Journal of Engineering Research and Studies

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Research Paper

METHANOLYSIS OF HIGH FFA KARANJA OIL IN AN OSCILLATORY BAFFLED REACTOR
Y.C.Bhattacharyulu*, V.N.Ganvir, S.A.Bahegankar, Pankaj Nikhare Address for Correspondence Department of Petroleum Refining & Petrochemical Technology, Laxminarayan Institute of Technology, Nagpur ABSTRACT
India currently imports about 70% of its petroleum requirements, spending more on foreign exchange. Vegetable oils have the potential to be considered as an appropriate alternative fuel as their properties are similar to that of diesel. The major problem associated with the direct use of vegetable oils is its high viscosity. One possible method to overcome this problem is transesterification of potential oils to produce esters i.e. biodiesel. Biodiesel is an alternative diesel fuel that is produced from vegetable oils and animal fats. It consists of the monoalkyl esters formed by a catalyzed reaction of the triglycerides in the oil or fat with a simple monohydric alcohol. Oscillatory baffled reactors are a novel type of reactor, it consisting of tube containing equally spaced orifice plate baffles. An oscillatory motion is superimposed upon the net flow of the process fluid, creating flow patterns conducive to efficient heat and mass transfer. That’s why in oscillatory flow reactor the reaction time is less that is 10 minutes at temperature in range of 20oC-25oC compared to batch reactor. Batch reactor takes minimum 1 hr and at temperature of about 50oC -55oC for reaction under similar conditions. KEYWORDS Biodiesel, oscillatory baffled reactor, transesterification, triglycerides, viscosity.

INTRODUCTION TO BIODIESEL Increased environmental concerns, tougher clean air act standards and depletion of fossil fuels, necessitate the search for a viable alternative fuel, which is more environment friendly [1].Majority of the worlds energy needs are supplied through petrochemical sources, coal and natural gases, with the exception of hydroelectricity and nuclear energy, of all, these sources are finite and at current usage rates will be consumed shortly [2]. The depleting reserves of fossil fuels, increasing demands for diesels and uncertainty in their availability is considered to be the important trigger for many initiatives to search for the alternative source of energy, which can supplement or replace fossil fuels [3]. Hence it is important to search for an alternate low cost fuel for every day usage which should be sustainable and also friendly to the environment. The use of vegetable oils as alternative fuels has been around for 100 years when the inventor of the diesel engine Rudolph Diesel first tested peanut oil, in his compression ignition engine. [5]It is interesting to note that Rudolph Diesel in the preface of his patent of 1912 wrote “Use of vegetable oil for engine fuel may seem insignificant today but such oil may become in the course of time ,as important as petroleum”.[18 ] Among the many possible sources biodiesel derived from vegetable oil attracts attention as a promising one for substitution or blending with conventional diesel based fuel [4].According to the American Society for Testing and Materials (ASTM)’s definition biodiesel is monoalkyl esters of long chain fatty acid derived from a renewable feedstock, such as vegetable oil animal fats and used cooking oils [5].Bio diesel is a liquid ; ester-based oxygenated fuel, similar to petroleum based diesel fuel but made from vegetable products ; either plants oils or animal fats.[17]. Bio diesel, having the chemical structure of fatty acid alkyl esters, is a clean burning fuel produced from renewable domestic sources such as vegetable oils and animal grease. It is biodegradable, non-inflammable, non-toxic and has a favorable combustion–emission profile, producing much less carbon monoxide, sulfur dioxide and unburned JERS/Vol. III/ Issue I/January-March, 2012/144-148

hydrocarbons than petroleum-based diesel [6]. Bio diesel is usually produced from food-grade vegetable oils that are more expensive than diesel fuel. Therefore, biodiesel produced from food-grade vegetable oil is currently not economically feasible. Waste cooking oils, restaurant grease ,animal fats and non edible oils are potential feedstock for biodiesel. [8] Table.1.1. List of different Feed stokes for Biodiesel production [3]:

Pongamia, Jatropha and Neem based methyl esters (biodiesel) can be directly used in diesel engines without any engine modifications [7].Karanja (Pongamia pinnata) is an underutilized plant which is grown in many parts of India. The main production area for the Karanja oil is in the village level and villagers use this oil in some of their daily activities [10]. Karanja oil is one of the potential oils with

Journal of Engineering Research and Studies yearly production of 200 t (metric ton), out of which 6% is being presently utilized .[11] The karanja oil contains primarily eight fatty acids viz. palmitic, stearic, oleic, linoleic, lignoceric, eicosenoic, arachidic and behenic. Of these, the four which are commonly found in most oils, including Pongamia, are the saturated acids, palmitic and stearic and the unsaturated acids, oleic and linoleic[12]. The freshly extracted Karanja oil is yellowish orange to brown and rapidly darkens on storage. It has a disagreeable odor and bitter taste. The presence of toxic Xavonoids makes the oil non-edible [13] .India’s transportation fuel requirements are unique in the world. India consumes almost five times more diesel fuel than gasoline, whereas, almost all other countries in the world use more gasoline than diesel fuel. Diesel burns roughly 64 Mt, or 450 million barrels, a year, as opposed to about 84 million barrels of Gasoline. So there is much importance for searching alternate to petro-diesel. At present, India is producing only 30% of the total petroleum fuel needed. The remaining 70% is being imported which cost about Rs 80000 cr. every year .[19] Following table shows oil producing species in india [3]

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spaced orifice baffles and schematic of baffle are shown in.

Figure 1: Assembly of the Oscillatory Flow Mix Reactor for Biodiesel Production The mechanism of mixing in the OFR is illustrated in which shows two half cycles over an oscillation period. Vortices are formed behind baffles on an upstroke, drawing fluid from near the walls into the eddies. On the reverse stroke, the vortices formed are pushed into the central region of the device while new vortices are generated at the same time behind the opposite baffles, and the cycle repeats. This provides an effective way to move fluid from the wall of the device to the centre, and leads to the axial velocity components being of the same order of magnitude as the radial ones.[16].

In this paper discussion is made on production of biodiesel in oscillatory baffled reactor. Oscillatory baffled reactors are used in biodiesel production, it consisting of tube containing equally spaced orifice plate baffles. An oscillatory motion is superimposed upon the net flow of the process fluid, creating flow patterns conducive to efficient heat and mass transfer, whilst maintaining plug flow [14]. That’s why in oscillatory flow reactor the reaction time is less that is 10 minutes at temperature in range of 20oC-25oC compared to batch reactor. Batch reactor takes minimum 1 hr and at temperature of about 50oC 55oC for reaction under similar conditions. Apparatus and experimental setup Oscillatory baffled reactors are a novel type of reactor, consisting of tubes containing equally spaced orifice plate baffles. These reactors exploit the uniform and efficient vortex mixing that can be achieved when an oscillatory fluid motion interacts with orifice plate baffles in a tube. Effective and energy efficient heat transfer can be obtained by oscillatory flow mixing for both the batch fluid oscillation situation and for the batch baffle oscillation, due to the mechanisms of vortex interaction.[15].The Oscillatory baffled reactor in shows a new relatively mixing device that is based upon superimposing periodic fluid oscillations within a cylindrical column containing equally

Figure 2 : Mechanism of mixing in an oscillatory baffled column[16] Properties of karanja oil

Experimental Procedure:. Since the FFA contents of Karanja oil collected is high, a two step process, i.e., acid catalyzed esterification followed by based- catalyzed transesterification process is selected for converting it into methyl ester. This is to avoid the problem of saponification. The first step, i.e., acid catalyzed esterification is for the reduction of FFA, which is mainly a pretreatment process. The process used sulphuric acid as acid catalyst. Once the FFA contents in Karanja oil reduces to the base catalyst transesterification is applied to get biodiesel.

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Journal of Engineering Research and Studies Karanja oil is contaminated with water and solid particles. Solid portion of Karanja oil is removed by filtering using a filter paper. Water is removed by mixing Karanja oil with silica gel followed by stirring the mixture and filtering with filter paper. This step is conducted twice to ensure complete removal of water. Then the Karanja oil is processed through two step process. Step – 1 Sulfuric Acid Catalyzed Pre-treatment Step: 1. Karanja oil is filtered with filter paper to remove impurities. It is then mixed with silica gel for 15 min and filtered. This will reduce the water content of oil. 2. 100 ml of Karanja oil is poured into the reactor. 3. The mixture of concentrated sulphuric acid with methanol is then added into the reactor and the oscillations are started. 4. Oscillations are carried out for 10 min at room temperature. 5. Mixture is settled for 6-8 hours. RESULTS AND DISCUSSION Run Summary Catalyst used: H2SO4 Reactiontime:10 minutes First stage:
Run No. Catalyst conc. (vol%) 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 Amount of oil (ml) 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Amount of Methanol (ml) 27 27 27 27 27 39 39 39 39 39 52 52 52 52 52 Mole ratio

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Two layers are formed. Upper layer is treated oil with lower acid value. Different methanol to oil molar ratio (6:1 , 9:1,12:1) and H2SO4 wt% (1, 2,3,4 and 5 vol%) were used to investigate their influence on the acid value of the Karanja oil. The optimum condition having lowest acid value was used for the main transesterification using KOH & NAOH as catalyst. Step – 2 Base (KOH) Catalysed Transesterification: 1. Treated Karanja oil is filtered with filter paper to remove impurities. 2. Treated Karanja oil is poured into the reactor. 3. The mixture of potassium hydroxide with methanol is then added into the reactor and the oscillations are started. 4. Oscillations are carried out for 10 min at room temperature. 5. Mixture is settled for 6-8 hours. Two layers are formed. Upper layer is methyl ester with lower acid value and bottom layer is glycerol.

6.

Amount of Biodiesel 89 92 87 87 82 95 92 91 93 88 104 101 98 104 107

Lower layer (ml) 7 15 15 18 21 18 14 24 24 30 21 22 33 39 34

Density (gm/ml)

Viscosity (cSt)

1a 2a 3a 4a 5a 6a 7a 8a 9a 10a 11a 12a 13a 14a 15a

1:6 1:6 1:6 1:6 1:6 1:9 1:9 1:9 1:9 1:9 1:12 1:12 1:12 1:12 1:12

0.9108 0.9115 0.9242 0.9147 0.9270 0.8675 0.8719 0.8916 0.8904 0.8977 0.9148 0.9145 0.9168 0.9146 0.9182

34.117 36.934 37.560 37.247 39.125 31.340 33.960 35.995 34.586 35.838 31.926 33.021 33.804 33.647 34.117

Acid Value (mg of KOH/gm of Sample) 3.569 5.563 5.099 6.119 6.629 3.059 3.824 5.864 6.374 7.139 6.887 7.379 7.134 8.118 8.364

Flash point O C 130 134 133 125 140 134 134 145 123 134 134 134 134 134 134

Second stage: Reaction time: 10minutes Catalyst used: KOH
Run No. 1b 2b 3b 4b 5b 6b 7b 8b Catalyst Conc. (wt%) 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 Mole ratio 1:9 1:9 1:9 1:9 1:9 1:9 1:9 1:9 Biodiesel collected Upper layer (ml) 85 84 80 83 83 80 84 95 Glycerin Lower layer (ml) 22 20 20 18 21 20 21 20 Density (gm/ml) 0.883 0.875 0.876 0.876 0.868 0.864 0.862 0.862 Viscosity (cSt) 9.634 7.947 7.379 6.792 5.859 5.605 5.365 5.316 Acid value (mg of KOH/gm of sample) 0.1501 0.1751 0.2202 0.2012 0.2005 0.1825 0.1276 0.1273 Flash point O C 155 150 146 140 138 135 133 130

DISCUSSION Karanja oil methyl ester in an oscillatory flow reactor:In this topic, effect of various parameters like oil to methanol ratio, concentration of catalyst on quality of biodiesel produced in terms of kinematic viscosity, JERS/Vol. III/ Issue I/January-March, 2012/144-148

density and acid value are discussed for karanja oil methyl ester in an oscillatory flow reactor operated in a batch mode. 1) Effect of molar ratio on properties of treated Karanja oil for first stage:-

Journal of Engineering Research and Studies Runs carried out with increasing mole ratio of oil to alcohol from 1:6 to 1:12 at catalyst concentration 1.0 to 5.0 vol% for 10 minutes are given. From the table I it can be seen that as the mole ratio increases from 1:6 to1:9,and then to 1:12 specific gravity first decreases then increases. In the range of mole ratio 1:6 to 1:12 viscosity first increases then decreases. But as the mole ratio increases, acid values also increases. From the data of table I i.e. RUN No 6a it was observed as for mole ratio is concerned 1:9 appears to be optimum value. Hence this mole ratio was to be chosen for second stage with potassium hydroxide as a catalyst. 2) Effect of physicochemical properties on biodiesel for second stage using KOH as catalyst:Runs are carried out with increasing catalyst concentration from 0.3 to 1 wt% of potassium hydroxide at 1:9 oil to alcohol ratio .From Table 2 it were observe that with the increasing in catalyst concentration from 0.3 wt% to 1 wt% 1. Viscosity of biodiesel goes on decreasing up to 0.8 wt% of catalyst and then nearly constant for 0.9 and 1 wt %. 2. Density remains almost constant for all values of catalyst concentration. 3. Acid value of biodiesel goes on increasing till 0.7 wt % and decreased for 0.8 wt % and nearly constant for 0.9 and 1 wt %. 4. Flash point goes on decreasing from 155 to 130 OC. Hence from the above discussion, the optimum conditions for biodiesel production are 1:9 oil to alcohol ratio ,catalyst concentration 1 vol % sulphuric acid, reaction time of 10 minutes for first stage and catalyst concentration 1 wt % of potassium hydroxide, mole ratio 1:9, reaction time of 10 minutes for second stage.

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JERS/Vol. III/ Issue I/January-March, 2012/144-148

Journal of Engineering Research and Studies

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5. Biodiesel production from Karanja needs less catalyst concentration and requires more mole ratios of oil to alcohol. 6. The transesterification reaction carried out in a batch operation is a long reaction involving immiscible liquid phases, thus the product yield is greatly dependant on effective mixing and agitation. This is efficiently achieved in the oscillatory flow reactor under study to give the product in much less periods of time. REFERENCES
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NPrakash,A Arul Jose ,M G Devanesan & T Viruthagiri , “Optimization of Karanja oil Transesterification” ,Indian Journal of Chemical Technology 2006 ,vol 13 ,pp 505-509 Srivastava A, Prasad R “Triglycerides-based diesel fuels.” Renewable Sustainable Energy Reviews 2000;4: pp 111– 133. S.P. Singh and Dipti Singh, “Biodiesel Production through the use of different sources and characterization of oils and their R. Jothiramalingam, M. K. Wang, “ Review of recent development in solid acid, base, and enzyme catalysts (heterogeneous) for biodiesel production via transesterification”, Ind. Eng. Chem. Res. 2009,48 pp 6162-6172. P. Nakpong and S. Wootthikanokkhan, “Biodiesel Production From Mixtures Of Vegetable Oil And Used Cooking Oil”, Asian journal on energy and environment, 2009, vol 10 (04), pp 221-229. S. Zheng, M. Kates, M.A. Dube, D.D. McLean. “Acidcatalyzed production of biodiesel from waste frying oil” .journal Biomass and Bioenergy 30 ,2006 ,pp 267–272. Shay EG. “Diesel fuel from vegetable oil: status and opportunities.” , Biomass Bioenergy 1993;4(4): pp227–42. M. Canakci, “The potential of restaurant waste lipids as biodiesel feedstocks” , Journal of Bioresource Technology, Volume 98, Issue 1, January 2007. T. Venkateswara Rao, G. Prabhakar Rao , and K. Hema Chandra Reddy, “Experimental Investigation of Pongamia, Jatropha and Neem Methyl Esters as Biodiesel on C.I. Engine”. Jordan Journal of Mechanical and Industrial Engineering. Volume 2, Number 2, Jun. 2008. pp 117 – 122. Malaya Naik, L.C. Meher, S.N. Naik, L.M. Das. “Production of biodiesel from high free fatty acid Karanja (Pongamia pinnata) oil.”, Biomass and Bioenergy 32 ,2008 , pp 354 – 357. Schwab AW, Bagby MO, Freedman B. Preparation and properties of diesel fuels from Vegetable oils. Fuel 1987;66:1372–8. Sanjib Kumar Karmee, Anju Chadha. Preparation of biodiesel from crude oil of Pongamia pinnata. Bioresource Technology 96 ,2005, pp1425–1429. L.C. Meher, Vidya S.S. Dharmagadda, S.N. Naik. Optimization of alkali-catalyzed transesteriWcation of Pongamia pinnata oil for production of biodiesel. Bioresource Technology 97 ,2006 ,pp 1392–1397. Adam P Harvey, Malcolm R Mackley and Thomas Seliger. ‘Process intensification of biodiesel production using a continuous oscillatory flow reactor’.J Chem. Technol Biotechnol. 2003 78: pp 338–341. G.G. Stephens , M.R. Mackley. “Heat transfer performance for batch oscillatory flow mixing.”, Experimental Thermal and Fluid Science 25 ,2002, pp 583–594 AW Fitch, X Ni_ and J Stewart., “Characterization of flexible baffles in an oscillatory baffled column”, Journal of chemical technology and biotechnology 76:1074-1079. Suresh kumar ,A .K.Gupta ,S.N. Naik , “Conversion of Non edible Oil into Biodiesel” Indian Journal of Chemical Technology 2003 ,vol 62 ,pp 124-132. Padma Vasudevan , Satyawati Sharma and Ashwini Kumar , “Liquid fuel from biomass :An overview” Indian Journal of Chemical Technology 2005 ,vol 64 ,pp 822-831. Annual Report 2006–2007. “Ministry of Petroleum and Natural Gas (MoPNG), Govt. of India”;2007.

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CONCLUSIONS The following conclusions may be drawn from the present study in the transesterification of Karanja performed in an oscillatory flow reactor operated under batch mode. 1. In oscillatory flow reactor at lower oil to methanol mole ratios gave biodiesel with highest viscosity. With increasing mole ratios of oil to alcohol, viscosity decreases. 2. In Oscillatory flow reactor the reaction time is less that is 10 minutes compared to batch reactor. 3. Oscillatory flow reactor can be operated at room temperature. 4. The optimum conditions for biodiesel production from Karanja oil in a batch oscillatory flow reactor appears to be for first stage, oil to methanol mole ratio 1:9, catalyst concentration (H2SO4) 1 vol % and reaction time of 10 minutes . Oil to methanol mole ratio 1:9, catalyst concentration (KOH) 1 wt% and reaction time of 10 minutes for second stage. JERS/Vol. III/ Issue I/January-March, 2012/144-148

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