) and are better approximation to temperature at which the vapour pressure reaches the lower flammability limit (LFL). Therefore, the closed cup device is selectable for this specific measure since ethanol is volatile. The only parameters can affect the flash point values are the height of flame above the liquid surface and the standard data of the flash point of ethanol water mixture is listed in next table 2.2 below. Table 2.2: Flash-point of ethanol-water mixture Ethanol-to-water Concentration (% v/v ratio) Flash-point (oF) (oC) 144 62 120 49 97 36 84 29 79 26 75 24 72 22 70 21 68 20 63 17 63 17 5 10 20 30 40 50 60 70 80 90 95

Materials with higher flash points are less flammable or hazardous than chemicals with lower flash points.

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Annex C:
Mole fraction ethanol-water mixture with its boiling point temperature Table: Mole fraction change of ethanol-water mixture with its boiling point Boiling point (oC) Liquid (x) Vapour (y) Liquid (x) Vapour (y) Mole Fraction Mass Fraction (g/g) Volume Fraction (mL/mL) Liquid (x) Vapour (y) 95.5 89 86.7 85.3 84.1 82.7 82.3 81.5 80.7 79.8 79.7 79.3 78.74 78.24 78.15 0.019 0.072 0.097 0.124 0.166 0.234 0.261 0.327 0.397 0.508 0.520 0.573 0.676 0.747 0.894 0.170 0.389 0.438 0.470 0.509 0.545 0.558 0.583 0.612 0.656 0.660 0.684 0.739 0.782 0.894 0.0472 0.1657 0.2147 0.2654 0.3374 0.4381 0.4743 0.5544 0.6269 0.7252 0.7346 0.7745 0.8423 0.8831 0.9558 0.3437 0.6196 0.6654 0.6943 0.7260 0.7535 0.7635 0.7811 0.8014 0.8301 0.8322 0.8470 0.8784 0.9014 0.9558 0.0591 0.2012 0.2573 0.3141 0.3923 0.4971 0.5334 0.6119 0.6804 0.7698 0.7782 0.8132 0.8713 0.9055 0.9648 0.3990 0.6736 0.7160 0.7422 0.7705 0.7948 0.8036 0.8189 0.8365 0.8609 0.8628 0.8753 0.9015 0.9206 0.9648

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Annex D:
Property of common fuels Table: Property of common fuels Parameters LFL-UFL (%) Flash-point (oC) Auto-ignition temperature (oC) Benzene Ethanol kerosene Methane() Methanol Gasoline 1.35-6.65 3.3-19 0.7-5 5-15 6.7-36 1.4-7.6 12 17 131 -221 52 -45 560 365 295 580 385 280

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Annex E:
Maximum monthly temperature of major cities of Ethiopia Table: The maximum monthly temperature of major cities of Ethiopia ( oC) of NMA in 2010 Cities AA Awassa A/Minch Asosa Bahir dar Jan 23 28.3 31 30 26.5 Feb 24 30 32 32 27.9 19 28 28.5 17 26.5 Mar 25 28.9 31.5 31.5 29.4 21 29 29 19 27 Apri 24 27.2 30 31 29.7 23 27 27 23 27.6 May 25 26.7 28 27 28.6 24 29 26 17 29 June 23 25 27 25 26.4 23 25 25 20 30 July 20 23.3 26 24 23.3 19 22 26 24 26.7 Aug 20 24.5 27 24.5 23.3 20 22 26 22 25 Sept 21 25 29 26 24.5 21 24 27 19 27 Oct 22 26 29 26 25 19 25 27 17 25 No 23 27 30 27 25 18 25 27 17 25 Dec 23 28 32 30 26.4 18 27 27 17 25

D/ Brihan 19 Gondar Jimma Jijiga Mekelle 27 28 22 26

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Annex F:
Property of alpha-terpineol alcohol Terpineol is a naturally occurring monoterpene alcohol that has been isolated from a variety of sources such as cajuput oil, pine oil, and petitgrain oil. There are three isomers, alpha-, beta-, and gamma-terpineol, and are differing by one another only by the location of the double bond. Terpineol is usually a mixture of these isomers with alpha-terpineol as the major constituent.

Alpha-terpineol (C10H18O) is the most recent invented alcoholic solvent which has a capability to increase the flash-point of high flammable solvents without damaging the current property of base total solvent system. It significantly increases the flash-point of solvent whose flash-point is less than 140 oF (60 oC). Alpha-terpineol is completely miscible in all alcoholic solvents and other organic solvent and is slightly soluble in water. Organic solvent consisting of a terpene alcohol present in an amount of at least from about 5 volume percent of the total solvent system, and less than about 20 volume percent of the total solvent system, and sufficient to increase the flash point for the solvent system to over 140 F (60 oC). Its flash-point varies between 94 to 96 oC depending up on the involvement of volatile impurities. The invention of alpha-terpineol is golden idea in reducing fire hazard of industries. Various solvents blending with alpha-terpineol in weight ratio, the flash-point increment is tabulated as below.

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Content of base solvent 82 % Acetone 86 % Methanol 85.5 % Isopropylalcoho 85 % Xylene 86 % Ethanol

Additive 18 % alpha-terpineol 14 % alpha-terpineol 14.5 % alpha-terpineol 15 % alpha-terpineol 14 % alpha-terpineol

Flash-point 62.0 oC 62.0 oC 63.0 oC 68.9.0 oC 63.6.0 oC

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Annex G:
Detail drawings of the stove parts 1. Upper surface of the burner

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2. Front sectional view of canister

3. Turbulence cover of stove

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4. Fuel storage-canister integration arrangement

5. Turbulence cover, canister, and fuel tank

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6. Outer surface small holed and solid inner flame guide turbulence cylinders

7. Sectional view of the assembled drawing of stove

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8. 3-D Assembled drawing of the stove

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