Bioresource Technology 97 (2006) 379384

Process optimization for biodiesel production from mahua (Madhuca indica) oil using response surface methodology
Shashikant Vilas Ghadge, Hifjur Raheman
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Agricultural & Food Engineering Department, Indian Institute of Technology, Kharagpur 721 302, India Received 16 November 2004; received in revised form 2 March 2005; accepted 20 March 2005 Available online 23 May 2005

Abstract A central composite rotatable design was used to study the eect of methanol quantity, acid concentration and reaction time on the reduction of free fatty acids content of mahua oil during its pretreatment for making biodiesel. All the three variables signicantly aected the acid value of the product, methanol being the most eective followed by reaction time and acid catalyst concentration. Using response surface methodology, a quadratic polynomial equation was obtained for acid value by multiple regression analysis. Verication experiments conrmed the validity of the predicted model. The optimum combinations for reducing the acid level of mahua oil to less than 1% after pretreatment was 0.32 v/v methanol-to-oil ratio, 1.24% v/v H2SO4 catalyst and 1.26 h reaction time at 60 C. After the pretreatment of mahua oil, transesterication reaction was carried out with 0.25 v/v methanol-to-oil ratio (6:1 molar ratio) and 0.7% w/v KOH as an alkaline catalyst to produce biodiesel. The fuel properties of mahua biodiesel so obtained complied the requirements of both the American and European standards for biodiesel. 2005 Elsevier Ltd. All rights reserved.
Keywords: Biodiesel; CCRD; FFA; Madhuca indica; Mahua; Optimization; Pretreatment; RSM

1. Introduction There has been renewed interest in the use of vegetable oils for making biodiesel due to its less polluting and renewable nature as against the conventional diesel, which is a fossil fuel leading to a potential exhaustion. The focus has been mainly on oils like soybean, rapeseed, sunower and saower (Lang et al., 2001), which are essentially edible in nature. Few attempts have been made for producing biodiesel from non-edible sources like used frying oil, greases, tallow and lard (Alcantara et al., 2000; Canakci and Gerpen, 2001; Dorado et al., 2002; Mittelbach et al., 1992). In India, with abundance of forest resources, there are a number of other non-edible tree borne oilseeds with an estimated annual producCorresponding author. Tel.: +91 3222 283160; fax: +91 3222 282244. E-mail address: hifjur@agfe.iitkgp.ernet.in (H. Raheman). 0960-8524/$ - see front matter 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.biortech.2005.03.014
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tion of more than 20 million tonnes, which have great potential for making biodiesel to supplement other conventional sources (Kaul et al., 2003). Among these, Karanja (Pongamia glabra) and Jatropha (Jatropha curcas) have been successfully proved for their potential as biodiesel (Pramanik, 2003; Raheman and Phadatare, 2004; Senthil Kumar et al., 2003). Mahua (Madhuca indica) is one such non-edible tree based seed oil, which has an estimated annual production potential of 181 thousand metric tonnes in India (Kaul et al., 2003). 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 (Ma and Hanna, 1999; Srivastava and Prasad, 2000). Transesterication refers 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

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aecting transesterication are the amount of alcohol and catalyst; reaction temperature, pressure and time; the contents of free fatty acids (FFA) and water in oils. Conversion is complicated if oil contains higher amounts of FFA (>1% w/w) that will form soap with alkaline catalyst. The soap can prevent separation of the biodiesel from the glycerin fraction (Demirbas, 2003). Crude mahua oil contains about 20% FFAs, which is far beyond the 1% level that can be converted to biodiesel using an alkaline catalyst. Hence, a procedure for converting high FFA mahua oil to biodiesel is required. Few researchers have worked with feedstocks having higher FFA levels using alternative processes (Canakci and Gerpen, 2001; Dorado et al., 2002). They used pretreatment step to reduce the free fatty acids of these feedstocks to less than 1% before transesterication reaction was completed with an alkaline catalyst to produce biodiesel. 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. The work focuses on the reaction parameters that aect conversion of FFAs from crude mahua oil in a simple esterication reaction with methanol using acid catalyst. The main objective was to develop an approach that would enable us to better understand the relationships between the variables (methanol-to-oil ratio, catalyst concentration and reaction time) and the response (acid value after pretreatment); and to obtain the optimum conditions for biodiesel production using central composite rotatable design (CCRD) and response surface methodology (RSM). The CCRD has the advantage to predict responses based on few sets of experimental data in which all factors are varied within a chosen range.

a laboratory-scale setup, which consisted of 500 cc glass asks with airtight caps that retained any vaporized methanol to the reacting mixture. The asks were kept in a water bath maintained at 60 C, 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. 2.1. Pretreatment Crude unrened mahua oil was greenish yellow in colour. The fatty acid prole of mahua oil is given in Table 1. Its free fatty acid (FFA) content was determined by a standard titrimetry method (ASTM, 2003). This oil had an initial acid value of 34 1 mg KOH/g corresponding to a FFA level of 17 0.5%, which is far above the 1% limit for satisfactory transesterication reaction using alkaline catalyst. Therefore, FFAs were rst converted to esters in a pretreatment process with methanol using an acid catalyst (H2SO4). After the reaction, the mixture was allowed to settle for one hour and the methanol water 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 less than 2 0.25 mg KOH/g was used for the main transesterication reaction. 2.2. Transesterication The transesterication reaction was carried out with 0.25 v/v methanol-to-oil ratio (i.e., 6:1 molar) using 0.7% w/v KOH as an alkaline catalyst. The amount of KOH (7 g per litre of pretreated mahua oil) was arrived at based on the amount needed to neutralize the unreacted acids (i.e., 2 mg KOH/g) in the second stage product plus 0.5% for catalyst. The reaction was carried out at 60 C for half an hour. The reaction product 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. 2.3. Fuel properties The fuel properties namely, density at 15 C, kinematic viscosity at 40 C, ash point, pour point, water

2. Methods Mahua oil was obtained from local oil industry near IIT Kharagpur, West Bengal, India. All chemicals including methanol (99.5%) and sulfuric acid (99% pure) were of analytical reagent (AR) grade. The KOH in pellet form was used as a base catalyst for transesterication reaction. Experiments were conducted in
Table 1 Fatty acid prole of mahua oil Fatty acid Palmitic Stearic Arachidic Oleic Linoleic 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

Source: Srivastava and Prasad (2000). a Carbons in the chain:double bonds.

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content, ash content, carbon residue, acid value and caloric value of mahua oil, mahua biodiesel and conventional diesel were determined as per the prescribed methods and compared with the latest American and European standards for biodiesel (ASTM, 2003; DIN EN 14214, 2003). 2.4. Experimental design A ve-level-three-factor CCRD was employed in this study, requiring 23 experiments (Cochran and Cox, 1992). Methanol-to-oil ratio (M), catalyst concentration (C) and reaction time (T) were the independent variables selected to optimize the reduction of acid value (AV) of crude mahua oil after pretreatment. The coded and uncoded levels of the independent variables are given in Table 2. Two replications were carried out for all design points except the center point (0, 0, 0) and the experiments were carried out in randomized order. 2.5. Statistical analysis The experimental data obtained by following the above procedure were analyzed by the response surface regression procedure using the following second-order polynomial equation: y b0
3 X i1

two variables. Conrmatory experiments were carried out to validate the equation, using combinations of independent variables which were not part of the original experimental design but within the experimental region.

3. Results and discussion 3.1. Pretreatment Experimental values obtained for acid value responses at the design points are given in Table 3. Multiple regression coecients indicated in Table 4 were obtained by employing a least square technique to predict quadratic polynomial model for the acid value. Analysis of these parameters with the t-test indicated that except C, other linear terms and all quadratic terms had signicant eect on the reduction of acid value. However, the interaction terms were found to be nonsignicant. The model was tested for adequacy by analysis of variance. The regression model for data was found to be highly signicant with a coecient of determination as 0.842. Using the coecients determined, the predicted model for acid value is:

bi xi

3 X i1

bii x2 i

3 XX i<j1

bij xi xj

Table 3 Central composite rotatable design arrangement and responsesa Design points Coded independent variable levelsb Methanolto-oil ratio (v/v) M 1 1 1 1 1 1 1 1 1.68 1.68 0 0 0 0 0 0 0 0 0 0 0 0 0 H2SO4 concentration (% v/v) C 1 1 1 1 1 1 1 1 0 0 1.68 1.68 0 0 0 0 0 0 0 0 0 0 0 Reaction time (h) T 1 1 1 1 1 1 1 1 0 0 0 0 1.68 1.68 0 0 0 0 0 0 0 0 0 Acid valuec (mg KOH/g) AV

where y is the response (acid value, mg KOH/g); xi and xj are the uncoded independent variables and b0, bi, bii and bij are intercept, linear, quadratic and interaction constant coecients respectively. SPSS package was used for regression analysis and analysis of variance (ANOVA). Response surfaces and contour plots were developed using the tted quadratic polynomial equation obtained from regression analysis, holding one of the independent variables at a constant value corresponding to the stationary point and changing the other

Table 2 Independent variables and levels used for central composite rotatable design Variables Symbols Levelsa 1.68 (a) Methanol-to-oil ratio (v/v) H2SO4 concentration (% v/v) Reaction time (h)
a

1 0.25 1.00

0 0.30 1.50

1 0.35 2.00

1.68 (a) 0.38 2.34

M C

0.22 0.66

0.16

0.50

1.00

1.50

1.84

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23
a b c

11.40 5.74 17.10 13.40 5.88 3.10 7.07 6.37 8.39 3.20 3.50 5.47 8.70 2.10 2.71 2.92 3.11 2.84 2.61 2.72 2.99 2.81 2.63

Transformation of variable levels from coded (X) to uncoded could be obtained as: M = 0.30 + 0.05X, C = 1.5 + 0.5X and T = 1 + 0.5X.

Randomized. Refer Table 1 for uncoded levels of independent variables. Average of duplicates except for design points 1523.

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Table 4 Regression coecients of predicted quadratic polynomial model Terms Linear b0 b1 b2 b3 Quadratic b11 b22 b33 Interaction b12 b13 b23 b123 R2 F ratio P value
a * **

Coecientsa 89.773** 434.400** 1.103 28.304* 703.340** 5.177** 6.474** 44.500 2.020 29.400 0.842 7.709 0.001

Standard error 25.193 134.547 11.101 10.608 205.845 2.058 2.058 28.961 2.896 28.961

1.5

Reaction Time (h)

1.0

0.5

(a)

1.0 1.5 2.0 Catalyst Concentration (% v/v)

Reaction Time (h)

Coecients refer to the model given in Section 2. Signicant at 0.05 level. Signicant at 0.01 level.

1.5

1.0

AV 89.773 434.400M 1.103C 28.304T 703.340M 2 5.177C 2 6.474T 2 44.500MC 2.020CT 29.400MT 2

0.5

From Table 4 and Eq. (2), it could be concluded that the linear and quadratic eects of M and T were the primary determining factors of the responses followed by quadratic eect of C. However, C had no signicant linear eect. The relationship between independent and dependent variables of the developed model is shown in Fig. 1ac in the form of contour plots. All Eigen values obtained for the analysis were positive indicating that the stationary point for the response was minimum. The critical values of three variables were found to be 0.32 v/v methanol-to-oil ratio, 1.24% v/v catalyst concentration and 1.26 h reaction time locating the stationary point in the experimental region. Verication experiments showed reasonably close value of 1.64 0.15 mg KOH/g to the predicted value for the stationary point (1.35 mg KOH/g) and thus conrmed the adequacy of the predicted model. The responses corresponding to the second-order model indicated that, for low catalyst concentration, FFA conversion increases with increasing methanol-tooil ratio (Fig. 1a) and reaction time (Fig. 1c). Maximum conversions were, therefore, obtained for large methanol amounts, due to the fact that it was the most signicant factor with negative eect. However, at higher catalyst concentrations, there seemed to be less eect of increasing methanol amount or reaction time. This could be due to the positive coecients of catalyst-time and methanol-time interactions.

(b)

0.25

0.30 0.35 Methanol-to-oil Ratio (v/v)

Catalyst Concentration (% v/v)

2.0

1.5

1.0

(c)

0.25

0.30 0.35 Methanol-to-oil Ratio (v/v)

Fig. 1. Contour plots of acid value (mg KOH/g) predicted from the quadratic model. (a) 0.32% v/v methanol-to-oil ratio, (b) 1.24% v/v catalyst concentration and (c) 1.26 h reaction time.

At low catalyst concentrations there was a moderate increase in conversion with reaction time, since the time eect was negative and greater than that of catalyst con-

S.V. Ghadge, H. Raheman / Bioresource Technology 97 (2006) 379384 Table 5 Fuel properties of mahua oil, mahua biodiesel and diesel Property Unit Mahua oil Mahua biodiesel Jatrophaa biodiesel Karanjab biodiesel Diesel Biodiesel standards ASTM D 6751-02 850 2.60 68 20 0.02 0.01 0.17 0.35 42 1.96.0 >130 <0.03 <0.02 <0.8

383

DIN EN 14214 860900 3.55.0 >120 <0.05 <0.02 <0.3 <0.50

Density at 15 C Viscosity at 40 C Flash point Pour point Water content Ash content Carbon residue Acid value Caloric value

kg/m3 mm2/s C C % % % 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

880 4.84 192 6 0.05 0.014 0.025 0.24 37.2

876 9.6 187 7 0.05 0.01 0.24 0.31 36.12

Source: a Becker and Francis (2002). b Raheman and Phadatare (2004).

centration. For higher catalyst concentrations the increase of conversion with time became smaller (as a result of the positive interaction). Therefore, the operating conditions of large catalyst concentration and reaction time should be avoided. It was also observed that increasing reaction time beyond one hour does not have much eect on reducing the acid value as desired (Fig. 1b and c). This might be due to the eect of water produced during the esterication of free fatty acids, which prevented further reaction. As more and more FFAs were esteried by methanol, the reaction might have produced more water with increasing time. It was observed that high amount of methanol (total 0.32 v/v methanol-to-oil) was required during the pretreatment step to bring down the FFA content below 1%. However, in a commercial application, this could be reduced by recovering part of it by fractional distillation of the water-mix, which would be separated from the top after pretreatment. Also it could be possible to further reduce the methanol consumption by continuously removing the 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 1.64 mg KOH/g. A 6:1 molar ratio of methanol (0.25 v/v methanol-to-oil) and an alkaline catalyst (0.7% w/v KOH) were used for the reaction. Following this process, an yield of 98% biodiesel was obtained form mahua oil. The fuel properties of mahua biodiesel obtained following the above-mentioned procedure are summarized in Table 5 along with crude mahua oil, Karanja and Jatropha biodiesel and diesel. It can be seen that the fuel properties of mahua biodiesel are similar to those of Karanja and Jatropha biodiesel except the viscosity of Karanja biodiesel. Moreover, mahua biodiesel had comparable fuel properties with those of diesel and conforming to the latest American and European standards for biodiesel.

4. Conclusions The high FFA (17%) level of crude mahua oil could be reduced to less than 1% by its pretreatment with methanol (0.32 v/v) using H2SO4 as catalyst (1.24% w/v) in 1.26 h reaction at 60 C temperature. A secondorder model was obtained to predict acid value as a function of methanol-to-oil ratio, catalyst concentration and reaction time. The model was found to describe adequately the experimental range studied. After pretreatment step, settling time of minimum one hour was required for removal of methanolwater mixture. The product was used for the nal alkali-catalyzed (0.7% w/v KOH) transesterication reaction with methanol (0.25 v/v) to produce biodiesel. This process gave an yield of 98% mahua biodiesel having properties satisfying both American and European standards for biodiesel.

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