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April 2011, Volume 2, No.

2 International Journal of Chemical and Environmental Engineering

Production of Biodiesel from Non-edible plant oils having high FFA content.
M.Mathiyazhagan1, A.Ganapathi2, B. Jaganath3, N. Renganayaki4, And N. Sasireka5
1, 2 & 3 4&5

Department of Biotechnology, Bharathidasan University, Tiruchirappalli, Tamilnadu, India. Department of Biotechnology, Srinivasan College of Arts and Science, Perambalur, Tamilnadu, India. * Corresponding author: mathibdu@gmail.com.

Abstract
Biodiesel is a more attractive alternative fuel to diesel engines. Because, it is a renewable and non-polluted fuel that can be produced from plant and animal fats. Biodiesel emits low pollutants (except NOx) than petroleum diesel. But the major problem arises for the commercialization of biodiesel is its cost. Since most of the biodiesels were derived from edible oils like soy bean, sunflower, rapeseed, palm etc. These oils are essentially edible in India and other developing countries. On the other hand, diversion of edible oils as feed stocks for biodiesel production leads to food crisis. Therefore this research mainly concentrates the non-edible oils as feed stocks for biodiesel production to reduce the cost of biodiesel. Normally alkali catalyzed method was followed for biodiesel production process. However the non-edible oils having high FFA content which is not suitable for normal transesterification process. Hence a two-step catalyzed method was used to prepare the biodiesel. For this study the following non-edible oil samples such as Jatropha, Pongamia, Madhuca and Azhadirachta were used to extract the biodiesel. For this study biodiesel yield from various nonedible oils and its cost optimization were discussed. Key words: Non-edible oils, Renewable fuel, Biodiesel, Pollution, Free Fatty Acid (FFA), Two-step catalyzed method.

1. Introduction
The concept of vegetable oils as fuel is not new. It was proposed by Rudolf diesel at the time of Second World War. He used pea nut oil as a fuel in diesel engine. The major obstacle for commercialization of biodiesel (BD) is its cost approximately 70-90% of biodiesel cost is arises from the cost of feed stocks (Canakci, M., Van Gerpen, J., 2001). Because most of the biodiesels were prepared from edible oils like soybean (de Oliveira, 2005), rapeseed (Jeong and Park, 1996), sunflower (Vicente, et al., 2004), safflower (Meka, et al., 2007), canola (Singh, et al., 2006), palm (Darnoko and Cheryman, 2000; Cheng, et al., 2004) and fish oil (El Mashad, et al., 2006). Cost of edible oils is very higher than PD (Petroleum Diesel) and we use edible oils for biodiesel production leads food oil crisis. The above problem can be solved by using cheapest, low cost non edible oils such as Jatropha, Pongamia, Madhuca and Azhadirachta as feed stocks for BD production. However the direct use of vegetable oils as fuel can cause numerous engine problems like poor fuel atomization, incomplete combustion and carbon deposition on fuel injector and engine fouling (Sridharan and Mathai, 1974; Encinar et al., 2002; Williamson, A. M.; Badr, O., 1998; Karaosmanoglu, F.; et al., 2000). This is due to the presence of higher viscosity (about 11-17 times higher than petroleum diesel) of vegetable oils. Hence the viscosity of vegetable oils can be reduced by several methods which include blending of oils,

microemulsification, pyrolysis and transesterification (Ma and Hanna, 1999). Among this transesterification is widely used for industrial biodiesel production. Because it gives high yield with low temperature, pressure and short reaction time. Transesterification is a chemical reaction involving triglycerides with alcohol in the presence of catalyst (Fig-1).

Fig-1: Transesterification of triglycerides

Based on the use of catalyst the transesterification can be divided in to three types they are acid catalyzed, alkali catalyzed and enzyme catalyzed method. For transesterification process methanol was commonly used. Because methanol is cheaper than ethanol and the recovery of unreacted methanol is easier (Zhou and Boocock, 2003). In the case of base catalyst potassium hydroxide (KOH) or sodium hydroxide (NaOH) are used, because it is less expensive and easy to handle in storage and transport. However most of the studies show best properties of biodiesel was obtained by using potassium hydroxide as catalyst (Encinar, et al., 2005; Jeong and

Park, 1996; Karmee, 2005; Dorado, et al., 2004; Dorado, et al., 2002; Darnoko and Cheryman, 2000; Ugheoke, et al., 2007; El-Mashad, et al., 2006). Besides some studies show best result with the use of sodium hydroxide as fuel (Felizardo, et al., 2006; Vicente, et al., 2004; Cheng, et al., 2004; de Oliveira, 2005). Nevertheless base catalyzed transesterification method is commonly employed for BD production. Since, it is more economical method than other methods (Singh, et al., 2006). But base method is not suitable if the oils having high FFA content such as above 3% (Dorado, et al., 2002). In general the unpurified oil samples having high FFA content (Free Fatty Acid) particularly non-edible oils. This high FFA content of oil samples consumes the catalyst to form soap, Soap formation reduces the catalyst effect leads to gel formation and makes the separation of glycerol from product (Guo and Leung, 2003) is difficult. In this situation a two step catalyzed method (Wang et al., 2007; Gerpen and Knothe, 2005 and Zhang et al., 2003) such as acid method followed by alkali method was used to prepare the biodiesel from the following non-edible oils like Jatropha, Pongamia, Madhuca and Azhadirachta.

as that of acid catalyzed method. The top layer was measured and it was saved for purification process.

2. Materials and Methods
This research was carried out in the Department of Biotechnology, Bharathidasan University, Tiruchirappalli, Tamilnadu. The main aim of this study is to achieve the maximum conversion of biodiesel from the oils having high FFA content by using a two step catalyzed transesterification method (acid method followed by alkali method). For this study the following non-edible oil samples such as Jatropha curcus L., (Kattamanakku) Pongamia pinnata L., (Pungam) Madhuca indica J.F. Gmel (Illupai) and Azhadirachta indica A. Juss (Neem) were collected from authorized oil industries (Renulakshmi Agro Industries, Coimbatore, and Saravana Oil Mills, Keeranoor, Tamilnadu). 2.1 Acid method In this method high FFA content of non-edible oils are reduced below 3% by using acid pretreatment. It comprises the preheating of oil samples in water bath at 60 °C for 30 min. The acid catalyst mixture (10 ml H2SO4 mixed with 200 ml methanol/ liter oil samples) was added to preheated oil samples and it kept in water bath for 3-4 hrs at 60 ºC. After the reaction, the sample shows two distinct layer such as upper ester layer and lower glycerol layer. The lower glycerol layer was decanted and the upper layer was measured and stored for further study (for alkali catalyzed method). 2.2 Alkali/Base catalyzed method For this study the pretreated (acid treated) oil samples were heated, addition of alkali catalyst mixture (7.5 gram KOH with 200 ml Methanol/liter oil samples). The mixture was shacked and incubated to water bath at 60 ºC for 1-2 hrs. Finally the samples show two distinct layers

Fig-2: Mechanism of base catalyzed transesterification

2.3 Purification of product After transesterification the ester layer may contain unreacted catalyst, methanol and residual glycerol. These impurities were removed by hot water treatment. The water washing method was continued (4-6 times) until the water layer becomes clear. For this process equal amount of hot distilled water was used to remove the impurities. 2.4 Drying of product After the completion of purification process the ester layer may contain some amount of water and methanol. This should be removed before the commercialization of fuel. Because methanol reduces the flash point of fuel and it have corrosive nature to fuel hoses. Water content is responsible for the growth of biological organisms and it also increases the acid value of fuel. Hence the ester layer was heated in hot plate with stirrer at 100°c for 15 to 30 min to remove the water and methanol content present in the product (biodiesel). Finally the dried biodiesel fuel was saved.

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obtained from Jatropha oil. Lower ester yield indicates higher removal of glycerol leading to reduction of viscosity than other oil samples.
Non-edible oils Table-2: Yield of Biodiesel using Alkali catalyst Source Oil H2SO4 Methan Glycer sample volume ol (ml) ol (ml) (ml) (ml/lit) Jatropha Pongamia Madhuca Azadirachta 1000 1000 1000 1000 10 10 10 10 200 200 200 200 125 160 180 135 Ester layer( ml/lit) 1185 1040 1020 1065

Methanol+ H2SO4

Pretreatment

Methanol +KOH

Pretreated oil

Transesterification

Glycerol

Crude Biodiesel

Purification

Hot Dis. Water

Washing tank

In alkali catalyzed method maximum ester conversion was achieved from Azadirachta oil and the lowest ester conversion was obtained from Pongamia oil. Similarly highest glycerol was achieved from Azadirachta oil and lowest glycerol was obtained from Madhuca oil sample. However on the basis of biodiesel quality alkali catalyzed method gives high purity biodiesel than acid method. Higher glycerol production indicates complete conversion of triglycerides in to esters resulting in the severe reduction of viscosity of vegetable oil. 3.1 Optimization of biodiesel cost:

Soap/Pears

Pure Biodiesel

Table-3: Comparison of non-edible oils Biodiesel cost optimization with edible oils and Petroleum diesel (PD). Cost of edible oils 4062$/liter Cost of Non edible oil seeds/kg 3-5 kg seeds produces one litter oil Oil extraction & other charges Total Less cost of oil cake 5 kg seeds produces 4 kg oil cake Less cost of oil cake Biodiesel Production cost (Chemicals+ EB + Equipment & Others) One litter oil produces 850900 ml BD One litter oil produces 300 ml glycerol Less cost of glycerol Cost of BD 226$/kg

Diesel Engine Fig-3: Flow chart of Biodiesel production from non-edible oils -

226$X226$ = 1128$ 90$/kg, 226$X90$ = 451$ 1128$+451$ = 1580$ 135$/kg 181$X135$ = 542$ 1580$-542$ = 1038$ 451$/litter 1038$+451$ = 1489$

3. Results and Discussion In the present study the high FFA content of nonedible oils such as Jatropha curcus, Pongamia pinnata, Madhuca indica and Azhadirachta indica are effectively converted in to biodiesel fuel by using two-step catalyzed method. After the transesterification, the ester layer was washed with hot distilled water to remove the impurities and the product was dried with hot plate in 100°C for 30 min to remove the water and methanol content. Finally the ester layers (biodiesel) from different non-edible oils were quantified to find out the maximum yield of biodiesel variety. The biodiesel yield using different methods was presented in table 1 and 2 respectively.
Table-1: Yield of Biodiesel using Acid Catalyst.

-

-

-

-

Biodiesel production cost (Chemicals+ EB + Equipment & Others) One litter oil produces 850900 ml BD One litter oil produces 400 ml glycerol Less cost of glycerol Cost of BD Cost of Petroleum Diesel

452$/liter 4062$+452$ = 4513$

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-

Source

Oil sampl e (ml) 1000 1000 1000 1000

KOH (g) 7.5 7.5 7.5 7.5

Methan ol (ml) 200 200 200 200

glycerol (ml/liter) 220 210 200 240

Ester layer(ml/ lit) 980 970 980 985

271$/300 ml 4513$-271$ = 4242$ 4242$/liter 1806$/liter

271$/300 ml 1489$-271$ = 1219$ 1219$/ liter -

Jatropha Pongamia Madhuca Azadirachta

In Acid method maximum ester was obtained from Jatropha oil lowest ester conversion was achieved from Madhuca oil. Similarly maximum glycerol byproduct was obtained from Madhuca oil and lowest glycerol was

The cost optimization of biodiesel from non-edible oils available in India and Tamilnadu was also examined

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to find out the suitability of biodiesel fuel for commercialization. The comparison of fuel price of different fuels from edible oils, non-edible oils with petroleum diesel was presented in table-3. From the table 3 the cost of biodiesel from non-edible oils is lower (Rs 27/liter) than other fuels. Where as cost of biodiesel from edible oils is very higher (Rs 97/liter) than other fuels including PD. But the cost of PD is (Rs 40/liter) unstable. Therefore this study recommends the commercial biodiesel production from non-edible oil sources such as Jatropha curcus, Pongamia pinnata, Madhuca indica and Azhadirachta indica.

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4. Conclusion
In this study the high FFA content of non-edible plant oil sources are efficiently converted in to biodiesel fuel. Yield of biodiesel from different non-edible oils which is commonly available in India as well as Tamilnadu were examined and the results recommend the biodiesel production from Azadirachta indica oil on the basis of high yield and quality of biodiesel.On the basis of cost effectiveness this study recommends BD production from non-edible oils (Jatropha, Pongamia, Madhuca and Azhadirachta).The main advantage for biodiesel fuel production from non-edible oils reduces the use of PD. Biodiesel production technology needs further study in the aspects of elimination of biodiesel purification process by using newly developed catalyst such as heterogeneous catalyst like MgO and ZnO etc instead of homogeneous catalyst (H2SO4 & KOH). Because, water washing method produces large amount of waste water which is discharged to environment leads to environment damage.

ACKNOWLEDGEMENT
The author Mr. M. Mathiyazhagan, gratefully acknowledge the Jawaharlal Nehru Memorial Fund, New Delhi, India and Indian Overseas Bank, Veppur Branch, Perambalur (DT), Tamilnadu, India for funding to carry out this work successfully REFERENCES
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