VOL. 3, NO.

3, JUNE 2008

ISSN 1819-6608

ARPN Journal of Engineering and Applied Sciences

2006-2008 Asian Research Publishing Network (ARPN). All rights reserved.

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EXTRACTION OF NEEM OIL (Azadirachta indica A. Juss) USING N-HEXANE AND ETHANOL: STUDIES OF OIL QUALITY, KINETIC AND THERMODYNAMIC
Maria Yuliana Liauw, F. A. Natan, P. Widiyanti, D. Ikasari, N. Indraswati and F. E. Soetaredjo
Department of Chemical Engineering, Widya Mandala Catholic University, Kalijudan, Surabaya, Indonesia E-Mail: [email protected]

ABSTRACT In this experiment, Neem oil extraction from Neem seeds (Azadirachta indica A. Juss) with n-hexane and ethanol are presented. Effects of particle size, temperature and type of solvent on the extraction kinetic and thermodynamic parameters were studied. Results showed that the maximum oil yields were 41.11% for ethanol and 44.29% for n-hexane at 50oC, and 0.425-0.71 mm particle size. Based on psycho-chemical characteristics analysis showed that increasing temperature decreased iodine value but caused saponification, acid, and peroxide value became higher, which means higher extraction temperature result on higher oil yield but lower oil quality. The kinetic of neem oil extraction was derived from mass transfer rate equation. It also found that H is positive, S is positive, and G is negative indicating that this process are endotermic, irreversible, and spontaneous.
Keywords: oil, neem, extraction, kinetic, thermodynamic.

INTRODUCTION Neem (Azadirachta indica A. Juss) is one of the very few trees known in the Indian subcontinent. This tree is belonged to Meliceae family, and grows rapidly in the tropic and semi-tropic climate. It is also observed that this tree could survive in very dry and arid conditions. Neem tree is an evergreen tree, but it may become leafless for a short period in certain conditions [1]. Neem tree also found in Indonesia in several areas such as Bali, Lombok, West Java, East Java (Situbondo, Ngawi), Central Java, and Nusa Tenggara Barat. All parts of Neem plant such as leaves, bark, flower, fruit, seed and root have advantages in medical treatment and industrial products. Its leaves can be used as drug for diabetes, eczema and reduce fever. Barks of Neem can be used to make toothbrush. Neem roots has an ability to heal diseases and against insects [1, 2]. However, this tree is not very popular in Indonesia because it is only used as a canopy tree. Neem seed is a part of Neem tree which has high concentration of oil. Neem oil is widely used as insecticides, lubricant, drugs for variety of diseases such as diabetes and tuberculosis [1-3]. This oil could also prolong leather goods when it is applied on them [1]. There are several methods to obtain Neem oil from the seeds like mechanical pressing, supercritical fluid extraction, and solvent extraction [1]. Mechanical extraction is the most widely used method to extract Neem oil from Neem seed. However, the oil produced with this method usually has a low price, since it turbid and contains a significant amount of water and metals contents. Extraction using supercritical fluid, the oil produced has very high purity; however the operating and investment cost is high. Extraction using solvent has several advantages. It gives higher yield and less turbid oil than mechanical extraction, and relative low operating cost compared with supercritical fluid extraction.

In this study we used solvent extraction to extract the oil from Neem seed. The effects of parameter process such as temperature and particle size were studied and kinetic and thermodynamics model were developed. As the solvents, we used ethanol and hexane. MATERIALS AND METHODS Material preparation Neem seed used in this study were obtained from Bali. This raw material has water content of 7.8% and oil content of 49.58%. Prior to use, the Neem seeds were repeatedly washed to remove dirt and other impurities material, and subsequently dried in oven at 50C until it reached constant moisture content. Then, Neem seeds were ground to get three different particle sizes (0.85-1.40 mm, 0.71-0.85 mm, and 0.425-0.71 mm). Oil extraction Neem seeds were extracted using two solvent (nhexane and ethanol) for 3 hours with ratio Neem seed powder weight to solvent volume of 1:5. In certain time intervals, the samples were taken and centrifuged to separate the solid fraction from solution. Filtrate was heated and evaporated to obtain solvent-free oil. Then the oil was weighed to calculate the concentration of oil in the solution. Extractions were conducted at 5 temperature level (30o, 35o, 40o, 45o and 50oC). RESULTS AND DISCUSSIONS Effect of temperature to quality of oil Oil quality was affected by temperature, hydrolysis, oxidation, lipase enzyme, and another compounds in the oil. The effect of extraction temperature to psychochemical characteristics of Neem oil is shown in Figure-1.

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VOL. 3, NO. 3, JUNE 2008

ISSN 1819-6608

ARPN Journal of Engineering and Applied Sciences

2006-2008 Asian Research Publishing Network (ARPN). All rights reserved.

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140

250

120

100

Saponification Value (mg/g)

25 30 35 40 45 50 55

200

Acid Value (g/g)

80

150

60

100

40

50

20

0 25 30 35 40 45 50 55

Temperature (C)
using n-hexane using ethanol
using n-hexane using ethanol

Temperature (C)

(a)
10
100

(b)

80

Peroxide Value (mg/g)

Iodine Value (g/g)

25 30 35 40 45 50 55

60

40

20

0 25 30 35 40 45 50 55

Temperature (C)
using n-hexane using ethanol
using n-hexane using ethanol

Temperature (C)

(c)

(d)

Figure-1. The effect of Neem oil extraction temperature on (a) acid value; (b) saponification value; (c) peroxide value; and (d) iodine value using n-hexane and ethanol. The quality of Neem oil decreased as the temperature increased. This is shown in Figure-1(a) to (d) where the acid, saponification and peroxide value increase while iodine value decrease. Acid value indicates the amount of free fatty acids presents in an oil. Acid value is good indicator of oil degradation caused by hydrolysis. Figure-1(a) shows that higher extraction temperature increased the acid value because the extraction temperature influenced the hydrolysis of Neem oil [5-6]. Vegetable oil contains lipase enzyme which has an optimum temperature about 35-40o C [7-9]. Lipase enzyme hydrolyzes oil become free fatty acid and glycerol. Saponification value indicates the average molecular weight of triglycerides in the oil [5-6, 10]. Figure-1(b) shows that an increase in temperature, increased the saponification value because higher temperature caused lipid to breakdown therefore reduced the average molecular weight of the oil [5, 10]. Peroxide value is used as an indicator of oil rancidity [5]. Figure1(c) shows that an increase in temperature increased the peroxide value. Increasing the temperature extraction caused the oil to be rancid, thus leading to reduce its oxidative stability. Rancidity is caused by aldehydes, ketones, and oxidation [4, 11]. Iodine value expresses the unsaturation level of the oil [9, 12]. Figure-1(d) shows that higher temperature reduced the iodine value, since higher temperature initiate the breakdown of carbon chain bonding thus leading to form the saturated carbon chain. This results on decrease the iodine value of oil. The type of solvent did not affect on the saponification and iodine value, however it influenced the acid value. It implies that n-hexane as non-polar solvent suitable for free fatty acid extraction compare to ethanol, which is polar solvent, is able to extract bio-active compounds [13]. Extraction kinetics A relevant kinetic data is required to analyze and design an extraction process especially in industrial scale. In these experiments, we used mass transfer kinetic model to represent our experiment data because there is no reaction between the Neem oil with both solvent, n-hexane and ethanol. Neem oil, as an organic material, contains several organic compounds such as nimbin, nimbidin, salannin, etc. Since Neem oil is an organic material, it readily dissolved in organic solvents like n-hexane and ethanol. Here, the mechanism control for extraction of Neem oil in n-hexane and ethanol is mass transfer, and we propose mass transfer kinetic model to represent the yield data of Neem oil extraction.

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VOL. 3, NO. 3, JUNE 2008

ISSN 1819-6608

ARPN Journal of Engineering and Applied Sciences

2006-2008 Asian Research Publishing Network (ARPN). All rights reserved.

www.arpnjournals.com For this model we assumed that the main mechanism which controls the rate of Neem oil extraction is mass transfer of Neem oil from Neem seeds (solid) to bulk liquid n-hexane and ethanol. Mass transfer rate of Neem oil from Neem seed to organic solvents can be written as,
dW A = k . A.(C Ai C A ) dt
50

40

yield (%)

30

20 Time (min) vs Temperature (30C) Time (min) vs Temperature (35C) Time (min) vs Temperature (40C) Time (min) vs Temperature (45C) Time (min) vs Temperature (50C)

(1)

10

Where dWA/dt is the mass transfer rate of neem oil (g/s), CA and CAi are the concentration of neem oil in bulk liquid (organic solvents) at time t (g/L) and at equilibrium (g/L), respectively. Here k is mass transfer coefficient and A is surface area for mass transfer process. Since the extraction was taken in batch process and its volume was kept constant during process, therefore

0 0 50 100 150 200

t (menit)

(b)
50

40

dW A A = k . .(W Ai W A ) dt V dW A = k .a.(W Ai W A ) dt
Where k.a is volumetric mass transfer coefficient. To solve Eq. (3), we used some conditions as follows: At the beginning of extraction process (t = 0), the mass of Neem oil in bulk liquid is zero, WA = 0. At any time t, mass of Neem oil in bulk liquid is WA = WAi. With those conditions, integration of Eq. (3) gives the following result,

Yield (%)

30

(2) (3)
Time (min) vs Temperature (30C) Time (min) vs Temperature (35C) Time (min) vs Temperature (40C) Time (min) vs Temperature (45C) Time (min) vs Temperature (50C)

20

10

0 0 50 100 150 200

t (menit)

(c) Figure-2. Extraction kinetic of Neem seeds powder at particle size (a) 0.85-1.40 mm; (b) 0.71-0.85 mm; (c) 0.425-0.71 mm using n-hexane as solvent.
50

W A = W Ai [1 exp( k .a.t )]
Eq. (4) can be rearrange so it can be written in terms of yield per mass of Neem seed,
% Yield

40

(4)

30

YA = YAi [1 exp( k.a.t )]

Where YA andi YAi are yield of Neem oil in bulk liquid at time t and at equilibrium per mass of Neem seed.

20 Time (min) vs Temperature (30C) Time (min) vs Temperature (35C) Time (min) vs Temperature (40C) Time (min) vs Temperature (45C) Time (min) vs Temperature (50C) 0 50 100 150 200 250

(5)

10

Waktu (menit)

(a)
50

50
40

40
30

yield (%)

20 Time (min) vs Temperature (30C) Time (min) vs Temperature (35C) Time (min) vs Temperature (40C) Time (min) vs Temperature (45C) Time (min) vs Temperature (50C)

% Yield

30

20 Time (min) vs Temperature (30C) Time (min) vs Temperature (35C) Time (min) vs Temperature (40C) Time (min) vs Temperature (45C) Time (min) vs Temperature (50C) 0 50 100 150 200 250

10

10

0 0 50 100 150 200

t (menit)

(a)

Waktu (menit)

(b)

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VOL. 3, NO. 3, JUNE 2008

ISSN 1819-6608

ARPN Journal of Engineering and Applied Sciences

2006-2008 Asian Research Publishing Network (ARPN). All rights reserved.

www.arpnjournals.com

50

40

% Yield

30

20 Time (min) vs Temperature (30C) Time (min) vs Temperature (35C) Time (min) vs Temperature (40C) Time (min) vs Temperature (45C) Time (min) vs Temperature (50C)

10

Figures 2 and 3 shows the experimental kinetic data from extraction of Neem oil in n-hexane and ethanol at various temperatures and the fits of mass transfer kinetic model. In these Figures, the experimental data are represented as bullets and kinetic model as solid lines. In the kinetic model, parameters YAi and k.a were estimated by the nonlinear least square fit from Eq. (5) to experimental data. Parameters from fitting of kinetic model are summarized in Tables 1 and 2.
250

0 0 50 100 150 200

Waktu (menit)

(c) Figure-3. Extraction kinetic of Neem seeds powder at particle size (a) 0.85-1.40 mm; (b) 0.71-0.85 mm; (c) 0.425-0.71 mm using ethanol as solvent. Table-1. Parameters fitting of Neem oil extraction kinetics using n-hexane. T ( C)
o

30 35 40 45 50

YAi fitted 35.8700 37.8300 39.1300 39.9800 41.0400

0.85-1.40 mm YAi experimental 35.8901 37.8522 39.1514 39.9902 41.1429

k.a 0.3587 0.3783 0.3943 0.3998 0.4104

YAi fitted 36.9500 38.5000 40.2100 41.4800 42.2900

0.71-0.85 mm YAi experimental 36.9612 38.5585 40.2264 41.4983 42.3060

k.a 0.3695 0.3850 0.4021 0.4148 0.4228

YAi fitted 38.0100 40.0000 41.6200 42.8800 43.7200

0.425-0.71 mm YAi experimental 38.0266 40.0123 41.6302 42.8911 43.7263

k.a 0.3801 0.4001 0.4162 0.4287 0.4372

Table-2. Parameters fitting of Neem oil extraction kinetics using ethanol. T ( C)

o

30 35 40 45 50

YAi fitted 30.9760 32.8000 34.1317 35.6329 37.2790

0.85-1.40 mm YAi experimental 33.43 34.85 35.63 37.64 39.1733

k.a 0.0594 0.0584 0.0651 0.0774 0.109

YAi fitted 31.4472 33.302 34.574 36.0747 37.7718

0.71-0.85 mm YAi experimental 33.6847 35.3500 35.9883 37.9400 39.7733

k.a 0.0635 0.061 0.0655 0.0776 0.1085

0.425-0.71 mm YAi YAi fitted experimental 32.4377 33.9500 33.7679 34.9842 36.5482 38.3562 35.9500 36.6300 38.5400 41.0823

k.a 0.0675 0.0615 0.0711 0.0777 0.1083

Thermodynamic parameters Thermodynamics parameters ( H , S , and G ) for the extraction of neem oil using n-hexane and ethanol as solvents can be estimated using following equations,
ln K = G 1 H 1 S = + R T R T R

K=

YT m L = Yu m S

Where K is equilibrium constant, YT is yield percent of oil at temperature T, Yu is percent of oil remaining in Neem seed, mL is amount of Neem oil in liquid at equilibrium

temperature T, mS is amount of Neem oil in solid at equilibrium temperature T, R is gas constant, while H , S , and G are enthalpy, entropy, and free energy of extraction, respectively. The values of K and G for extraction of Neem oil using n-hexane and ethanol as solvents were calculated using Eqs. (6) and (7) are given in Tables 3 and 4. The (6)in values of enthalpy and entropy of extraction are given Table-5. The negative values of G indicate that the extraction of Neem oil using n-hexane and ethanol are spontaneous process. The positive value of enthalpy (7) indicates that the process is endothermic and requires energy during process.

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VOL. 3, NO. 3, JUNE 2008

ISSN 1819-6608

ARPN Journal of Engineering and Applied Sciences

2006-2008 Asian Research Publishing Network (ARPN). All rights reserved.

www.arpnjournals.com Table-3. Equilibrium constant of Neem oil extraction using n-hexane and ethanol. Equilibrium constant (K) T (K) 303 308 313 318 323 1/T (1/K) 0.00330033 0.003246753 0.003194888 0.003144654 0.003095975 0.85-1.40 mm n-Hexane 3.3872 4.3930 5.6973 6.9588 8.4149 Ethanol 4.3516 5.5650 6.4991 10.840 20.2028 0.71-0.85 mm n-Hexane 3.1268 3.7434 4.7115 5.6973 6.5535 Ethanol 4.5351 6.1347 7.0235 11.9598 29.7037 0.425-0.71 mm n-Hexane 2.9447 3.7062 4.3930 4.8067 5.5845 Ethanol 4.7401 6.9640 8.1721 14.9827 55.4572

Table-4. Free energy of Neem oil extraction using n-hexane and ethanol.

G (J/mol)
T (K) 303 308 313 318 323 1/T (1/K) 0.00330033 0.003246753 0.003194888 0.003144654 0.003095975 0.85-1.40 mm n-Hexane -2663.0574 -3336.3060 -3714.3888 -3962.3262 -4298.2758 Ethanol -4298.1595 -5158.0664 -5777.2473 -7951.8484 -12855.1204 0.71-0.85 mm n-Hexane -2759.5630 -3232.9716 -3910.6174 -4137.4696 -4723.4840 Ethanol -4425.2737 -5485.8683 -6056.1254 -8437.8957 -13370.9323 0.425-0.71 mm n-Hexane -3252.0303 -3515.1134 -4413.4913 -5054.1845 -5451.8852 Ethanol -4562.6751 -5928.8767 -6627.2622 -9763.0717 -16968.0632

Table-5. Enthalpy and entropy of Neem oil extraction using n-hexane and ethanol at various particle size. Particle size (mm) 0.85-1.40 0.71-0.85 0.425-0.71

H (J/mol)
n-Hexane 37.03 31.02 25.33 Ethanol 115505.1730 86687.0813 75340.2695 REFERENCES n-Hexane 0.13 0.11 0.09

S (J/mol)
Ethanol 392.0458 299.2475 263.7695

CONCLUSIONS The maximum yield obtained from extraction of neem oil research were 44.29% for n-hexane and 41.11% for ethanol at 50C and 0.425-0.71 mm particle size. Based on psycho-chemical characteristics analysis, increasing temperature decreased iodine value but increased saponification, acid, and peroxide value which means increasing temperature increased neem oil yield but decreased neem oil quality. This extraction follows first order kinetic with smaller k .a value as decrease of temperature. It also found that H is positive, S is positive, and G is negative indicating that this process are endotermic, irreversible, and spontaneous. ACKNOWLEDGEMENTS The authors are grateful for the financial support from TPSDP (Technological and Professional Skills Development Sector Project, ADB Loan No. 1792-INO) from Chemical Engineering Department of Widya Mandala Catholic University Surabaya, Indonesia.

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