Escolar Documentos
Profissional Documentos
Cultura Documentos
A R T I C L E I N F O A B S T R A C T
Article history: Two operating solvent extraction conditions, i.e. average particle size and extraction time, were
Received 10 June 2014 optimized by a response surface method using BoxBehnken design to obtain high oil yields. The
Received in revised form 9 September 2014 extraction was conducted by the soxhlet method using ethanol, n-hexane and petroleum ether as
Accepted 12 October 2014
solvents. Statistical analyses and analysis of variance indicated that the operating conditions are
Available online 7 November 2014
signicant factors affecting the yield. For the modeled extraction, yields of 59.8%, 52.3% and 49.9% were
determined for optimized average particle sizes and extraction times of 1.30 mm and 2.88 h, 1.26 mm
Keywords:
and 2.65 h and 1.25 mm and 2.55 h, respectively. The physicochemical properties of castor bean oils
Solvent extraction
were evaluated. The extracted oils contain refractive indices of 1.4771, 1.4770 and 1.4772,
Response surface methodology
Optimization unsaponiable contents of 0.6, 0.45 and 0.5%, volatile contents of 0.48, 0.55 and 0.28%, free fatty
Castor contents of 0.8, 0.3 and 0.27%, phospholipid values of 0.03, 0.05 and 0.03%, peroxide values of 12.4, 3.3
Ricinoleic acid and 3.5 meq O2/kg, iodine values of 85.6, 84.5 and 85.0 g/I2/100 g of oil, saponication values of 174.6,
Physicochemical properties 176.3 and 173.8 mg of KOH/g of oil, acid values of 1.60, 0.60 and 0.53 mg KOH/g, respectively. The
analyses indicate that the oil is suitable for use in the oleo-chemicals industry.
2014 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jtice.2014.10.012
1876-1070/ 2014 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
100 J.M. Danlami et al. / Journal of the Taiwan Institute of Chemical Engineers 47 (2015) 99104
2.3. Soxhlet extraction Methylated injection samples were prepared prior to gas
chromatographic (GC) analysis. GC of the fatty acid content was
Ten grams of crushed castor seed were inserted into a soxhlet conducted using a Clarus 580 equipped with a ame ionization
extractor connected to a 1000 mL ask containing 250 mL of detector. The carrier gas used was nitrogen at a ow rate of 1 mL/min.
ethanol. The extraction was conducted at the boiling temperature A 1.5 mL of methylated samples of ethanol, n-hexane or petroleum
of ethanol for 1, 2 and 3 h for particle sizes of 1, 2.26 and 3.35 mm. ether was injected using the split mode (50:1). The injector and
After extraction, the solvent was evaporated at its boiling point detector temperatures were maintained at 235 8C and 250 8C,
until a complete removal of ethanol was ascertained for respectively. The column temperature was initially 160 8C, and the
determining the extract weight. The same procedure was repeated heating was programmed to increase by 2 8C/min to 195 8C for 1 min
in duplicate for n-hexane and petroleum ether as extraction and a subsequent increase of 1 8C/min to 210 8C. The retention
solvents as well. indices were then determined relative to the retention times,
whereas the composition percentages were obtained using electronic
2.4. Yield calculation integration measurements based on the area of normalization.
After the extraction process, the castor bean seed cake was oven 3. Results and discussion
dried for 24 h at 50 8C for the purpose of determining the weight of
the dry seed. The dry seed was used in determining the oil yield 3.1. Experimental data and regression model
from the different extraction solvents as follows:
The results on yield based upon the experimental design were
Weight of extracted oil 100% the subject of multiple regression analysis using the polynomial
Yield (1)
Weight of total sample model given in Eq. (3) for the prediction of the optimum responses
of the oil yield. To predict the optimum oil yield, the coefcients of
2.5. Experimental design the model given by Eq. (3) were solved by regression analysis, and
are shown as the following equations:
BoxBehnken design was chosen as the experimental design
Y 1 51:297 0:302X 1 0:805X 2 5:775X12 1:142X22 0; (4)
and optimized by RSM. The method used in this study includes a
two-factorial design with second-order quadratic polynomial
estimation for optimizing the responses over a range of variables. Y 2 37:398 4:948X 1 2:341X 2 3:35X12 1:667X22 0; (5)
The RSM was conducted to attain the optimum degree of
extraction, as measured by the optimum oil yield. Thus, the Y 3 37:873 6:568X 1 2:618X 2 3:525X12 1:992X22 0; (6)
J.M. Danlami et al. / Journal of the Taiwan Institute of Chemical Engineers 47 (2015) 99104 101
Table 2
Results of the experimental design based upon the coding given in Table 1 and the predicted responses of oil yield.
No. of run Extraction Average particle %Oil yield for Predicted % %Oil yield Predicted % oil yield %Oil yield for Predicted %
time (X1) size (X2) ethanol for hexane petroleum ether oil yield
oil yield
where Y1, Y2 and Y3 represent the yields of ethanol, n-hexane and the linear and quadratic terms were highly signicant in affecting
petroleum ether solvent extraction, respectively, and the tested the oil yield. Among the linear terms, for Eq. (4), average particle
variables, extraction time (X1) and average particle size (X2) remain size of the sample was found to have the highest impact on the
in their coded forms. Both the experiment results and their yield of extracted oil as given by the highest linear coefcient
predicted values are listed in Table 2. (0.805) followed by extraction time (0.302). While the linear
terms for Eqs. (5 and 6), extraction time was found to have the
3.2. Signicance of variables and coefcients highest impact on the oil yield. The positive coefcient of
extraction time in Eqs. (4, 5 and 6) indicate a linear effect to
The signicance of each of the variables was tested by ANOVA, increase the yield of oil extraction, while the negative coefcient of
listed in Table 3, for a F-value of the model at a 95% condence the average particle size in Eqs. (4, 5 and 6) of the sample shows a
level. The lack of t having F-values of 29.0, 14.16 and 11.0, P- linear effect to decrease the yield. In addition, the quadratic
values of 0.1978, 0.0811 and 0.0756, respectively, for ethanol, n- coefcient of X22 and X12 for Eqs. (4 and 6) has a strong negative
hexane and petroleum ether shows that it is not signicant, this effect that decreases the oil yield, whereas the quadratic
implies that the model has a good t for prediction. It has been coefcients of X12 for Eqs. (4 and 6), X22 for Eqs. (5 and 6) had
reported that regression models with P values less than 0.05 indi- positive effects that increase the yield.
cate statistical signicance [14]. Plots of the experimental and predicted oil yields versus
The ANOVA results of the model indicate a good model experimental runs are shown in Figs. 13. The plots qualitative
performance with an R2 value of 0.9005, 0.9216 and 0.9587, illustrate uniformly distributed experimental values around the
adjusted determination coefcients R2 of 0.8699, 0.8975 and predicted values representative of a close t. Therefore, a multiple
0.9460 for ethanol, n-hexane and petroleum ether, respectively. A regression correlation between the independent variables (X1 and
high R2 value, of at least 0.80, is required and a reasonable X2) and the responses (Y1, Y2 and Y3) is possible, and second-order
agreement with adjusted R2 is necessary for a model to t polynomial model can be applied for interpreting the correlation
[17]. Therefore, the oil yield percent indicates that the modeling is between the chosen parameters.
signicant, because the calculated F-values representing the three
extraction solvents from Table 3 are much greater than the table
experimental value of F(2,15,0.05) = 3.68. Eqs. (4)(6), showed that all
6.0
Experimental and predicted oil yield (%)
Table 3
ANOVA results for the effects of extraction time and average particle size on oil yield 5.8
(%).
5.6
Sources SS df MS F-value P>F Remark
Ethanol
5.4
Regression 170.47 2 85.23 29.00 <0.00002 Signicant
Residual 44.08 15 2.94
5.2
Total 214.55 17
n-Hexane
5.0
Regression 472.94 2 236.47 14.16 <0.000001 Signicant
Residual 250.43 15 16.69
Experimental values
4.8
Total 723.36 17 Predicted values
Petroleum ether 0 2 4 6 8 10 12 14 16 18 20
Regression 413.08 2 206.54 11.01 <0.000001 Signicant Experimental runs
Residual 281.28 15 18.75
Fig. 1. Comparison between experimental and predicted values of oil yield (%) for
Total 694.35 17
ethanol.
102 J.M. Danlami et al. / Journal of the Taiwan Institute of Chemical Engineers 47 (2015) 99104
55
Experimental and predicted oil yield (%)
50
45
40
35
30
Experimental values
Predicted values
25
0 2 4 6 8 10 12 14 16 18 20
Experimental runs
Fig. 2. Comparison between experimental and predicted values of oil yield (%) for n- Fig. 4. Contour plot of oil yield for ethanol, as affected by extraction time and
hexane. average particle size.
51.9% and 49.6%, which were more than that obtained from the
analysis of plots in Figs. 46. A conrmatory experiments were
conducted using optimum experimental parameters determined, level, demonstrated the validity of RSM. The experimental and the
to evaluate these predicted results. A mean oil extraction values of predicted results demonstrate the accuracy and the adequacy of
59.8%, 52.3% and 49.9% were obtained experimentally, which was the response model reecting the expected optimization of the oil
not signicant due to variation between 59.7% and 59.8%, 51.9% extraction process.
and 52.3%, 49.6% and 49.9%, respectively, below the 5% signicant
50
Experimental and predicted oil yield (%)
45
40
35
30
Experimental values
Predicted values
25
0 2 4 6 8 10 12 14 16 18 20
Experimental runs
Fig. 3. Comparison between experimental and predicted values of oil yield (%) for Fig. 6. Contour plot of oil yield for petroleum ether, as affected by extraction time
petroleum ether. and average particle size.
J.M. Danlami et al. / Journal of the Taiwan Institute of Chemical Engineers 47 (2015) 99104 103
3.4. Physicochemical properties of castor seed oil found in the present study. The ndings reveals no signicant
deviations in the fatty acid proles due to lack of selectivity of the
The physicochemical properties of the oil, i.e. refractive index soxhlet method, except for the case of eicosenoic acid, which was
(physical property), unsaponable matter, volatile matter, free highest for the n-hexane extracted oil with a value of 6.1%,
fatty acid, phospholipid, peroxide value, iodine value, saponica- followed by the ethanol extracted oil with 4.3% and nally, the
tion value and acid value (chemical properties) of the castor seed petroleum ether extracted oil with 3.7%. The rich source of
oil were characterized. The ethanol, n-hexane and petroleum ether ricinoleic (C18:1vOH), suggested that the oil is suitable for use as a
extracted oils show refractive indices of 1.4771, 1.4770 and 1.4772, new material for paints, coatings, inks, lubricants, plasticizers as
respectively, which indicate a saturation level of the oil [19]. All well as a broad scope of various merchandise. This vegetable oil is
oils were within the range of 1.476 to 1.479 according to the unique due to the presence of an elevated concentration of
American Standard for Testing Materials (ASTM) [20]. The ethanol, hydroxyl fatty acid [25].
n-hexane and petroleum ether extracted oils were determined to
contain unsaponiable contents of 0.6, 0.45 and 0.5%, volatile 3.6. Polarity effect
contents of 0.48, 0.55 and 0.28%, free fatty contents of 0.8, 0.3 and
0.27%, phospholipid values of 0.03, 0.05 and 0.03%, respectively. Various seed materials typically contain solute molecules with
The peroxide value, a measure of the extent of primary oxidation, more than one functional group. Therefore, the solubility of these
for ethanol, n-hexane and petroleum ether extracted oils of 12, solutes in a particular solvent is generally difcult to predict. The use
3.3 and 3.5 meq/kg of oil, respectively exhibited low values for n- of the concept of polarity is considered another means of evaluating
hexane and petroleum ether. Iodine values of 85.6, 84.5 and 85 of solubility. Polarity is the ability of molecules to interact with other
gI2/100 g of oil, respectively, indicating the degree of unsaturation, polar molecules [26]. Therefore, the ability of a molecule to enter
were high; therefore, all the oils could be classied as non-drying into interactions of all types is referred to as polarity, and the relative
because their iodine values are lower than 100 gI2/100 g of oil. An polarity is regarded as the sum of all the interactions [27].
iodine value of 180 signies a good drying oil [21]. Saponication The oil yield extracted using a polar organic solvent containing
values for ethanol, n-hexane and petroleum ether extracted oils of hydroxyl groups, namely ethanol, was higher than that using non-
174.6, 176.3 and 173.8 mg of KOH/g of oil, respectively, observed polar organic solvents, such as n-hexane and petroleum ether. The
were within 175250 established in some seed oils as safower, solubility properties of ethanol are higher because of the hydroxyl
corn, sunower and raspberry [22]. These values obtained indicate group, which is hydrophilic. Fatty acids contain a polar hydrocar-
the requirement to neutralize the available free fatty acid liberated bon molecule, and therefore, they dissolve better in ethanol
by the oil with more alkali. The average molecular weight of the [28]. Ethanol has a higher boiling point than either n-hexane or
fatty acids in the oil fraction is reported to be inversely related to petroleum ether. The problems associated with high temperature
the saponication value [21]. Oil with saponication values of are that the reaction is accelerated, including the side reactions.
200 mg KOH/g and above; is reported to have low molecular fatty Thus, the use of this polar solvent increases the solubility, and
weight acids [21]. Acid values for ethanol, n-hexane and petroleum subsequently the yield of the extracts. Solvents of low polarity,
ether were 1.60, 0.60 and 0.53 mg of KOH/g of oil, respectively. The such as n-hexane and petroleum ether, do not extract much oil as
acid value is indicative of spoilage, and it also represents free fatty ethanol. Therefore, the use of a polar solvent might be favoured
acid content due to enzymatic activity. An acceptable maximum when the removal of undesirable components may be necessary in
level is 4 mg KOH/g oil as per recommended international the pre-extraction step.
standards [23]. The high acid value shown by the ethanol extract
is the result of the presence of free fatty acids. Thus, in n-hexane 4. Conclusions
and petroleum ether extracts, the hydrolytic and lipolytic activities
are at low levels due to the presence of low levels of free fatty acids Three solvents were employed for extracting oil from the seeds
in the oils. Thus, the acid value can be reduced by subjecting the oil of the castor oil plant (R. communis L.) using the soxhlet method,
to rening [21]. Therefore, these physicochemical characteristics and the characteristics of the extracted oils were evaluated.
demonstrate that the castor seed oil extracted in the present study Statistical analyses showed that the average particle size and
is an excellent candidate for use in the oleo-chemical industry. the extraction time were signicant parameters for determining
the oil yield. The oil yield obtained was modeled as a function
3.5. Fatty acids in castor seed oil of the independent variables, i.e. average particle size and
extraction times, and optimum values of 1.30 mm and 2.88 h,
The fatty acid compositions of ethanol, n-hexane and petroleum 1.26 mm and 2.65 h and 1.25 mm and 2.55 h with predicted yields
ether extracted oil exhibited the presence of eight leading fatty of 59.8%, 52.3% and 49.9% were obtained for ethanol, n-hexane and
acids, as estimated by GC. The relative concentrations of these petroleum ether extracted castor oil, respectively. The optimum
acids for the ethanol extracted oil were determined using (FAME- conditions were within the experimental design, which
mix standards supplied from Sigma-Aldrich Chemical Company) to accounted for 99% of the oil yield after an extended extraction
be palmitic C16:O (1.2%), stearic C18:0 (1.0%), oleic C18:1 (3.9%), time. The refractive indices of ethanol, n-hexane and petroleum
linoleic C18:2 (6.3%), linolenic C18:3 (0.6%), arachidic C20:0 (0.9%), ether extracted oil were 1.4771, 1.4770 and 1.4772, respectively.
eicosenoic C20:1 (4.3%) and ricinoleic C18:1vOH (81.8%). The The extracted oils were determined to contain unsaponiable
relative concentrations of these acids for the n-heaxne extracted oil contents of 0.6, 0.45 and 0.5%, volatile contents of 0.48, 0.55 and
were palmitic C16:0 (1.2%), stearic C18:0 (1.0%), oleic C18:1 (3.7%), 0.28%, free fatty contents of 0.8, 0.3 and 0.27%, phosphorlipid
linoleic C18:2 (6.7%), linolenic C18:3 (0.5%), arachidic C20:0 (1.2%), values of 0.03, 0.05 and 0.03%, respectively. The peroxide values
eicosenoic C20:1 (6.1%) and ricinoleic C18:1vOH (79.6%). The were 12, 3.3 and 3.5 meq of O2/kg, the iodine values were 85.6,
relative concentrations for the petroleum ether extracted oil were 84.5 and 85.0 g of I2/100 g of oil, the saponication values were
palmitic C16:0 (1.2%), stearic C18:0 (1.1%), oleic C18:1 (4.2%), 174.6, 176,3 and 173.8 mg of KOH/g of oil and the acid values were
linoleic C18:2 (7.1.%), linolenic C18:3 (0.5%), arachidic C20:0 1.6, 0.6 and 0.53 mg of KOH/g of oil, respectively. For the ethanol,
(1.0%), eicosenoic C20:1 (3.7%) and ricinoleic C18:1vOH (81.2%). n-hexane and petroleum ether extracted oils palmitic C16:0 (1.2,
The dominant fatty acids within castor seed oil have previously 1.2 and 1.2%), stearic C18:0 (1.0, 1.0 and 1.1%), oleic C18:1 (3.9,
been determined [24], which are similar to the concentrations 3.7 and 4.2%), linoleic C18:2 (6.3, 6.7 and 7.1%) and ricinoleic
104 J.M. Danlami et al. / Journal of the Taiwan Institute of Chemical Engineers 47 (2015) 99104
C18:1vOH (81.8, 79.6 and 81.2%) were determined to be the major [11] Montgomery DC. Design and analysis of experiments. 6th ed. New York, U.S.A.:
John Wiley & Son Inc.; 2005.
fatty acids, and the physicochemical compositions indicated a rich [12] Liu z, Mei L, Wang Q, Shao Y, Tao Y. Optimization of subcritical uid extraction
source of ricinoleic acid, which has signicant potential as an of seed oil from Nitraria tangutorum using response surface methodology.
industrial oil. LWTFood Sci Technol 2014;56:16874.
[13] Mitra P, Hosahalli SR, Chang KS. Pumpkin (Cucurbia maxima) seed oil extrac-
tion using supercritical carbon dioxide and physiocochemical properties of the
Acknowledgements oil. J Food Eng 2009;95:20813.
[14] Ixtaina V, Veag a, Nolasco SM, Tomas MC, Gimeno M, Barzana E, et al.
Supercritical carbon dioxide extraction of oil from Mexican chia seed (Salvia
The authors would like to express their sincere appreciation to hispanica L.): characterization and process optimization. J Supercrit Fluids
Universiti Teknologi Malaysia (UTM), 81310 Johor Bahru, Malaysia, 2010;55:1929.
for nancial support of this work under the grant (No. 07J58) and [15] Shehu MSZ, Abdul Manan SR, Wan Alwi. Optimization of thermo-alkaline
disintegration of sewage sludge for enhanced biogas yield. Bioresour Technol
International Doctoral Fund and to the director of the Centre of 2012;114:6974.
Lipid Engineering and Applied Research (Clear), Dr. Mohd Azizi Che [16] Cornell JA. How to apply response surface methodology. Revised edition.
Yunus, 81310 UTM Johor Bahru, Malaysia. Tammy Grifn, United State of America: Book Crafters; 1990.
[17] Guan X, Yao H. Optimization of viscozyme L assisted extraction of oat bran
protein using respond surface methodology. Food Chem 2008;106:345435.
References [18] Muralidhar RV, Chirumamila RR, Marchant R, Nigam P. A response surface
approach for the comparison of lipase production by Candida cylindracea using
[1] Cosmetic Ingredient Review Expert Panel. Final report on the safety assess- two different carbon sources. Biochem Eng J 2001;9:1723.
ment of Ricinus communis (Castor) seed oil. Int J Toxicol 2007;26:3177. [19] Oderinde RA, Ajayi IA, Adewuyi A. Characterization of seed and seeds oil of
[2] Weiss E. A. Castor. In Oilseed Crops, 2nd Edition, Blackwell Scientic Ltd, Hura Crepitans and the kinetics of degradation of the oil during heating.
Oxford, 2005: 13-52 Electron J Environ Agric Food Chem 2009;8:2018.
[3] Mutlu H, Meier ARM. Castor oil as a renewable resource for the chemical [20] ASTM International. Standard test method for oxidation onset temperature of
industry. Eur J Lipid Sci Technol 2010;112:1030. hydrocarbons by differential scanning calorimetry. Annual book of standards
[4] Food and agriculture organization of the united nations (FAOSTAT). FAO; 2008, section 12.10, West Conshohocken: ASTM International; 2002.
Online http://faostat.fao.org. [21] Abayeh OJ, Aina EA, Okuonghae CO. Oil content and oil quality characteristics
[5] Danh LU, Mammucari R, Truong P, Foster N. Response surface method applied of some Nigerian oil seeds. J Pure Appl Sci 1998;1:1723.
to supercritical carbon dioxide extraction of vetiveria zizanoides essential oil. [22] Yong OY, Salimon J. Characteristics of Elateriospermum tapos seed oil as a new
Chem Eng J 2009;155:61726. source of oilseed. Ind Crops Prod 2006;24:14651.
[6] Rezzoug SA, Boutekedjiret C, Allaf K. Optimization of operating conditions of [23] CODEX Alimentarius Commission. Recommended international standards for
rosemary essential oil extraction by a fast controlled pressure drop process edible Arachis oil. 1st ed, Rome: FAO/WHO; 1982.
using response surface methodology. J Food Eng 2005;71:917. [24] Scholz V, Silva JND. Prospect and risks of the use of castor oil as a fuel. Biomass
[7] Akpan UG, Jimoh A, Mohammed AD. Extraction, characterization and modi- Bioenergy 2008;32:95100.
cation of castor seed oil. Leonardo J Sci 2006;8:4352. [25] Ogunniyi DS. Castor oil: a vital industrial raw material. Bioresour Technol
[8] Shridhar BS, Beena KV, Anita MV, Paramjeet KB. Optimization and characteri- 2006;97:108691.
zation of castor seed oil. Leonardo J Sci 2010;17:5970. [26] Barwick VJ. Strategies for solvent selectiona literature review. Trends Anal
[9] Salimon J, Dina AMN, Nazrizawati AT, Firdausi MYM, Noraishah A. Fatty acid Chem 1997;16:293309.
composition and physicochemical properties of Malaysian castor beans Ricinus [27] Kumoro AC, Hassan M, Singh H. Effects of solvent properties on soxhlet
communis L. seed oil. Sains Malays 2010;39:7614. extraction of diterpenoid lactones from andrograhis paniculata leaves. Sci Asia
[10] Bas D, Boyaci IH. Modeling and optimization I: usability of response surface 2009;35:3069.
methodology. J Food Eng 2007;78:83645. [28] Wade Jr LG. Organic chemistry. Prentice-Hall, NJ: Englewood Cliffs; 1987.