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BIOMASS AND BIOENERGY 32 (2008) 354 – 357

Available at

Production of biodiesel from high free fatty acid Karanja
(Pongamia pinnata) oil

Malaya Naika, L.C. Meherb, S.N. Naikb, L.M. Dasa,
Centre for Energy Studies, Indian Institute of Technology, Delhi, Hauz Khas, New Delhi 110016, India
Centre for Rural and Development and Technology, Indian Institute of Technology, Delhi, Hauz Khas, New Delhi 110016, India

ar t ic l e i n f o abs tra ct

Article history: Non-edible oil contains several unsaponifiable and toxic components, which make them
Received 26 July 2006 unsuitable for human consumption. Karanja (Pongamia pinnata) is an underutilized plant
Received in revised form which is grown in many parts of India. Sometimes the oil is contaminated with high free
8 October 2007 fatty acids (FFAs) depending upon the moisture content in the seed during collection as
Accepted 15 October 2007 well as oil expression. The present study deals with production of biodiesel from high FFA
Available online 28 November 2007 Karanja oil because the conventional alkali-catalyzed route is not the feasible route. This
paper discusses the mechanism of a dual process adopted for the production of biodiesel
from Karanja oil containing FFA up to 20%. The first step is acid-catalyzed esterification by
Karanja oil
using 0.5% H2SO4, alcohol 6:1 molar ratio with respect to the high FFA Karanja oil to produce
methyl ester by lowering the acid value, and the next step is alkali-catalyzed
transesterification. The yield of biodiesel from high FFA Karanja oil by dual step process
has been observed to be 96.6–97%.
Methyl esters
& 2007 Elsevier Ltd. All rights reserved.

1. Introduction of soap with alkaline catalyst. In the present set of experi-
ments, the alternative route of using acid catalyst was
adopted for biodiesel production from Karanja oil [7–9].
In consideration of its production potential and emission
Typically Karanja oil, collected for the present investigation,
characteristics, biodiesel derived from locally available non-
was observed to contain 3.2% of free fatty acid (FFA). Oleic
edible oils is being considered as a substitute to diesel fuel in
acid was added in measured quantity to the Karanja oil with a
India. Production of biodiesel from non-edible oil seeds and
view to increase the level of FFA in the oil. It is relevant to
its utilization in diesel engine is being actively pursed in
emphasize here that oleic acid happens to be the major
Engine and Un-conventional Fuel Laboratory at Indian
constituent of Karanja oil. Oleic acid was added to Karanja oil
Institute of Technology Delhi [1–5].
in desired proportion so as to increase the high FFA content of
Karanja oil is one of the potential oils with yearly
the Karanja oil, 20%, 15% and 5%. Such steps were adopted to
production of 200 t (metric ton), out of which 6% is being
evaluate the effect of FFA level on the production of biodiesel.
presently utilized [6]. The main production area for the
Karanja oil is in the village level and villagers use this oil in
some of their daily activities. This paper highlights the efforts
made to develop biodiesel from Karanja oil, which is available 2. Materials and methods
in rural India. Our experiment in the lab closely agrees with
the reported literature that the presence of high FFA makes In context of the present series of tests, the high FFA
transesterification reaction difficult because of the formation Karanja oil was first converted to esters in a pretreatment

Corresponding author. Tel.: +91 11 2659 1260; fax: +91 11 2658 1121.
E-mail addresses:, (L.M. Das).
0961-9534/$ - see front matter & 2007 Elsevier Ltd. All rights reserved.

The fuel properties of Karanja methyl esters were determined as per the ASTM (D6751) 20 standards.50 Oleic acid 51.2. Esterification was continued till the transesterification reaction acid value was lowered and remained constant.65 5 Srearic acid 7. Pretreatment of high FFA Karanja oil with acid- to 65 1C and the mixture of methanol and KOH was catalyzed esterification added to the oil. and it was again passed 45 over anhydrous Na2SO4. The oil layer was separated from the mixture 3.2. The fatty acid methyl esters composition is given in Table 1. Purification and characterization of biodiesel FFA (%) After the reaction was complete. Similarly. the biodiesel was washed alkali-catalyzed transesterification. catalyst and traces of glycerol. The fuel properties of the 40 Karanja biodiesel were compared with the ASTM D6751 35 Acid Value (mgKOH/g) specifications. . A Spheri-5 C-18 column (PerkinElmer Brown.59 0 Lilonic acid 16. that need to be removed before alkali-catalyzed transe- sterification. 1. Results and discussion The reaction was conducted at 65 1C with MeOH/oil at a molar ratio of 6:1 and an acid catalyst concentration 3. It has been observed that the yield of terification. which is the optimum condition for ment is shown in Fig. pretreatment of oil containing 20% FFA.970. Subse- quently. The washed ester layer was dried at 70 1C under the required vacuum to remove the moisture and methanol. ARTICLE IN PRESS BIOMASS AND BIOENERGY 32 (2008) 354 – 357 355 process with methanol using acid catalyst (H2SO4). A Bronsted acid such as H2SO4 is used for methyl esterification of FFA [7]. The sample injection was 20 ml and comparing their respective standards 40 made peak identification.1. Perkin Elmer Series 200 equipped with a refractive index detector (Shodex RI 71).3% to 5. Analysis of biodiesel Ester content of Karanja methyl esters was determined 100 using high-performance liquid chromatography.3%. Subsequently. The decrease in the yield of methyl esters with different levels treated oil before the second step alkaline-catalyzed transes.6 mm with 5 mm particle size) with 1 ml min 1 flow rate of methanol was used as a carrier Ester (%) 60 solvent with the column kept at 40 1C. At the first step. 2.1. The reaction was carried out with MeOH/ The acid-catalyzed pretreatment of high FFA Karanja oil at a molar ratio of 6:1 and catalyst concentration of oil results in the value during acid-catalyzed pretreat- 1% w/w of oil at 65 1C.64 0 15 30 45 60 75 90 105 120 1 Time (Min) Free fatty acid (mg KOH g ) 5–20 Fig.5 mgKOH/g 25 20 mgKOH/g 40 mgKOH/g Table 1 – Fatty acid composition of Karanja oil 20 9.9 to 3. Effect of FFA on single-step alkali-catalyzed of 0. the alcohol layer was removed from the pre. with hot distilled water to remove the excess methanol. As evident in the graph during Karanja oil [10]. 1 – Effect of FFA on the yield of methyl ester during were separated.3 mg KOH/gin 1 h. Dual step process and passed over anhydrous Na2SO4 before alkali-catalyzed transesterification. biodiesel and glycerol Fig. 2 – Decrease in acid value with time in minutes.1. 2. the acid value decreases from 41. 30 6. 3.9 mgKOH/g 15 Fatty acids (Wt %) 10 Palmitic acid 11. 80 lee Column) (220  4. of FFA is shown in Fig.5% w/w of oil. oil was preheated 3. 0 0 1 2 3 4 5 6 7 2.2. methyl esters decreases from 97% to 6% by increasing the FFA The pretreated oil contains water and acid catalyst content oil from 0.

0015/. which is well within the limits of ASTM The tests conducted proved extremely useful as the pretreat. % vol. Experimental results show that the yield of methyl ester ranged between 96. 3 closely indicates that Karanja oil with FFA upto 20% is also capable of producing the appropriate quality of biodiesel. transesterification was very specification.020 ASTM D6584 102 ppm Total glycerin. Conclusion having 20%. Thus. However. The acid value of the biodiesel was found the acidity due to H2SO4 and the remaining part acted as to be 0.020 ASTM D874 0. Hence.viscosity at 40 1C (cSt) 1. when produced from oil 4.05 ASTM D5453 15 ppm Cetane number 47 ASTM D613 57.80 ASTM D974 0.240 ASTM D6584 1867 ppm Phosphorous content. 1C 4130 ASTM D93 174 Water and sediments. 3 – Effect of FFA on the yield of methyl ester on dual step ‘‘an experimental evaluation of Karanja based biodiesel as a process.470. 40 20 Acknowledgement 0 The authors wish to express their gratitude to General Motors.001 Sulfur. %mass 0.0 ASTM D445 4.3. because of the oxygen value to an extent. max 0. The conventional alkali-catalyzed route of biodiesel production does not work out effectively with high FFA 80 feedstock such as Karanja oil. expelling and storage condition. ARTICLE IN PRESS 356 BIOMASS AND BIOENERGY 32 (2008) 354 – 357 the acid value decreases up to 3. the dual-step process Yield of ester (%) of transesterification using acid-catalyzed and followed by 60 base-catalyzed reaction proves effective in producing the appropriate quality of biodiesel as per the ASTM specification.6% and 97%. This shows that the acid-catalyzed esterification results in significant reduction of the FFA in After successful completion of the series of reaction results in the oil. higher than that of the conventional diesel. which is suitable for alkali-catalyzed content.001 ASTM D4951 o10 ppm Distillation temperature 360 max ASTM D1160 356 . Alkali-catalyzed transesterification reaction with the in the table. supplementary diesel fuel’’. Fig. the viscosity of Karanja-based biodiesel is found pretreated acid-catalyzed Karanja oil to be 4. %mass ma 0. max 0. As evident 3. Its calorific value was found ment of high FFA Karanja oil resulted in the reduction of acid to be lower than that of the diesel. 15% and 5% FFA contents. All other properties like total glycerin and free effectively carried out.005 Kin. which is transesterification. Table 2 – Fuel quality of Karanja biodiesel formed by dual step process Properties Limits Test methods Biodiesel quality Flash point. 0 5 10 15 20 USA. as shown in Table 2.6 Acid value. % mass.23 mg KOH g 1. and contamination of oil/oilseed with 100 moisture. the production of KOME (Karanja Oil Methyl Ester). which resulted in the desired products. % mass. %mass 0. glycerin are also in the range prescribed in the ASTM 6751 biodiesel and glycerol layer. mg/KOH 1 g 1 0.3 mg KOH/g for the oil 3. specification of biodiesel. all the phisico-chemical properties were experimentally evaluated as per the ASTM specification.33 cSt.2. The Indian non-edible oils are often contaminated with FFAs. which is within the limit of ASTM transesterification catalyst.33 Sulfated ash.050 ASTM D2709 0. Fuel properties of Karanja biodiesel containing 5–10% FFA. for the financial support in carrying these tests in IIT FFA (%) Delhi as part of the GM-sponsored on going project entitled Fig.2.23 Free glycerin. The flashpoint of Karanja biodiesel is 174 1C.9–6. storing Then the conventional alkali-catalyzed transesterification biodiesel and biodiesel diesel blend are safe as compared to of pretreated oil was used in the reaction to compensate for storing diesel alone. max 0. depending on the process of oilseed collection. specifications.

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