Applied Energy 87 (2010) 779785

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Okra (Hibiscus esculentus) seed oil for biodiesel production

Farooq Anwar a,*, Umer Rashid a,b, Muhammad Ashraf c, Muhammad Nadeem a
a

Department of Chemistry and Biochemistry, University of Agriculture, Faisalabad 38040, Pakistan Department of Industrial Chemistry, Government College University, Faisalabad 38000, Pakistan c Department of Botany, University of Agriculture, Faisalabad 38040, Pakistan
b

a r t i c l e

i n f o

a b s t r a c t
Biodiesel was derived from okra (Hibiscus esculentus) seed oil by methanol-induced transesterication using an alkali catalyst. Transesterication of the tested okra seed oil under optimum conditions: 7:1 methanol to oil molar ratio, 1.00% (w/w) NaOCH3 catalyst, temperature 65 C and 600 rpm agitation intensity exhibited 96.8% of okra oil methyl esters (OOMEs) yield. The OOMEs/biodiesel produced was analyzed by GC/MS, which showed that it mainly consisted of four fatty acids: linoleic (30.31%), palmitic (30.23%), oleic (29.09%) and stearic (4.93%). A small amount of 2-octyl cyclopropaneoctanoic acid with contribution 1.92% was also established. Fuel properties of OOMEs such as density, kinematic viscosity, cetane number, oxidative stability, lubricity, ash point, cold ow properties, sulfur contents and acid value were comparable with those of ASTM D 6751 and EN 14214, where applicable. It was concluded that okra seed oil is an acceptable feedstock for biodiesel production. 2009 Elsevier Ltd. All rights reserved.

Article history: Received 14 May 2009 Received in revised form 20 September 2009 Accepted 20 September 2009 Available online 17 October 2009 Keywords: Okra seeds Oil extraction Transesterication Biodiesel Gas chromatography/mass spectrometry Fuel properties

1. Introduction The depletion of world petroleum reserves due to rapidly growing energy demands coupled with environmental concerns has prompted the efforts to explore some alternative sources of petroleum-based fuels [1]. In this context, biodiesel has gained considerable ground in public world-over [2]. Currently, biodiesel is mainly prepared from conventionally grown edible oils such as sunower, soybean and palm oils [1,3,4] thus leading to alleviate food versus fuel issue [5]. Exploration of some non-food and newer resources of vegetable oil for biodiesel production is becoming important not only due to appreciably high cost of commonly consumed edible oils but also due to their ever-increasing demand. Several non-edible oils like Jatropha-, Neem-, Karanja-, Tobacco-, and Moringa-seed oils, used frying oil, grease, tallow and lard have been previously investigated for biodiesel production [611]. Okra (Hibiscus esculentus) is widely distributed in the tropical to subtropical regions from Africa to Asia, Southern European and Mediterranean countries, and America [12,13]. In Pakistan, okra is locally known as bhindi. Okra is mainly grown as a vegetable in the plain areas of Pakistan. It grows well under warm climatic conditions (temperature above 26 C) [14]. Total area under okra

cultivation in Pakistan is 2.21 105 hec producing about 2.86 106 tons of green pods [15]. The seeds of mature okra pods, sometimes used for poultry feed are also consumed after roasting and as a coffee substitute. These are considered to be a stomachic stimulant, antispasmodic, and nervine [16]. The okra seeds have been used on a small scale for oil production. Andras et al. [13] reported the okra seed from Greece to be a potential source of oil with concentration varying from 15.9% to 20.7%. The oil mainly consisted of linoleic acid (up to 47.4%). Savello et al. [17] found okra seed oil as one of the rich sources of unsaturated fatty acids. Some other studies also revealed the potential of okra seed as a source of oil and protein for both the temperate regions and the tropics [12,18]. The principal aim of the present investigation was to assess whether or not the okra seed oil could be used as a potential nonconventional feedstock for biodiesel production. As far as we know, okra seed oil has not yet been investigated for biodiesel production. Optimization of key reaction parameters such as catalyst type and its concentration and molar ratio of methanol to oil for the methanolysis of okra seed oil was performed. Furthermore, the fuel properties of methyl esters of okra oil were investigated and compared with biodiesel ASTM and EU specications. 2. Materials and methods 2.1. Materials

* Corresponding author. Fax: +92 41 9200764. E-mail addresses: fqanwar@yahoo.com (F. Anwar), umer.rashid@yahoo.com (U. Rashid). 0306-2619/$ - see front matter 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.apenergy.2009.09.020

The seeds of okra (H. esculentus) were procured from the Ayub Agricultural Research Institute (AARI), Faisalabad, Pakistan.

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n-Hexane, methanol, sodium methoxide, sodium hydroxide, potassium hydroxide, potassium methoxide and anhydrous sodium sulfate were purchased from Merck (Darmstadt, Germany). Pure fatty acid methyl esters used as standards were procured from Sigma Chemical Co. (St. Louis, MO). 2.2. Extraction of oil The seeds (500 g) of each batch of okra were crushed using a coffee grinder. The extraction was done in n-hexane (0.8 L) on a water bath for 6 h, using the Soxhlet extractor. The solvent was distilled off at 45 C using a rotary evaporator. 2.3. Degumming of oil The okra seed oil placed in a beaker was heated at 70 C on a water bath. A calculated amount of hot water was then added into the oil to bring it to a nal volume of 18%. The contents of the beaker were mixed thoroughly with a glass rod. On cooling, the mixture was centrifuged using a refrigerated centrifuge machine (Model CHM-17; Kokusan Denki, Tokyo, Japan) at 3000 rpm for 15 min to separate the oil. The recovered oil was stirred with anhydrous sodium sulfate for 5 min and then subjected to ltration through a lter paper in an oven (EYELA, VOC-300 SD, Tokyo, Japan) at 50 C. 2.4. Experimental conditions for transesterication Experiments were performed to evaluate the effects of methanol/oil ratio and type and concentration of catalyst on transesterication reaction of crude okra seed oil. The reaction time (120 min), reaction temperature (65 C) and agitation intensity (600 rpm) was kept constant throughout the experiment. The molar ratio methanol/oil was varied as 3:1, 4:1, 5:1, 6:1, 7:1, 8:1 and 9:1. The catalysts used were sodium hydroxide (1.0%), potassium hydroxide (1.0%), sodium methoxide (1.0%) and potassium methoxide (1.0%). The concentration of NaOCH3 (the most effective catalyst) found in the present study was varied as 0.00%, 0.50%, 0.75%, 1.00%, 1.25% and 1.50% (w/w of oil). 2.5. Transesterication reaction The transesterication reaction was performed in a lab scale biodiesel reactor consisted of 1 L round-bottomed ask, tted with mechanical stirrer, thermostat, sampling outlet, and condensation systems. In brief, the okra seed oil (500 g) was preheated to 65 C on a hot plate before starting the reaction. For preliminary screening experiments of catalysts, a known amount of freshly prepared methanolic solutions of the catalyst salts such as NaOH, KOH, NaOCH3 and KOCH3 were separately added to the oil and mixed. In order to ensure complete transformation of the okra seed oil into fatty acid methyl esters (FAMEs), each experiment was conducted for 120 min. As soon as the reaction was completed, the contents of the reactor were transferred into a separating funnel and allowed to cool and equilibrate for the partitioning of two distinct phases. Of the two separated phases, the upper layer consisted of methyl esters with small amounts of impurities such as residual alcohol, glycerol and partial glycerides, while the lower phase contained glycerol with other materials such as unused methanol, catalyst, soaps derived during the reaction, some suspended methyl esters and partial glycerides. The upper layer consisting of methyl esters was collected and further puried by distilling off residual methanol at 80 C (external bath temperature). The traces of the remaining catalyst, methanol and glycerol were removed by repeated washings with distilled water. Any left over water was then removed by drying esters with sodium sulfate, followed by

ltration using Whatman lter paper No. 42. The quantity of methyl esters produced was calculated using the following formula;

Yield of methyl esters%

grams of methyl esters produced grams of oil used in reaction 100

2.6. Fatty acid prole by GC/MS The okra oil methyl esters (OOMEs)/biodiesel were analyzed by the Agilent-Technologies GC/MS (Little Falls, CA, USA) equipped with 6890 N Network GC system and an Agilent-Technologies 5975 inert XL Mass selective detector. The OOMEs were separated on Agilent-Technologies capillary column HP-5MS (30 m 0.25 mm; lm thickness 0.25 lm). A sample volume of 1.0 lL was injected into the column using the split mode (split ratio 1:100). The carrier gas used was helium at a ow rate of 1.2 mL min1. The column oven temperature ranged from 150 C to 250 C at a linear ramp rate of 4 C min1 and initial and nal hold up time was 1 and 5 min, respectively. An electron ionization mode (ionization energy 70 eV) was used for GC/MS detection. The injector and MS transfer line were set at 250 C and 260 C, respectively. The scanning mass range varied from 30 to 650 m/z. The identication of unknown fatty acid methyl esters (FAMEs) was performed by comparing their relative and absolute retention times with those of pure standards of FAMEs. FAMEs were further identied by comparing their MS spectra with those from the NIST mass spectral library [19] of the GC/MS system. The fatty acid composition is reported as a relative percentage. 2.7. Fuel properties of OOMEs The fuel properties of the biodiesel/OOMEs produced were determined following ASTM and EU specications. Determinations of density (ASTM D 5002), lubricity (ASTM D 6079), kinematic viscosity (ASTM D 445), oxidative stability (EN 14112), cetane number (ASTM D 613), cold lter plugging point (ASTM D 6371), cloud point (ASTM D 2500), pour point (ASTM D 97), ash point (ASTM D 93), sulfur content (ASTM D 4294), ash content (ASTM D 874), water content (ASTM D 95), copper strip corrosion (ASTM D 130), acid value (ASTM D 664), ester contents (EN 14103) and mono-, di- and tri-glycerides (EN 14105) were made [20,21]. Triplicate determinations were performed for every experiment and the data presented as means standard deviation. 3. Results and discussion 3.1. Okra seed oil Okra seeds were found to contain 12% (w/w) oil, which is higher than that reported in the previous literature [22]. The okra seed oil had an acid value of 3.4 mg KOH/g and required a slight acid pretreatment proceeding to base-catalyzed transesterication. The iodine-, and saponication-values of the okra seed oil extracted were 111.00 g I2/100 g and 180.60 mg KOH/g, respectively. 3.2. Optimization of okra oil methanolysis The effect of catalyst type on OOMEs production was evaluated using four different alkaline catalysts (NaOH, KOH, NaOCH3 and KOCH3) at 1.00% (w/w) concentration. A methanol/oil molar ratio of 7:1, 600 rpm agitation intensity and 65 C reaction temperature were employed in all the experiments. As is evident from Fig. 1, the maximum yield of OOMEs was derived with NaOCH3. Furthermore,

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the methoxides (NaOCH3 and KOCH3) offered higher ester yields than the corresponding hydroxides (NaOH and KOH). Lower ester yield using hydroxide type catalysts may be due to the reason that upon mixing of sodium-, and potassium-hydroxides with methanol, a small amount of water is often produced. This may give rise to hydrolysis of some of the produced esters, resulting in soap formation thus leading to lower ester yields [7]. However, our present catalyst screening results are contradictory to the literature reports on the methanolysis of Pongamia pinnata [9], Brassica carinata [23] and rapeseed [24] oils, which concluded that KOH was the most effective catalyst. Such deviations might be ascribed to the varied chemical nature of the feedstock oils used for biodiesel production [24]. While appraising the effect of catalyst amount on OOMEs production, a range of six experiments were conducted with varying concentrations (0%, 0.50%, 0.75%, 1.00%, 1.25% and 1.50% w/w) of NaOCH3. In all experiments, methanol/oil molar ratio of 7:1, agitation intensity 600 rpm and reaction temperature 65 C were utilized. Fig. 2 depicts the optimum yield of OOMEs at 1.00% catalyst. As predictable, no product appeared with 0% catalyst. The catalyst concentrations higher than 1.00% exhibited adverse effects on OOMEs yield, which is in line with the work of Dorado et al. [23] and Encinar et al. [25] who reported that the soap formation in the presence of high catalyst amount increases the viscosity of reaction leading to lower methyl ester yields. The methanol/oil molar ratio (3:1, 4:1, 5:1, 6:1, 7:1, 8:1 and 9:1) was varied to establish the effect of varying amount of methanol on OOMEs production. In all seven experiments, 600 rpm rate of agitation, 65 C reaction temperature and 1.00% NaOCH3 were em-

Fig. 2. Effect of NaOCH3 concentration on the yield of okra oil methyl esters (7:1 methanol/oil molar ratio, 600 rpm rate of agitation, 65 C reaction temperature).

ployed. The optimum yield (96.8%) of OOMEs was gained at methanol/oil molar ratio of 7:1 (Fig. 3). On the other hand, the stoichiometric ratio of methanol/oil (3:1) offered the lowest OOMEs yield (61%). Higher quantities (beyond 7:1) of methanol had an adverse effect on OOMEs production. This is evident by steadily lowering yields with increasing molar ratio from 7:1 to 9:1 (Fig. 4). At methanol to oil molar ratios greater than 7:1, separation of esters from glycerol was difcult. The unreacted methanol, when present, can suppress the gravity decantation so that the apparent yield of OOMEs decreases because traces of glycerol may remain in the biodiesel phase [6,26]. These results are almost comparable with earlier studies [6,9,24,2729] which investigated optimum ester yield from different vegetable oils at methanol/oil molar ratio of 6:1. 3.3. Fatty ester prole and quality of optimized OOMEs The fatty methyl ester prole of OOMEs, as shown in Table 1, is in close agreement with a prior report on okra seed oil [30]. As indicated by Table 1, linoleic acid (30.31%) is the predominate constituent of OOMEs. The amounts of palmitic, oleic and stearic acids were found to be 30.23%, 29.09% and 4.93%, respectively. A small amount of 2-octyl cyclopropaneoctanoic acid and 2-hexyl cyclopropaneoctanoic acid with contribution 1.92% and 0.25%, respectively, was also established. Some minor fatty acids which included arachidic (0.73%), behenic (0.34%), palmitoleic (0.28%), myristic (0.21%) and margaric (0.15%) were also detected. Table 2 shows the quality of optimized OOMEs as established by accepted ASTM [20] and EU methods [21], which included water content (0.020% by mass), free glycerin (0.012% by mass), total

Fig. 1. Effect of catalyst type on the yield of okra oil methyl esters (1.0% catalyst, 7:1 methanol/oil molar ratio, 600 rpm rate of agitation, 65 C reaction temperature).

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as a function of temperature at 40 C was 4.01 mm2/s (Table 2). The kinematic viscosity determined for OOMEs/biodiesel was found to be lower than that of the parent oil. With the values of kinematic viscosity at 40 C of methyl linoleate, methyl palmitate and methyl oleate, the three major components of OOMEs being 3.65 mm2/s, 4.38 mm2/s and 4.51 mm2/s [32], respectively. The experimental kinematic viscosity of 4.01 mm2/s for OOMEs was understandable in relation to the fatty acid prole studied. The kinematic viscosity of OOMEs was also within the ranges specied in biodiesel standards i.e. ASTM standard D 6751 (1.96.0 mm2/s) and EN 14214 (3.55.0 mm2/s). 3.4.3. Oxidative stability Rancimat method EN 14112 was used to appraise the oxidative stability of OOMEs. The rancimat induction time of 1.71 h was observed for OOMEs. This value coincides with the minimum limits specied in ASTM D 6751 (P3 h) and EN 14214 (6 h). This is mainly due to the low rancimat induction period of neat methyl linoleate (0.94 h) and methyl linolenate (0.00 h), while the rancimat induction period of methyl oleate of 2.79 h [33] also does not fulll biodiesel standards. Loss of antioxidants during transesterication probably is the reason that can cause the reduction of oxidative stability of OOMEs compared to the parent oil. Addition of some antioxidant compounds may reinstate the oxidative stability of OOMEs to an acceptable level. 3.4.4. Lubricity Lubricity of biodiesel is an important property which affects the performance of a diesel engine. Poor lubricity is linked with the failure of engine parts. Two tests of OOMEs using the HFRR lubricity tester gave an average ball wear scars of 139.5 lm which was found to be below the maximum values prescribed in the European petro-diesel standard EN 590 and the American petro-diesel standard ASTM D975. These standards prescribed maximum wear scars of 460 lm and 520 lm, respectively, showing that OOMEs would be acceptable with respect to lubricity. 3.4.5. Cloud, pour and cold lter plugging points Poor ow properties often indicated by somewhat high cloud points (CP), pour points (PP) and cold lter plugging points (CFPP) are some of the key problems related to the use of biodiesel. The cloud and pour point values of the biodiesel produced in the present study were found to be 1 C and 2 C, respectively (Table 2). Cold lter plugging point (CFPP) tests were performed using the ASTM D 6371 method. This value was 1 C. These points need to be considerably low, because if the OOMEs are frozen, the motor will not start. In view of ASTM standard D 6751, no limit is mentioned; rather a report is specic for cloud, pour and cold lter plugging points. The explanation is that the global climatic conditions vary signicantly and therefore the needs of the biodiesel users vary accordingly. 3.4.6. Flash point The ash point which is determined by ASTM D 93 is the temperature at which the fuel is mixture-like and is ready to ignite when exposed to a ame. Table 2, indicates that the biodiesel produced from okra oil had a ash point (156 C) greater than that of the conventional petro-diesel. It is generally accepted that a higher value of ash point decreases the risk of re. This is an advantage of biodiesel over to petro-diesel. 3.4.7. Sulfur and ash contents The concentration of sulfur in the OOMEs samples was measured by ASTM D 4294, using the wavelength-dispersive X-ray uorescence spectrometery. As depicted in Table 2, unlike the conventional petro-diesel fuels (sulfur content of 50 ppm), the biodiesel

Fig. 3. Effect of methanol/oil molar ratio on the yield of okra oil methyl esters (1.0% NaOCH3, 600 rpm rate of agitation, 65 C reaction temperature).

glycerin (0.220% by mass), methanol contents (0.181% by mass), ester contents (97.09%), mono- (0.38%), di- (0.13%) and tri-glycerides (0.07%). 3.4. Fuel properties of OOMEs Fuel properties of optimized OOMEs were evaluated following the established ASTM and EU methods (Table 2). These included density, kinematic viscosity, cold lter plugging point, ash point, cetane number, acid value, cloud point, and copper strip corrosion (3 h at 50 C). 3.4.1. Cetane number The cetane number is an appraisal of ignition quality of diesel fuel. The greater the cetane number, the more ignitable the fuel is. The cetane number was determined using an Ignition Quality Tester (IQTTM) as described previously [31]. As depicts in Table 2, the cetane number of the biodiesel produced from okra seed oil was 55.2. The cetane numbers of methyl palmitate, methyl oleate and methyl linoleate are reported to be 85.9, 59.3 and 38.2, respectively, in the IQTTM [31]. Keeping in view the fatty acid composition of okra seed oil, the determined cetane number of OOMEs could be well-explained. 3.4.2. Kinematic viscosity Kinematic viscosity is an important fuel property which affects the atomization of a fuel upon injection into the combustion chamber and nally may lead to the formation of soot and engine deposits [32]. The kinematic viscosity of the OOMEs in the present work

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Fig. 4. Gas chromatography/mass spectrometry (GC/MS) chromatogram of okra oil methyl esters (OOMEs).

produced from okra oil in the present study showed negligible sulfur content (0.0112%). The sulfur content in OOMEs was less than 1 ppm, which is one of the main advantages of biodiesel. Low sulfur is known to help both engine life and environment. The level of ash content represents the magnitude of inorganic

contaminants, such as abrasive solids and catalyst residues, and the amount of soluble metals contained in a fuel sample. ASTM D 874 is a standard test method for determining sulfated ash from lubricating oils and additives. It could be observed from Table 2, that OOMEs had the sulfated ash 0.010% by weight.

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Table 1 Fatty acids (FA) composition (%) of okra oil methyl esters (OOMEs). FAa Myristic acid (C14:0) Palmitic acid (C16:0) Palmitoleic acid (C16:1) Margaric acid (C17:0) Stearic acid (C18:0) Oleic acid (C18:1), cis9 Linoleic acid (C18:2) Linolenic acid (C18:3) Arachidic acid (C20:0) Behenic acid (C22:0) Erucic acid (C22:1) 2-Octylcyclopropaneoctanoic acid 2-Hexylcyclopropaneoctanoic acid Othersc RTb 16.73 20.86 20.39 22.72 24.57 24.16 24.04 28.89 36.21 26.13 22.24 Relative percentage (%) 0.21 0.07 30.23 0.81 0.28 0.08 0.15 0.10 4.93 0.15 29.09 0.58 30.31 0.75 ND 0.73 0.06 0.34 0.10 ND 1.92 0.05 0.25 0.06 1.56 0.09 Pham et al. [30] 0.2973 32.23 0.3089 NR 3.943 30.13 30.05 0.3814 0.3619 0.8145 0.2754 NR NR NR

to estimate the extent of copper corrosion that may occur under biodiesel application, particularly when metals such as copper are present. The values of copper strip corrosion test for the OOMEs were within the limits specied by the standard ASTM D 6751 (No. 3 max) and EN 14214 (No. 1 min). 3.4.9. Density In the present study, the density of OOMEs/biodiesel produced from okra oil was 876 kg/m3. The density of the okra biodiesel was higher than that of conventional diesel (825835 kg/m3), however, the biodiesel produced from okra oil in the present study was within the prescribed limits by the standard EN14214. 4. Conclusion The optimum conditions established for the methanolysis of crude okra seed oil in the present investigation were recorded to be: 7:1 M ratio of methanol to oil and 1.00% (w/w) NaOCH3 catalyst. This set of optimized conditions provided 96.8% OOMEs yield. Fuel properties of OOMEs were quite comparable with those of ASTM D 6751 and EN 14214. Therefore, it can be concluded that OOMEs are acceptable substitute for D2 and other oilseed crop methyl esters. As the environment and soil in Pakistan is very suitable for okra cultivation so this crop should be cultivated on large scale production yielding non-conventional oil that can be usefully converted into biodiesel. Acknowledgements Financial support by the Pakistan Science Foundation (PSF), Islamabad, Pakistan is highly acknowledged. The authors are also grateful to Muhammad Aamir from the Attock Renery Limited (ARL), Rawalpindi, Pakistan for his technical assistance. References
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Values are means SD for triplicate determinations. ND = not detected; NR = not reported. a Fatty acids are listed in order of elution on HP-5MS column. b Retention times in min. c Not identied fatty acid.

Table 2 Properties of okra oil methyl esters (OOMEs) in comparison with biodiesel standards. Property Cetane number Kinematic viscosity (mm2/s; 40 C) Oxidative stability (h) Lubricity (HFRR; lm) Cloud point (C) Pour point (C) Cold lter plugging point (C) Flash point (C) Sulfur content (%) Ash content (%) Acid value (mg KOH/g) Copper strip corrosion (50 C, 3 h) Density (25 C), kg/m3 Methanol content (%) Free glycerin (%) Total glycerin (%) Ester contents (%) Monoglyceride (%) Diglyceride (%) Triglyceride (%) OOMEs 55.2 2.00 4.01 0.10 1.71 0.15 138 3.50 1.00 0.10 2.00 0.12 1.00 0.10 156 3.80 0.012 0.001 0.010 0.001 0.39 0.05 1a 876 14.9 0.181 0.004 0.012 0.001 0.220 0.020 97.09 2.39 0.38 0.05 0.13 0.02 0.07 0.01 ASTM D6751 47 min 1.96.0 3 min a Report c c 93 min 0.05 max 0.02 max 0.50 max No. 3 max 0.020 max 0.240 max EN 14214 51 min 3.55.0 6 min a b b b 120 min 0.02 max 0.50 max No. 1 min 860900 0.2 max 0.020 max 0.250 max 96.5% min 0.80% max 0.20% max 0.20% max

Values are means SD of triplicate determinations. a Not specied. Maximum wear scar values of 460 lm and 520 lm are prescribed in petro-diesel standards EN 590 and ASTM D975. b Not specied. EN 14214 uses time and location-dependent values for the cold lter plugging point (CFPP) instead. c Not specied.

3.4.8. Acid and copper strip corrosion values The acid value is a simplistic method for examining the fuel quality which was estimated using the ASTM D 664. The acid value of the biodiesel produced in the current work was 0.39 mg KOH/g (Table 2). The ASTM and EN 14214 specify a limit of 0.5 (max) mg KOH/g of an acid value for a biodiesel. The ASTM D 130 was chosen

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