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Biomass and Bioenergy 28 (2005) 601605 www.elsevier.com/locate/biombioe

Biodiesel production from mahua (Madhuca indica) oil having high free fatty acids
Shashikant Vilas Ghadge, Hifjur Raheman
Agricultural & Food Engineering Department, Indian Institute of Technology, Kharagpur, India Received 23 August 2004; received in revised form 10 November 2004; accepted 11 November 2004 Available online 2 March 2005

Abstract A technique to produce biodiesel from mahua oil (Madhuca indica) having high free fatty acids (19% FFA) has been developed. The high FFA level of mahua oil was reduced to less than 1% by a two-step pretreatment process. Each step was carried out with 0.300.35 v/v methanol-to-oil ratio in the presence of 1% v/v H2SO4 as an acid catalyst in 1-hour reaction at 601C. After the reaction, the mixture was allowed to settle for an hour and methanolwater mixture that separated at the top was removed. The second step product at the bottom was transesteried using 0.25 v/v methanol and 0.7% w/v KOH as alkaline catalyst to produce biodiesel. The fuel properties of mahua biodiesel were found to be comparable to those of diesel and conforming to both the American and European standards. r 2005 Elsevier Ltd. All rights reserved.
Keywords: Mahua oil; Madhuca indica; Biodiesel; Free fatty acids; Pretreatment

1. Introduction Recently, biodiesel has been receiving increasing attention due to its less polluting nature and because it is a renewable energy resource as against the conventional diesel, which is a fossil fuel leading to a potential exhaustion. Mostly, biodiesel is prepared from oils like soybean, rapeseed, sunower, safower, etc. throughout the world [1]. These oils are essentially edible in nature. Few
Corresponding author. Tel.: +91 3222 283160; fax: +91 3222 282244. E-mail address: hifjur@agfe.iitkgp.ac.in (H. Raheman).

attempts have been made for producing biodiesel with non-edible oils like karanja and jatropha, especially in India [2]. However, there remain a number of other tree based oilseeds like sal, neem, undi and mahua with an estimated annual production potential of more than 20 Mt, of which mahua contributes 181 kt [2]. These oils have great potential to make biodiesel for supplementing other conventional sources. There are at least four ways in which oils and fats can be converted into biodiesel, namely, transesterication, blending, micro-emulsions and pyrolysistransesterication being the most commonly used method [3,4]. Transesterication refers

0961-9534/$ - see front matter r 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.biombioe.2004.11.009

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to a catalyzed (KOH/NaOH) chemical reaction involving oil/fat (triglyceride) and an alcohol (methanol/ethanol) to yield fatty acid alkyl esters (i.e., biodiesel) and glycerol. The main factors affecting transesterication are the amount of alcohol and catalyst; reaction temperature, pressure and time; the contents of free fatty acid (FFAs) and water in oils. Conversion is complicated if oil contains large amounts of FFA (41% w/w) that will form soap with alkaline catalyst. The soap can prevent separation of the biodiesel from the glycerin fraction [5]. Few researchers have worked with feedstocks having higher FFA levels using alternative processes [6,7]. Canakci and Gerpen [6] used a two-step pretreatment to reduce the FFAs of yellow grease from 12% and brown grease from 33% to less than 1%, the transesterication reaction was completed with an alkaline catalyst to produce biodiesel. Crude mahua oil generally contains about 20% FFAs and a procedure for converting this mahua oil to biodiesel is very much required. This paper discusses the ndings of experiments carried out to optimize the pretreatment process for reducing the FFA content of mahua oil below 1% for maximum biodiesel production.

initial acid value of 38 mg KOH/g corresponding to a FFA level of 19%, which is far above the 1% limit for satisfactory transesterication reaction using alkaline catalyst. Therefore, FFAs were rst converted to esters in a two-step pretreatment process using an acid catalyst (H2SO4 1% v/v) to reduce the acid value of mahua oil below 2 mg KOH/g. Experiments were conducted in a laboratory-scale setup which consisted of 500 cc glass asks with air tight caps that retained any vaporized methanol to the reacting mixture. The asks were kept in a water bath maintained at 60 1C, just below the boiling point of methanol. The mixture was stirred at the same rate for all runs by manually shaking the asks at every 5-min interval. The progress of the reaction was monitored by measuring the acid value. 2.1. Pretreatment The pretreatment process comprised of two steps. In each step, different methanol-to-oil ratios (0.15, 0.20, 0.25, 0.30, 0.35 and 0.40) and reaction times (0.5, 1.0, 1.5, 2.0 h) were used to investigate their inuence on the acid value of crude mahua oil. After the reaction, the mixture was allowed to settle for 1 h and the methanolwater fraction that separated at the top was removed in a separating funnel. The acid value of the product separated at the bottom was determined. The product having acid value below 5 mg KOH/g by using lowest quantity of methanol in minimum reaction time was used as the raw material for the second step. Again the effect of methanol-to-oil ratio and reaction time on reduction of acid value of this raw material was studied. The nal product having acid value less than 2 mg KOH/g using lowest

2. Materials and methods Mahua oil is obtained from the kernel of mahua tree (Madhuca indica), which is a medium to large tree found in most parts of India. The unrened but ltered crude mahua oil is greenish yellow in colour. Fatty acid prole of mahua oil is given in Table 1. Its FFA content was determined by a standard titrimetry method [8]. This oil had an
Table 1 Fatty acid prole of mahua oil Fatty acid Palmitic Stearic Arachidic Oleic Linoleic
a

Systemic name Hexadecanoic Octadecanoic Eicosanoic cis-9-Octadecenoic cis-9,cis-12-Octadecadienoic

Formula C16H32O2 C18H36O2 C20H40O2 C18H34O2 C18H32O2

Structurea 16:0 18:0 20:0 18:1 18:2

wt% 16.028.2 20.025.1 0.03.3 41.051.0 8.913.7

Carbons in the chain: double bonds.

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methanol amount and reaction time in the second step was used for the main transesterication reaction.
Acid value, mg KOH/g

25
0.5 h

20

1.0 h 1.5 h 2.0 h

2.2. Transesterication The transesterication reaction was carried out with 0.25 v/v methanol (6:1 molar ratio) and 0.7% w/v KOH as an alkaline catalyst. The KOH amount was arrived at based on 0.5% for catalyst plus the amount needed to neutralize the unreacted acids (i.e. 2 mg KOH/g) in the second stage product. The reaction was carried out at 60 1C for half an hour. The mixture was allowed to settle overnight before removing the glycerol layer from the bottom in a separating funnel to get the ester layer on the top, separated as biodiesel. The fuel properties namely, density at 15 1C, kinematic viscosity at 40 1C, ash point, pour point, water content, ash content, carbon residue, acid value and caloric value of mahua oil, mahua biodiesel and conventional diesel were determined as per the standards prescribed by ASTM for comparison with the latest American and European standards [8,9].

15

10

0 0.10

0.15

0.20 0.25 0.30 0.35 Methanol-to-oil ratio, v/v

0.40

0.45

Fig. 1. Effect of methanol quantity and reaction time on reduction of acid value of mahua oil during the rst step pretreatment for biodiesel production. Initial acid value was 38 mg KOH g1 of oil.

4.0
0.5 h

3.5 Acid value, mg KOH/g 3.0 2.5 2.0 1.5 1.0 0.10

1.0 h 1.5 h 2.0 h

3. Results and discussion 3.1. Effect of methanol amount and reaction time on acid value The changes in the acid value of the mixture on the rst and second step pretreatment are shown in Figs. 1 and 2, respectively. From these gures, it can be seen that the rate of reaction was greatly inuenced by both the quantity of methanol and reaction time. The reaction progressed rapidly during the rst 1 h showing over 50% reduction in acid values at low-methanol and over 80% for high-methanol ratios. After 1 h, there was no signicant reduction in the acid value. This might be due to the effect of water produced during the esterication of FFAs, which prevented further reaction. With 0.20 v/v methanol-to-oil ratio, acid value could not go below 10 mg KOH/g even after 2-h reaction during the rst stage. It was reported that to get FFA below 2 mg KOH/g after the

0.15

0.20 0.25 0.30 0.35 Methanol-to-oil ratio, v/v

0.40

0.45

Fig. 2. Effect of methanol quantity and reaction time on reduction of acid value of mahua oil during the second step pretreatment for biodiesel production. The initial acid value from the rst stage g pretreatment was 4.54 mg KOH g1 of oil.

second pretreatment step, the FFA level after the rst step should be below 5 mg KOH/g [10]. As increasing reaction time was not effective after one hour, therefore the methanol quantity was increased. With the methanol-to-oil ratio increased beyond 0.30, the acid value could be lowered in the desirable range of less than 5 mg KOH/g. The combination of 0.35 v/v methanol-to-oil ratio and 1-h reaction time, which reduced acid value from 38 to 4.84 mg KOH/g, was selected as optimum for the rst pretreatment step.

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Table 2 Fuel properties of Mahua oil, Mahua biodiesel and diesel Property Unit Mahua oil Mahua biodiesel Diesel Biodiesel standards ASTM D 6751-02 Density at 15 1C Viscosity at 40 1C Flash point Pour point Water content Ash content Carbon residue Acid value Caloric value kg/m3 mm2/s 1C 1C % % % Mg KOH/g MJ/kg 960 24.58 232 15 1.6 0.90 3.70 38.0 36 880 3.98 208 6 0.04 0.01 0.20 0.41 37 850 2.60 68 20 0.02 0.01 0.17 0.35 42 1.96.0 4130 o0.03 o0.02 o0.8 DIN EN 14214 860900 3.55.0 4120 o0.05 o0.02 o0.3 o0.50

In the second step relatively less amount of methanol was required for decreasing the acid value to less than 2 mg KOH/g. This was because some of the FFAs were already esteried during the rst step and less amount of water was produced during the reaction. The reaction time showed the same trend as in case of rst step. Methanol-to-oil ratio of 0.30 v/v was found to be the optimum for the second step reaction to reduce the acid value below 2 mg KOH/g in 1-h reaction time. It was observed that high amount of methanol (total 0.65 v/v) is required during both pretreatment steps to bring down the FFA content below 1%. However, this high consumption of methanol can be reduced in a commercial application by recovering part of it by fractional distillation of the water-mix that is separated from the top after each step. Also it is possible to further reduce the methanol consumption by continuous removal of water from the mixture during the reaction. 3.2. Transesterication A test case of alkaline-catalyzed transesterication was run using a pretreated sample that had an acid value of 1.62 mg KOH/g. Following this process, an yield of 98% biodiesel was obtained from mahua oil. The fuel properties of mahua biodiesel along with crude mahua oil and diesel are summarized in Table 2. It can be seen that mahua

biodiesel had comparable fuel properties with those of diesel and were within the limits prescribed in the latest American and European standards for biodiesel.

4. Conclusions The high FFA (19%) level of crude mahua oil can be reduced to less than 1% in a 2-step pretreatment process of esterication using acidcatalyzed (1% v/v H2SO4) reaction with methanol (0.300.35 v/v) at 60 1C temperature and 1-h reaction time. After each step, a settling time of minimum 1 h is required for removal of methanolwater mixture. The second step product having acid value less than 2 mg KOH/g is used for the nal alkalicatalyzed (0.7% w/v KOH) transesterication reaction with methanol (0.25 v/v) to produce biodiesel. This process gives an yield of 98% mahua biodiesel, which has comparable fuel properties with that of diesel and are within the limits prescribed by the American and European standards for biodiesel.

References
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