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Physicochemical characterization of seven Mexican Ricinus communis L. seeds & oil contents
s A. Acosta-Osorio b, G. Herrera b, Jose F. Vasco-Leal b, Felipe A. Perdomo a,*, Andre D. Mosquera-Artamonov b, Beatriz Millan-Malo a, Mario E. Rodriguez-Garcia a Jose
noma de Me xico, Departamento de Nanotecnolog a, Centro de F sica Aplicada y Tecnolog a Avanzada, Universidad Nacional Auto taro, A.P. 1-1010, C.P. 76000, Mexico Campus Juriquilla, Quere b n de Investigacio n y Posgrado, Facultad de Ingenier noma de Quere taro, Cerro de las Campanas s/n, Divisio a, Universidad Auto taro, Qro, Mexico C.P. 76010 Quere
a

article info
Article history: Received 20 June 2012 Received in revised form 26 July 2012 Accepted 23 October 2012 Available online 23 December 2012 Keywords: Castor oil Physicochemical characterization Fatty acid composition Ricinus communis seeds Non edible oils

abstract
This paper presents a rigorous study and characterization of seven Mexican Ricinus communis L. seeds and its respective extracted oil. Several physicalechemical properties were measured in order to know moisture, total lipid content, ber content, starch presence, morphology, acidity, free fatty acid prole, ricinoleic acid content, viscosity and crude oil density. Three different methodologies were implemented for the oil extraction in each variety (extraction with chemical solvents and mechanical compression heated and nonheated). The yield percentage of the oil extraction was evaluated as well as the extraction method inuence over the oils nature. 2012 Elsevier Ltd. All rights reserved.

1.

Introduction

Castor oil, also known as Ricinus oil, is a fatty acid triglyceride within the seed of the castor plant, Ricinus communis L. It is one of the few naturally high purity glycerides since the fatty acid portion contains nearly 900 g kg1 of ricinoleic acid. Castor oil is rich in a very unique hydroxyl fatty acid, ricinoleic acid C18H34O3 structurally known as cis-12hydroxyoctadeca-9-enoic acid, 18 carbon hydroxylated fatty acid having one double bond. The presence of ricinoleic acid provides castor oil its unique properties and unusual versatility.

Castor oil differs from other oils with its high acetyl or hydroxyl value and forms oil of comparable iodine value with a high viscosity and specic gravity. Unlike other oils, it is mixable with alcohol, but only slightly soluble in petroleum ether at room temperature. Castor oil also has excellent emollient and lubricating properties as well as marked capability to wet and disperse dyes, pigments and llers. Usually, the castor bean has been cultivated for the seeds obtaining its respective viscous, pale yellow, non-volatile, and non-drying oil; yet the presence of the hydroxyl group, double bonds and ester linkages in castor oil provides a reaction sites in the preparation of many useful industrial derivates. Castor oil has been used for the

* Corresponding author. Tel.: 52 4422381141; fax: 52 4422381165. E-mail address: faperdomoh@fata.unam.mx (F.A. Perdomo). 0961-9534/$ e see front matter 2012 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.biombioe.2012.10.020

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coating of fabrics and other protective coverings, in the manufacture of high grade lubricants, transparent typewriter and printing inks, in textile dyeing, in the production of Rilsan monomer (11eamino-undecanoic acid), in the manufacture of synthetic avors and fragrances, lower molecular weight aviation fuels, fuel additives, and biopolymers [1]. R. communis L. is considered as an important source of oil. A large variability of seed oil content has been observed ranging from 39.6 g kg1 to 59.5 g kg1. Ricinus oil has a worldwide demand estimated to be about 220,000 tons per year; such important production is in part due to the ricinoleic acid that has been found to be useful to replace sulfur based diesel fuel lubricating components, helping to reduce sulfur emissions. Additionally, in the context of growing interest for renewable energy sources; liquid bioenergy production from vegetable oils, Ricinus oil is proposed as one of the possible options to reduce the greenhouse gas (GHG) emissions [2]. Against this background, biodiesel production from the oil of R. communis L. has been identied as an important potential source of raw material for the local production of biodiesel in several places around the world and has become a booming business [3,4]. The characteristic of castor oil from other countries such as Brazil, Nigeria, India, China, and Africa had been studied. For example, the evaluation of physicochemical characteristics and fatty acid composition of Malaysian castor bean oil extracted through Soxhlet extraction method [5]; the analysis of variability for oil and fatty acid composition in thirty-six different Brazilian castor bean varieties [6] or the study of castor genetic resources to provide important information on current status of global castor collections, and its existent germplasm throughout the world [7]. However, only a few researches have been conducted on Mexican castor oil. An important research was made about the morphology and some chemical and physical properties of castor oil plant seeds from Michoacan, Mexico [8], but such research only concentrated in the importance of the analysis in the endosperm micro-structural study and seed morphology, and neither the oil extraction yield, nor the physicalechemical oil properties and composition were approached. The objective of this work is to determine the most relevant physicochemical properties of crude Mexican castor oils and their fatty acid composition, as well as the triacylglycerols composition. This paper is aimed towards the extraction, characterization and rening of seven different castor oil seeds from the Mexican Baj o region (Queretaro state). In view of the high losses suffered by farmers and producers during the droughts in recent years in the State of Queretaro and Mexico, our study is quite relevant to the viability analysis being confronted in order to substitute several crops with castor crops in region with low rainfall precipitation season. The specic goals in our study were achieved through the realization of the following steps: sample recollection, classication, sample preparation, extraction of Castor Oil from Castor beans through solvent extraction process and by means of applying pressure, and physicochemical characterization of oil and waste biomass. Besides the neat physicochemical analysis, x-ray diffraction was included, scanning electron microscopy to study some morphology of the seeds,

and important rheological properties like cinematic viscosity and density.

2. Materials and methods for seed and oil analysis

2.1. Sample recollection, classication, and preparation

At this point it is very important in the case of these samples to follow the procedure dened by Barton (1984) [9] in relation to the sample denition and we took some of that parameter to identify our samples.

2.1.1.

Harvest

Castor beans were recollected at twenty different sites of Queretaro state. The geographic location, including elevation, of the sites where the harvest was carried out is summarized on Table 1. The soils type observed in the harvest sites were predominantly well drained sandy, gravelly and heavy soils. In all places we could observe the presence of water settlements like puddles, strainers and slope rivers. The branches distribution in the R. communis L. is periodic and ramied, that is to say each branch end with a raceme in the tip and, here, appears again a branch. The height of the raceme where the samples were taken from plants was variable between the several Castor plants, and according to the literature review, these variability is due to precocity level in the plant [10], and also the luminosity level exposition. The racemes were cut and the castor beans were broken off, this procedure allowed to accelerate the beans drying process.

2.1.2.

Drying

The castor bean varieties were packed in net bags, and then dried in a greenhouse until the shells split and the seeds shed

Table 1 e Site coordinates where the castor beans were taro state. harvested in all Quere Site
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Altitude (m)
1914 1876 1932 1854 1932 1876 1856 1877 1818 1842 2013 2617 2646 1830 1823 2063 2072 1932 1901 1819

Latitude
20 20 20 30 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20


Longitude
100 280 W 100 280 W 100 260 W 92 230 W 100 220 W 100 260 E 100 270 E 100 240 E 100 250 E 100 260 E 100 260 E 100 080 E 100 080 E 100 240 E 100 240 E 99 480 E 99 490 E 100 030 E 100 020 E 100 260 E

39 410 420 250 300 410 400 400 380 400 480 110 100 340 330 410 420 460 470 320

N N N N N N N N N N N N N N N N N N N N

N north direction; E east direction; W west direction.

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(except for VQ-1 and VQ-7 where the seed cannot leave the shell and must be removed manually).

the images on the surfaces with the backscattering electron signal.

2.1.3.

Cleaning

2.4.

X-ray diffraction characterization

The castor bean shells and seeds had some foreign materials and dirt, which were separated with a custom built set sieve. After that, the seeds were hand selected and separated accordingly.

2.1.4.

Storage

Once the seeds are clean, all samples are packed in vacuum boxes for storage at room temperature in dark conditions.

The X-ray diffraction patterns of each one of the cleaned post extraction defatted samples, were recorded with a (Rigaku MiniFlex) diffractometer operating at 35 kV and 15 mA, with a Cu Ka radiation and l 1.5406  A, wavelength, from 10 to 80 on a 2q scale with a 0.05 size step. The measurements were recorded at room temperature.

2.1.5.

Classication

2.5.

Oil extraction and characterization

The different seeds were classied according to size, color, plant characteristics, and weight. This classication generated seven different varieties. The physical properties and seeds particular details are summarized on Table 2.

2.1.6.

Hulled

The oil contained in the castor seeds was extracted through two different methods as follows: the rst extraction process through solvent (chemical extraction) and the second implementing a mechanical expeller. Details of both methodologies are shown as follows.

In order to achieve a high yield in the Soxhlet extraction (see Section 3), the seed shells were taken off from the cotyledon by means of light compression and hand picking.

2.5.1.

Chemical extraction

2.2.

Moisture content determination of seeds

5 102 kg of cleaned sample of all varieties was weighted and oven dried at 95  C for seven hours and then the weight recorded every two hours. The procedure was repeated until a constant weight was obtained. After every two hours, the samples were removed from the oven and placed in desiccators to cool. The result from such process was then removed and reweighted.

2.3.

Microscopic observation

The morphologic analysis of the R. communis seeds were performed with a low-vacuum scanning electron microscopy (LVSEM, JSM 5600LV), with a 5 nm resolution in LV mode, tted with an energy dispersive X-ray spectrometer (Noran instrument, model Voyager 4.2.3). Before the analysis, the Ricinus samples were xed on the specimen holder with carbon tape mounted on an aluminum specimen holder. The analysis was done by using a 20 kV electron acceleration voltage and 12e20 Pa pressure in the specimen chamber, thus obtaining

The chemical oil extraction implemented in this work was the n-hexane oil extraction through a Soxhlet apparatus (or Soxhlet extraction) [11]. Following the protocol method and implementing, according to other reported works of castor seed oil extraction [12] or other oil seeds [13], 300 mL of nhexane was poured into a round bottom ask. 5 102 kg of the sample was placed in a thimble and inserted in the center of an extractor. The Soxhlet was heated at 63  C. When the solvent was boiling, the vapor ascended through the vertical tube and up to the top condenser. The condensate dripped into the paper lter thimble that contained the solid sample to be extracted. The extract seeped through the pores of the thimble and lled the siphon tube through which it owed back down into the round bottom ask. Such procedure continued for six hours. At the end of the extraction, the resulting mixture that contained the oil and solvent were heated to recover the hexane from the castor oil.

2.5.2.

Mechanical compress extraction

0.2 kg of the seeds of each one of the samples varieties was placed in a mechanical extruder. Then, the endosperm seeds were compressed with a hydraulic press (Mikels model PHB 15, with 150 mm stroke hydraulic and weight 132 kg) for 2 min

Table 2 e Classication criteria and characteristics of seeds in seven varieties of Ricinus communis L. from Queretaro state. Seed variety Qualitative description Width (mm) Mean
VQ-1 VQ-2 VQ-3 VQ-4 VQ-5 VQ-6 VQ-7 Big brown Small brown Small green Medium white Small black Stained medium black Medium brown 9.69 6.87 6.18 7.15 6.34 6.50 8.55

Thickness (mm) Mean

7.09 4.88 4.76 5.01 4.60 4.68 6.30

Large (mm) Mean

15.78 11.33 10.25 11.41 10.53 10.40 14.21

Weight (g) Mean

0.400 0.187 0.132 0.209 0.162 0.172 0.310

S.D.
0.29 0.42 0.82 0.43 0.37 0.40 0.35

S.D.
0.26 0.26 0.61 0.29 0.37 0.23 0.28

S.D.
0.48 0.66 1.24 0.79 1.40 0.52 0.95

S.D.
0.056 0.018 0.025 0.018 0.012 0.013 0.042

S.D. standard deviation; VQ-1 Queretaro variety 1.

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at 490 kPa and raised the pressure again to 784 kPa for 2 min too. Later the cake was reused and the process was repeated. After the extraction, the castor oil was centrifuged twice for 16 min at 1300 r min1 in order to clean the oil and remove suspended solids. This procedure was conducted at room temperature as well as heating samples to 60  C.

2.5.3.

Viscosity studies in castor oils

The dynamic and kinematic viscosity, as well as the density of the samples was done with the use of a VM 3000 Stabinger Viscosimeter (Anton Park, Austria), at 40  C and using 5 mL of oil sample.

2.5.4.

Acid value

The acid number was used to quantify the amount of acid within the oil samples. It is the quantity of potassium hydroxide, expressed in milligrams; that is required to neutralize the acidic constituents or free fatty acids in one gram of castor oil. The procedure was applied to each one of the samples, for solvent and mechanical extraction according to ISO 660:1983 titrimetric methods for determination of the acid value and the acidity in animal and vegetable fats and oils [14,15]. The procedure must be made in duplicate and the value cannot vary around 0.25%; the nal result was the average of both measurements.

heated up to 100 C for 25 min. Latter 6 mL of HCl methanolic solution, cHCl 3.5 103 mol m3, were placed into the solution and heated again up to 80  C for 10 min, followed by the addition of 3.75 mL of an equimolar hexane e MTBE solution. The upper phase was removed and mixed with 9 mL of NaOH solution, cNaOH 3 102 mol m3, and its volume was measured. The fatty acids were analyzed using a HP 5890 series II GC (at the phytochemical laboratory of Autonomous University of Queretaro) equipped with an FID, a HP Innowax column (30 m 0.25 mm i.d 0.25 mm lm thickness). Carrier gas was He at 1.8 ml min1, the temperature program was: 180e220  C at 1.5  C min1. The injector and detector temperatures were 250  C and 270  C respectively. The peaks were integrated with the use of a GC Chem. Station Rev. A 0803 Software.

3.

Results and discussion

2.5.5.

Fatty acid prole

For the free fatty acid, methylation [16] 100 mL of fatty acids were measured and mixed with 1 mL of NaOH methanolic solution (cNaOH 3.75 103 mol m3). The samples were

The moisture percentage for all seeds was calculated according to the procedure exposed above in Section 2.2, such results are summarized in Table 2. From this result we cannot observe a lineal correspondence between moisture and the seed weight. The differences in the seeds moisture content can be explained through the morphology, specic biomass composition and by means of other factors such as immature seeds and storage conditions. Fig. 1 shows the SEM images of the endosperm, taken at 1000 (a and b) and 2000 (c and d) of sample VQ-3. Fig. 1 a and b shows the starch granules approximately 10 mm in diameter,

Fig. 1 e Environmental scanning electron microscopy micrograph of VQ-3, R. communis seed of a several endosperm sections.

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that are located in the most external layers of the seed as well as some protein bodies (formed with hexagonal bodies) showed into the circles. The starch granules are formed by a protein matrix covering two macromolecules known as amylose and amylopectin. These macromolecules can be ordered or disordered and such fact can be detected by means of x-ray diffraction [18]. Additionally, in Fig. 1 c and d fatty bodies with lengths between 10 mm and 15 mm can be observed, such being located in a ber chamber. A more detailed analysis of the fatty bodies showed that these were also formed by small close packed fatty bodies that may be protein or ber matrix surround. Fig. 2 shows the x-ray diffraction patterns of amylose and amylopectin from Sigma Aldrich, taken as references for structure determination, as well as some of the defatted samples VQ-3, VQ-5, and VQ-7. By direct comparison between these pattern, it is clear that the defatted samples and in this case the starch granules shown in Fig. 1 a and b are formed by amorphous structures (amylose) and also no crystalline structures are forming the endosperm. Table 3 shows the density measured at room temperature (25  C) for the extracted oil of each variety. The density value herein reported is the global average of mean values in oil density obtained per extraction, which was made in triplicate for each variety. Similarly, the oil extraction yield represents the percentage of extracted oil (heated and without solvent traces) regarding the weight of the sample charged to Soxhlet

Table 3 e Determination of moisture content of seven castor seeds from Queretaro state. Seed variety Moisture content% (kg kg1 100) Mean
VQ-1 VQ-2 VQ-3 VQ-4 VQ-5 VQ-6 VQ-7 3.650 3.319 3.851 3.552 3.895 3.498 3.466

S.D.
0.221 0.312 0.121 0.235 0.149 0.250 0.193

S.D. standard deviation; VQ-1 Queretaro variety 1.

Amylopectin Intensity (a.u)

Amylose

VQ-3 VQ-5 VQ-7

10

20

30

40

50

60

70

80

2 (Degrees)
Fig. 2 e X-ray diffraction patterns of several cleaned post extraction defatted samples.

apparatus. The effective oil extraction represents the volume of neat oil obtained per mass of charged sample; this quantity is quite relevant for estimating the production costs and process design at the time when large industrial quantities of seed are processed. Tables 4 and 5 show the results for the same parameters, but implementing a mechanical extraction by means of heating and compressing the samples at 60  C, as well as by compressing the seeds at room temperature, respectively. The yield extraction achieved in Soxhlet extraction is higher than the mechanical compression in both cases due to the direct solvent chemical action into the lipid bodies (see Fig. 1). However, when it would be required to process high amounts of seed extraction through solvents, it would neither be an economical option nor efcient solution; therefore, for a best yield in oil extraction it is necessary to heat the seeds before compressing. According to Table 4 the best yield for castor oil extraction is about 37 g kg1, which corresponds to small brown variety (or Queretaro variety 2, VQ-2), whereas for room extraction (see Table 5), the higher quantity of extracted castor oil corresponds to medium brown variety (Queretaro variety 7, VQ-7) with about 28 mL kg1 of castor oil, This variability is due to the inuence of heating in the breakup process of lipid bodies in each seed variety [7]. In the absence of heating factor, other parameters such as maturity, development, and seed weight (mass quantity) had been taken into account. Consequently the Soxhlet extraction will represent the limit value in the yield extraction and other factors like relative solubility, solvent chemical afnity and liquid activity play an important role in the oil extraction process [17]. Fig. 3 shows the density values of the Castor oil for each one of the methods. At this point, it is interesting to refer to the density values obtained in the three different extraction forms. All castor oil densities were measured at 25  C. The density values for the oil extracted mechanically are very similar, in contrast to the values for oil extracted through solvent, being higher. The discrepancy in these values is due mainly to two factors: The rst is due to the fact that Soxhlet extraction is cleaner than mechanical extraction, in the sense that the implemented solvent (n-hexane) has afnity and solubility for the oil and it is the only compound washed down in the Soxhlet operation. Whereas through mechanical compression, other compounds like gum ber are being pressed out.

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Table 4 e Density and yield for extracted oil of seven castor seeds from Queretaro state implementing Soxhlet method. Seed variety Densitya (g cm3) Mean
VQ-1 VQ-2 VQ-3 VQ-4 VQ-5 VQ-6 VQ-7 0.937 0.943 0.931 0.949 0.938 0.946 0.949

Oil extraction yield% (kg kg1 100) Mean

50.163 47.225 40.175 56.218 47.725 45.749 54.359

Effective oil extraction (L kg1) Mean

0.530 0.502 0.430 0.608 0.511 0.482 0.579

S.D.
0.013 0.001 0.010 0.001 0.002 0.004 0.002

S.D.
0.923 0.015 1.332 1.445 0.515 1.856 0.413

S.D
0.029 0.002 0.011 0.030 0.007 0.022 0.111

S.D. standard deviation; VQ-1 Queretaro variety 1. a Densities were measured at 25  C.

Table 5 e Density and yield for extracted oil of seven castor seeds from Queretaro state implementing mechanical extraction at T [ 60  C. Seed variety Densitya (g cm3) Mean
VQ-1 VQ-2 VQ-3 VQ-4 VQ-5 VQ-6 VQ-7 0.9586 0.9568 0.9576 0.9577 0.9573 0.9562 0.9560 3 6 6 2 1 3 7

Oil extraction yield% (kg kg1 100) Mean

33.0717 36.5976 26.3340 35.0758 35.8575 35.2399 31.5480

Effective oil extraction (L kg1) Mean

0.3450 0.3825 0.2750 0.3662 0.3750 0.3688 0.3300

S.D.
10 104 104 104 104 104 104
4

S.D.
1.9172 1.1960 0.4788 0.3591 1.1953 1.7929 2.8680

S.D.
0.0200 0.0125 0.0050 0.0380 0.0125 0.0188 0.0300

S.D. standard deviation; VQ-1 Queretaro variety 1. a Densities were measured at 25  C.

Furthermore, they were centrifuged and few particle materials remained. The second one is due to presence of n-hexane traces within the oil (extracted through Soxhlet) before distillation. We could verify experimentally that a few solvents within the oil generate high density value variation (low values). Table 6 shows the acidity or percent of fatty acids within the oil (FFA%), expressed like oleic acid percent, and the acid value

Table 6 e Density and yield for extracted oil of seven castor seeds from Queretaro state implementing mechanical extraction at T [ 60  C. Seed variety Densitya (g cm3) Mean
VQ-1 VQ-2 VQ-3 VQ-4 VQ-5 VQ-6 VQ-7 0.9598 0.9600 0.9581 0.9609 0.9601 0.9610 0.9596 1 4 2 2 2 1 2

Oil extraction yield % (kg kg1 100) Mean

23.9950 23.1600 18.2039 22.2208 22.4423 20.9017 26.9887

Effective oil extraction (L kg1) Mean

0.2500 0.2162 0.1900 0.2313 0.2338 0.2175 0.2812

S.D.
10 104 104 104 104 104 104
4

S.D.
1.1998 2.0400 0.4791 1.3212 2.0402 0.4805 1.7992

S.D.
0.0125 0.0212 0.0050 0.0137 0.0213 0.0050 0.0187

Fig. 3 e Density values for two different extraction oil methods: circles represent Soxhlet extraction, square represent mechanical extraction at room temperature, and triangles represent mechanical extraction at 60  C.

S.D. standard deviation; VQ-1 Queretaro variety 1. a Densities were measured at 25  C.

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Table 7 e Acidity and acid value for extracted oil of seven castor seeds from Queretaro state implementing Soxhlet method, mechanical compression at room and 60  C. Extraction method Varieties
VQ-1 VQ-2 VQ-3 VQ-4 VQ-5 VQ-6 VQ-7

Soxhlet FFA%
0.0547 0.0409 0.0413 0.0409 0.0411 0.0291 0.0557

Mechanical (room temperature) AV

1.0879 0.8136 0.8222 0.8141 0.8193 0.5790 1.1098

Mechanical (60  C) FFA%

0.0562 0.0552 0.0950 0.0413 0.0416 0.0420 0.0698

FFA%
0.0419 0.0418 0.0272 0.0400 0.0538 0.0393 0.1504

AV
0.8344 0.8325 0.5428 0.7962 1.0707 0.7833 2.9933

AV
1.1186 1.0997 1.8912 0.8232 0.8272 0.8366 1.3904

AV acid value or acid number (mg KOH g1); FFA% free fatty acid (kg kg1 100); VQ-1 Queretaro variety 1.

Table 8 e Fatty acids composition (%) of extracted oil of seven castor seed oil from Queretaro state. V and M.
VQ-1 Soxhlet VQ-1 comp. (60  C) VQ-2 Soxhlet VQ-3 Soxhlet VQ-4 Soxhlet VQ-5 Soxhlet VQ-6 Soxhlet VQ-6 comp. (60  C) VQ-6 comp. (room) VQ-7 Soxhlet

Palmitic
0.06 0.23 0.23 0.00 0.41 0.12 0.18 0.21 0.30 0.27

Stearic
0.67 1.46 0.72 0.04 2.82 0.52 0.89 18.86 6.42 1.58

Oleic
1.50 1.88 2.08 0.32 2.54 0.48 1.10 5.73 4.61 1.72

Linoleic
1.99 2.30 2.38 6.58 13.69 3.20 14.78 1.01 23.28 21.69

Linolenic
0.30 0.20 0.29 0.20 0.42 0.41 0.86 0.13 0.58 0.05

Ricinoleic
95.49 93.93 94.30 92.86 80.12 95.27 82.19 74.06 64.81 74.68

V and M seed variety and oil extracted method; comp. extraction by compression; room oil extraction made at room temperature.

(AV) expressed in milligram of KOH per gram of oil sample for each one of the seeds extracted through the three different extraction methods in order to determine the inuence of heating over oil quality. From the values contained in this table, we can infer that heating oil generate an increase in the percent of free fatty acids, and consequently an increase in acid value, thereby the castor oil extracted through the Soxhlet method and mechanical compression, heating at 60  C, have a higher acidity than the castor oil extracted through the compressing method at room temperature. The differences of acid value between castor oil extracted with the same method can be explained due to the quality of the oil and other factors such as immature seeds and poor storage conditions [4]. In order to sustain the above insights in regards to change in acid value, a gas chromatography analysis (GC) was conducted to study their free fatty acid prole. Table 8 shows the results obtained through GC for the free fatty acid prole of several castor seed oils. The fatty acid proles of oils extracted from variety VQ-1 by Soxhlet and through mechanical extraction at 60  C show concordance in the composition of different fatty acid and present a high content of ricinoleic acid. On the other hand, the fatty acid proles extracted from variety VQ-6 through Soxhlet, compressing to 60  C and compressing at room temperature show a reduction in the percentage of ricinoleic acid when the oil is extracted without heating. Hence, we can conclude based upon the study of acidity (Table 7) and fatty acid composition proles in the oils extracted at different temperatures, that the

heat effect in extraction of castor oil induce a rupture in its triacylglycerols generating a rise in free fatty acids and diacylglycerols (for example, the rupture in a molecule of triricinolein generate a molecule of ricinoleic acid and one diricinolein).

Fig. 4 e Viscosity values for the different extraction oil methods: triangles represent Soxhlet extractions, square represent mechanical extraction at room temperature and circles represent mechanical extraction at 60  C.

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One of the most important parameter of the oil relates to the transport properties, Fig. 4 shows the viscosity of the castor oil extracted for the three different methods. Higher values in castor oil viscosities are obtained when the oil is extracted at room temperature; whereas the viscosity decreases when the heating is implemented. Another important topic that could be concluded from the aforementioned results is the fact that if the oil extraction is done by compressing it at room temperature, the castor oil nature is not altered and preserves the initial genotype, yet in contrast the oil yield extraction is low in comparison if heating is implemented.

references

4.

Conclusions

According to the SEM images it is clear that the fatty and protein bodies are located in the internal part of the endosperm and that some protein bodies and starch are located in the most external layers of the endosperm. The x-ray diffraction showed that non-crystalline compounds form the endosperm. In the case of the methods used to obtain the oils, we can conclude that the solvent extraction allows obtaining clean oil in relation to the mechanical methods. The oils obtained through mechanical methods even the centrifugation exhibit the presence of small particles such as gums and ber (soluble and non-soluble). However, for oils obtained through solvent methods, it is very important to take into account the recovering process of the solvent because the presence of hydroxyl groups in ricinoleic acid increase the solubility of the solvent within the oil, and traces of solvent (n-hexane) generated variation in the physicochemical properties of the nal product. The results showed that quality, composition, physicochemical properties, and the nature of castor oil vary according to the implemented extraction method. The insights exposed here will be of high relevance when the nal use of castor oil is required (i.e. lubricant, biodiesel or crude). An option to improve this kind of process is to make an extraction through solvents only in the cake generated post compression, due to the fact that the oil content of the seed cake will be higher because of the lower efciency of the mechanical compression and therefore enhance the oil extraction recovery.

Acknowledgments
This work was partially supported by Centro de F sica Aplicada y Tecnolog a Avanzada de la UNAM, Project 2012. F. A. Perdomo wants to thank CTIC-Centro de F sica Aplicada y Tecnolog a Avanzada de la UNAM for the nancial support of his post-doctoral position and M. en C. Alicia del Real for the SEM images.

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