Middle-East Journal of Scientific Research 12 (12): 1758-1765, 2012 ISSN 1990-9233 © IDOSI Publications, 2012 DOI: 10.5829/idosi.mejsr.2012.12.12.1204

Performance and Emission Analysis of Pongamia Oil Methyl with Diesel Blend

12M. Venkatesan, C.J. Vikram and 3 P. Naveenchandran

1P.G. Student, Department of Automobile Engineering, Bharath Institute of Science and Technology, Bharath University, Chennai, India 2Assistant Professor, Department of Automobile Engineering, Bharath Institute of Science and Technology, Bharath University, Chennai, India 3Professor and Head, Department of Automobile Engineering, Bharath Institute of Science and Technology, Bharath University, Chennai, India

Abstract: Presently the world’s energy needs are met through non-renewable resources such as petrochemicals, natural gas and coal. Since the demand and cost of petroleum based fuel is growing rapidly, and if the present pattern of consumption continues, these resources will be depleted in few years. Hence, efforts are being made to explore for alternative source of energy. The high energy demand in the industrialized world as well as in the domestic sector and pollution problems caused due to the widespread use of fossil fuels make it increasingly necessary to develop the sources of limitless duration and smaller environmental impact than the traditional one .An alternative fuel must be technically feasible, economically competitive, environmentally acceptable and readily available methyl derived from renewable sources such as vegetable oils has gained importance as an alternative fuel for diesel engines.

Key words: Vegetable oils Calorific value Pongamia oil Cetane number

INTRODUCTION Disadvantages Higher Vegetable Oils: Vegetable oils have the potential to Lower volatility replace a fraction of the petroleum distillates and The reactivity of unsaturated hydrocarbon chains. petroleum-based petro chemicals in the near future. However, their direct use in compression engines was Types of Vegetable Oils restricted due to high viscosity which resulted in poor Vegetable oils are classified into two types, fuel atomization, incomplete combustion and carbon deposition on the injector and the valve seats causing Edible oils serious engine fouling. Tea, germ, seed, Amarnath, poppy seed, tallow, apricot,…etc Advantages Ready availability Non edible oils Renewability Pongamia oil, Rubber seed oil, Algae oil, Lower sulphur Jatropha oil, Neem oil, Mahua oil, Jojoba oil, etc... Aromatic content The non edible oils are very less cost than the edible Biodegradability. oils.

Corresponding Author: M. Venkatesan, Department of Automobile Engineering, Bharath Institute of Science and Technology, Bharath University, Chennai, India 1258 Middle-East J. Sci. Res., 12 (12): 1758-1765, 2012

Pongamia Oil (Karanja Oil): Karanja is an oil seed Blending of bio-diesel with diesel fuel increases bearing tree, which is non-edible and does not Wand any engine efficiency. suitable application with only 6% being utilized out of The higher flash point makes the storage safer. 200 million tons per annum. Karanja is a native to humid and subtropical environment shaving annual rainfall Disadvantages of Biodiesel ranging from 500 to 2500 mm in its natural habitat [1]. The Fuel pumping difficulty due to high viscosity. maximum temperature ranges from 27 to 38°C and the Lower engine speed and power. minimum 1 to 16°C. It has lower energy content. It can grow on most soil types ranging from stony to sandy to clay, including verticals. It does not do well in LITERATURE REVIEW dry sands. It is highly tolerant to salinity [2]. It can be propagated either by seeds or by suckers. The yield Malaya Naika et al. [1] has discussed the mechanism of kernels per tree is between 8 and 24 kg. of a dual process adopted for the production of biodiesel The freshly extracted Karanja oil is yellowish orange from Karanja oil containing FFA up to 20%. The first step

to brown and rapidly darkens on storage. It has a is acid-catalysed esterification by using 0.5% H2 SO4, disagreeable odour and bitter taste. The oil contains alcohol 6:1 molar ratio with respect to the high FFA several furan Xavones such as karanjin, ponga pin, and Pongamia oil to produce methyl ester by lowering the acid pongamia brin. The presence of toxic Xavonoids makes value, and the next step is alkali-catalysed the oil non-edible [3]. At present the oil is being used as transesterification [6]. The yield of biodiesel from high a raw material for , and after sulphonating and FFA Karanja oil by dual step process has been observed sulphation in the leather tanning industries, the main to be 96.6-97%. The Indian non-edible oils are often constraints for its more usage are the colour and odour. contaminated with FFAs, depending on the process of oilseed collection, expelling and storage condition, and Biodiesel: Bio diesel is referred to as the mono-alkyl contamination of oil/oilseed with moisture. The esters of long chain fatty acids derived from renewable conventional alkali-catalysed route of biodiesel lipid sources. Bio diesel is the name for a variety of ester production does not work out effectively with high FF a based oxygenated fuel from renewable biological sources. feedstock such as Karanja oil. However, the dual-step It can be used in diesel engines with little modifications process of transesterification using acid-catalysed and [4]. It is biodegradable non toxic and possesses low followed by base-catalysed reaction proves effective in emission profiles. Also, the uses of bio diesels are producing the appropriate quality of biodiesel as per the environmentally beneficial. The name biodiesel was ASTM specification. introduced in the United States during 1992 by the Md. Nurun Nabi et al. [2] have presented National Soy Diesel Development Board which has production of biodiesel from non-edible renewable pioneered the commercialization of biodiesel in the US. Pongamia Pinnata oil, extermination of Biodiesel One hundred years ago, Rudolf Diesel first tested properties and influence of BD on engine performance as fuel for this engine [5]. Bio diesel has the and emissions. Bangladesh imports 2.4 million metric ton potential to reduce the level of global warming. DF each year. It has 0.32 million hectare of unused land. It has been found that cultivating of Karanja plant in such Advantages of Biodiesel unused land; Bangladesh can reduce DF import by 28%. Biodiesel is bio-degradable and non toxic. Karanja methyl ester (KME), which is termed as BD, It is renewable fuel that can be made from agricultural has been produced by well-known transesterification crops. process [7]. Bangladesh can reduce 28% diesel import Low sulphur content and hence environmental from foreign countries if Karanja is cultivated in the friendly. unused land of Bangladesh. KME was produced by well Flash point of biodiesel is higher than the diesel and known esterification followed by transesterification hence it has the high personal safety. method. A maximum of 97% FAME was produced from Bio-diesel can be used directly in compression Karanja oil. The FTIR analysis showed that DF was ignition engines with no substantial modifications of contained alkanes and alkenes, while the KME mainly the engine contained esters.

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P.K. Sahoo et al. [3] has described various methods quantified by HPLC and 1HNMR method. The yield of of preparation of biodiesel from non-edible filtered methyl esters from Karanja oil under the optimal condition Jatropha, Pongamia pinnata and Polanga oil has been was 97-98%.The experimental study revealed that the described. Biodiesel produced and blended with diesel optimum reaction conditions for methanol sis of Karanja were evaluated. The technical tools and processes for oil was 1% KOH as catalyst, alcohol/oil molar ratio 6:1, monitoring the transesterification reactions like TLC, GC reaction temperature 65°C, rate of mixing 360 rpm for a and HPLC have also been used. It has been conclusively period of 3 hr. The yield of methyl esters was >85% in observed that biodiesel production from feed stocks with 15 min and reaction was almost complete in two hours high FFA is extremely difficult using alkaline catalysed with a yield of 97-98%. The reaction was incomplete with transesterification process [8]. This is because the alkaline a low rate of stirring at 180 rpm, whereas stirring at high catalysts react with FFAs to form soap that prevents the rpm was a time efficient process. separation of the glycerin and ester. A twostep Sanjib Kumar Karmee et al. [6] has prepared the transesterification for Jatropha and Karanja are developed biodiesel from the non-edible oil of Pongamia pinnata by to convert the high FFA oils to its ester. The first step transesterification of the crude oil with methanol in the reduces the FFA content of the oil to less than 2% for presence of KOH as catalyst. A maximum conversion of Jatropha and Karanja oils. The alkaline catalysed 92% yield was achieved using a 1:10 molar ratio of oil to transesterification process converts the products of the methanol at 60°C. Tetra hydro furan, when used as a first step for Jatropha and Karanja and products of co-solvent increased the conversion to 95%. Solid acid second step to its mono-esters and glycerol. The catalysts viz. Hb-Zeolite, Montmorillonite K-10 and ZnO viscosity of biodiesel is nearer to that of diesel. The flash were also used for this transesterification. Important fuel point of biodiesel is greater than that of diesel and properties of methyl esters of Pongamia oil compare well calorific value is slightly lower than that of diesel. with ASTM and German biodiesel standards. Crude Prafulla D. Patil et al. [4] has investigated the Pongamia oil was transesterified using KOH as catalyst analysis of different oil properties, fuel properties and and methanol to form Biodiesel. The conversion was process parameter optimization of non-edible and edible 92% at 60°C with 1:10 molar ratio (oil: methanol) for KOH vegetable oils were in detail. A two-step and single-step (1% by wt) catalysed transesterification. ZnO, Hb-Zeolite transesterification process was used to produce biodiesel and Montmorillonite K-10 also catalyse the from high free fatty acid non-edible oil and edible transesterification of Pongamia oil. They require longer vegetable oils, respectively. This process gives yields of reaction time of 24 hr and the conversion is 83% for ZnO about 80-85% for Pongamia oil using potassium hydroxide but low (47-59%) for Hb-Zeolite and MontmorilloniteK-10. as a catalyst. The fuel properties of biodiesel produced The fuel properties especially viscosity and flash point were compared with ASTM standards for biodiesel .A (150°C) of the transesterified product (biodiesel) compare two-step transesterification process was used to convert well with accepted biodiesel standards i.e. ASTM and the high FFA jatropha and Karanja oil to its esters [9]. It German biodiesel standards. was found that the high FFA oils could not be transesterified with the alkali catalyst transesterification Methods For the Production of Biodiesel: The problem process. For Karanja oil, the methanol to oil molar ratio of with substituting for diesel fuel is mostly

6:1 favoured the 1% H24 SO acid catalysed esterification associated with high viscosity, low volatility and process at 50 ± 5°C while molar ratio of 9:1 favoured the polyunsaturated characters. These can be changed in at 0.5% KOH alkali catalysed transesterification reaction at least four ways and these types are explained below. the same temperature. This two-step esterification process gives yield of 80% for Karanja biodiesel. Blending: The blending of vegetable oil with diesel fuel L.C. Meher et al. [5] has carried out on were experimented successfully by various researchers. A transesterification of Karanja oil with methanol for the diesel fleet was powered with a blend of 95% filtered used production of biodiesel. The reaction parameters such as and 5% diesel in 1982. A blend of 20% catalyst concentration, alcohol/oil molar ratio, oil and 80% diesel was found to be successful. It has temperature, and rate of mixing were optimized for been proved that the use of 100% vegetable oil was production of Karanja oil methyl ester. The fatty acid also possible with some minor modifications in the fuel methyl esters content in the reaction mixture were system.

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Micro-emulsification: A micro emulsion is defined as the Water, originated either from the oils and fats or colloidal equilibrium dispersion of optically isotropic fluid formed during the saponification reaction, retards the microstructures with dimensions generally in the range of transesterification reaction through the hydrolysis 1-150 nm formed spontaneously from two normally reaction. It can hydrolyse the triglycerides to diglycerides immiscible liquids and one or more ionic or non ionic and forms more FFA. The typical hydrolysis reaction is amphiphiles [10]. All micro emulsions with butanol, shown in Eq. (3). hexanol and octanol will meet the maximum viscosity limitation for diesel engines.

Cracking or Pyrolysis: Cracking is the process of conversion of one substance into another by means of heat or with the aid of catalyst. It involves heating in the absence of air and cleavage of chemical bonds to yield small molecules. The pyrolysed material can be vegetable However, the FFA can react with alcohol to form oils, animal fats, natural fatty acids and methyl esters of ester by an acid-catalysed esterification reaction fatty acids. Normally, the catalyst for this reaction is concentrated sulphuric acid .This reaction is very useful for handling Transesterification: Transesterification is otherwise oils or fats with high FFA, as shown in the equation known as alcoholysis. It is the reaction of fat or oil with an below: alcohol to form esters and glycerin. A catalyst is used to improve the reaction rate and yield. Among the alcohols, methanol and ethanol are used commercially because of their low cost and their physical and chemical advantages. They quickly react with tri-glycerides and NaOH and are Normally, the catalyst for this reaction is easily dissolved in them. concentrated sulphuric acid. Due to the slow reaction rate Common vegetable oils are esters of saturated and and the high methanol to oil molar ratio that is required, unsaturated mono carboxylic acids with the tri hydric acid-catalysed esterification has not gained as much alcohol glyceride. These esters are called triglycerides, attention as the alkali-catalysed transesterification. which can react with alcohol in the presence of a catalyst, a process known as transesterification. The simplified Properties of Pongamia Oil form of its chemical reaction is presented in equation Flash point: Flash point of a fuel is found the lowest temperature at which vapour of a substance momentarily have taken fire in the form of flash. There are two basic types of flash point measurement, open cup and closed cup. In open cup devices the sample is contained in an open cup which is heated, and at intervals a flame is brought over the surface. The measured flash point will actually vary with the height of the flame above the liquid where R1, R2, R3 are long-chain hydrocarbons. surface, and at sufficient height the measured flash point Vegetable oils and fats may contain small amounts of temperature will coincide with the fire point. There are two water and free fatty acids. For an alkali-catalysed types of closed cup testers, non-equilibrium, such as transesterification, the alkali catalyst that is used will react Pesky-Martens where the vapours above the liquid are with the FFA to form soap. Figure the saponification not in temperature equilibrium with the liquid, and reaction of the catalyst (sodium hydroxide) and the FFA, equilibrium, where the vapours are deemed to be in forming soap and water. temperature equilibrium with the liquid. In both these types the cups are sealed with a lid through which the ignition source can be introduced [11]. Closed cup testers normally give lower values for the flash point than open cup and are a better approximation to the temperature at

1261 Middle-East J. Sci. Res., 12 (12): 1758-1765, 2012 which the vapour pressure reaches the lower flammable In experimental the oil are taken 20 or 25 ml of the oil limit. sample in the tube and fitted a zeal thermometer along In experimental oil is taken approximately 75 ml of the with ,placed it in the manner as mentioned above, sample in the flash point cup or filled the oil in the cup up allow to cooled the oil sample slowly by adding ice cubes. to the marked, placed it on a circular plate, inserted a zeal Stirred uniformly till flow of the oil is seized or the oil thermometer, applied heat slowly have been using un sen should not poured in the tube if it is tilted. The burner or electrically, checked the flash of the oil for every temperature at which the oil does not flow or pour is rise of 5°C temperature in the case of high flash oil and called pour point. The pour point of the oil is found 1°C. 2 for low flash oil by have been applying small flame on it. The temperature at which the vapours of the oil cached Specific gravity: Specific Gravity is a relative measure of flash is called flash point. The flash point of Pongamia oil the density of a substance. It is defined as the ratio of is obtained 243°C. density of the substance ( ), to a reference density ( ref). The most common reference density used in the Fire point: Fire point is the lowest temperature at which measurement of specific Gravity is the density of water at the fuel gets ignited and burns under specific conditions 15°C... of test. After flash point, it was continued at such a rate Weight of 50 ml or 25 ml capacity empty specific that the increase in temperature recorded by the gravity bottle along with stopper(note:W1), fill the given thermometer was neither less than 5°C nor more than 6°C oil sample into the bottle up to the mark, kept the bottle in per minute. The test flame was lighted and adjusted. The the water bath or vessel has been containing water and fire point of pongamia oil is obtained for 255°C. maintained temperature at 15°C for 30 to 40 minutes, if the level of the oil in the bottle is below the mark, added sufficient oil to level the mark or if the level of the oil is Cloud point: Cloud point of a fluid is the temperature at above the mark removed the excess of oil from the bottle, which dissolved solids are no longer completely soluble, then weigh the bottle (note:W2). Removed the oil, cleaned precipitating as a second phase giving the fluid a and dried it, now filled the distilled water in the bottle and cloudy appearance. In the petroleum industry, cloud cooled it in the same manner as mentioned above, weight point refers to the temperature below which in diesel the bottle again (note: W3) or bio wax in form a cloudy appearance. The presence of solidified thickens the oil and Specific gravity = (W2-W1) / (W3-W1) clogs fuel filters and injectors in engines. The wax also accumulates on cold surfaces and forms an emulsion with The specific Gravity of Pongamia oil is obtained 0.9413. water. In experimental the oil are taken 20 to 25 ml of the oil Density: Density is also defined as its weight per unit in the pour point tube and fit a zeal thermometer along volume, although, this quantity is more properly called with cork, then the pour point tube is placed in the vessel specific weight. Followed the same procedure in the same containing water, cooled the liquid by adding small pieces way as mentioned in the specific gravity, calculated the of ice or ice cubes, stir the liquid continuously by stirrer, density as follow, the level of the oil in the tube should be immersed in the water. The temperature of the oil dropped slowly and Density = (W2-W1) / (Volume of water) observed the appearance of cloud in the oil. The temperature at which appearance of cloud in the oil is The density of pongamia oil is obtained 0.9413. called cloud point. This value is obtained for 9°C. Pour point Kinematic Viscosity: Viscosity is defined as the Pour point of a liquid is the lowest temperature at resistance to flow of a liquid, Biodiesel. A high viscosity which oil will pour or flow under prescribed conditions. It means that the Fuel will not flow easily. A low viscosity is a rough indication of the lowest temperature at which means that the liquid flows very easily. A viscometer is a oil is readily pumpable. Also, the pour point can be device for testing the viscosity. Viscosity is a defined as the minimum temperature of a liquid, after fundamental property and has units of mm2/s or cost. which, on decreasing the temperature, the liquid ceases to Temperature has a big influence on the viscosity of a flow. liquid. When the temperature is lowered the viscosity

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increases. Viscosity is a measure of the fluids The bomb calorimeter is immersed in a vessel adhesive/cohesive or frictional properties. containing water Kinematic Viscosity is the ratio of absolute or Oil is Rotated with the help of stirrer to get constant dynamic viscosity to density-a quantity in which no force temperature is involved. Kinematic viscosity can be obtained by dividing the absolute viscosity of a fluid with density. Once constant temperature is reached supply is The viscosity of a fluid is highly temperature dependent switched on and for either dynamic or kinematic viscosity to be Temperature is noted till oil gets stable condition and meaningful, the reference temperature must be noted. again it comes down C.V for this Pongamia oil is 9976 kcal/kg Oil is poured into the U-tube ( till the mark) and fitted to the clamp Purification of Pongamia oil: Suitable amount of The whole apparatus is immersed in a water bath and Pongamia oil was added into container flask containing allowed it to maintain at a constant temperature of hot water, and wait for 30 minutes till impure particles 40°C. settles down. Using rubber bulb the oil is sucked above the mark and allowed oil to flow freely Separation of Pongamia oil: Hot water containing Once the oil reaches the mark stop watch is started. Pongamia oil was collected into the separating funnel and When it reached at bottom level of the U-tube stop shaked it vigorously for 5 to 10 minutes. Because of low watch is stopped and time required for this is noted density of Pongamia oil settles on the top of the funnel Kinematic viscosity for Pongamia oil is obtained and high density water and impurities settled at bottom of 51.5cSt. the funnel. Then disperse water and impure particles by opening the funnel valve, after that the purified Pongamia Cetane Number: Cetane number is a measure of the oil was collected into the jar. Thus they are prone to ignition performance of a diesel fuel obtained by corrosion when in contact with water. Hence it is comparing it to a reference fuels in standardized engine necessary to dry the water washed biodiesel product. test. Satisfactory diesel combustion demands self-ignition of the fuel as it is sprayed near TDC (top dead centre) into the hot swirling compressed cylinder gas. Long ignition delay is not possible as it leads to knock. Therefore, the cetane number of the substitute fuel should be high enough, which is a measure of knock tendency of the fuel. The cetane number is predicted ± 10% using the esters composition. Cetane index = 46.3 + 5458/X-0.225Y : X- Saponification number: Y-Iodine number. The cetane number of Pongamia oil is obtained 49.8.

Calorific Value: Heating value of a fuel is the amount of heat released during the combustion of a specified amount of it. It is measured in units of energy per unit of the substance such as kcal/kg, kJ/kg. Heat of combustion is the energy released as heat when a compound undergoes complete combustion with oxygen under standard conditions. The chemical reaction is typically a Fig. 1: Separation of Impurities from pongamia oil hydrocarbon reacting with oxygen to form carbon dioxide, water and heat Collected purified Pongamia oil was heated to 60°C to remove FFA and moisture contamination in oil. 1 gm of oil is taken into the Nichrome crucible/oil crucible and inserted it in the Bomb calorimeter Experimental Setup and Steps: Transesterification was 25-30 pounds of oxygen is supplied in order to burn carried out in a batch type reactor. This reactor consists the oil of following components

1263 Middle-East J. Sci. Res., 12 (12): 1758-1765, 2012 i. Magnetic stirrer with heater arrangement. ii. Single necked round bottomed glass beaker. iii. Temperature controller iv. Stirrer controller.

Single necked round bottomed glass beaker is used to collect sample of mixture (oil + Methanol + catalyst). Magnetic stirrer and heater provide the stirring and heating effect simultaneously. Temperature controller is used to control the desired heating effect. Stirrer controller is used to control the stirring effect.

First step Transesterification of Pongamia oil Fig. 3: Second step transesterification reaction with KOH catalyst

speed for all test runs. And heat up to 3 hours and switch off the apparatus and wait until the mixture gets cooled. The resultant mixture is taken into the separating funnel containing biodiesel and glycerol. After 3 to 4 hours glycerol settles down at the bottom of biodiesel. The glycerol is separated by opening the value of the separating funnel.

CONCLUSION

Fig. 2: First step transesterification reaction with H24 SO catalyst In the present work the properties of pongamia oils were found out and compared with diesel. From the A round bottom flask of 1000 ml is used for the comparison it is concluded that the pongamia oil is present analysis. The Pongamia oil in the flask was suitable for biodiesel production. The production of heated on a hot plate having magnetic stirrer biodiesel from pongamia oil has been carried out using arrangement. The mixture was stirred at the same two step transesterification. The maximum yield of speed for all test runs. Initially 489 ml Pongamia oil is biodiesel was obtained from the transesterification of 6:1 heated to 65°C. Then the methanol 86 ml and the molar ratio of methanol/oil in the presence of 3 ml Sulphuric acid 3 ml are mixed. The mixture is transferred to sulphuric acid in the first step process after that acidic oil a reactor. The temperature maintained for the whole with 6 mole of methanol in the presence of 0.6 gram KOH transesterification process is about 60°C. And heat up to as catalyst in the second step process at 60°C reaction 3 hours and switch off the apparatus and wait until the temperature and 3 hr reaction time to each mixture gets cooled. The resultant mixture is taken into the transesterification process. separating funnel containing acidic oil and impurities with glycerol. After 3 to 4 hours impurities settles down at the REFERENCES bottom of acidic oil. Impurities with small amount of glycerol are separated by opening the value of the 1. Malaya, N., L.C. Meherb, S.N. Naikb and L.M. Dasa, separating funnel. 2008. Production of biodiesel from high free fatty Initially obtained acidic oil from first step acidKaranja(Pongamiapinnata) oil. Bio mass energy transesterification reaction is heated to 65°C. Then the 32: 354-357. methanol 86 ml and the KOH0. 5 gram are mixed. The 2. Thooyamani, K.P., V. Khanaa and R. Udayakumar, mixture is transferred to a reactor. The temperature 2013. Weed control system of tea garden using GIS maintained for the whole second step transesterification based database Management system. Middle-East J. process is about 60°C. The mixture was stirred at the same Sci. Res., 5(12): 1702-1706.

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