Professional Documents
Culture Documents
1 - Extraction of Oil From Uncrushed Olives Using Supercritical Fluid PDF
1 - Extraction of Oil From Uncrushed Olives Using Supercritical Fluid PDF
a r t i c l e i n f o a b s t r a c t
Article history: Many countries around the world grow olive trees as olives and olive oil are considered very important
Received 2 August 2014 food constituents. Current extraction methods are considered classical methods which mainly imply size
Received in revised form 23 October 2014 reduction of olives, and then separation of the extracted oil. This study aimed at studying the propen-
Accepted 23 October 2014
sity of supercritical fluid extraction (SCFE) of olives from Jordan without prior size reduction (crushing).
Available online 31 October 2014
Different parameters were investigated including operating pressure, operating temperature, and extrac-
tion duration. The study involves both experimental design analysis and parameter investigation. Results
Keywords:
have indicated that it is possible to perform SCFE of olives without any size reduction. It was found that
Supercritical extraction
CO2
the maximum yield obtained at the conditions of this study was 12.3 wt% while these results have shown
Olive that the most effective parameter is the extraction time, followed by the operating temperature and lastly
Olive oil by the operating pressure. An experimental model was developed in this study to predict the extraction
yield as a function of these mentioned parameters.
© 2014 Elsevier B.V. All rights reserved.
1. Introduction this process requires more labor than other extraction methods.
The pressing process is not continuous, and the filter mats can eas-
Olive oil is considered among the important edible oils. Olive oil ily become contaminated. Selective filtration or Sinolea process is
is mainly used in cooking, and it is also used as a cosmetic mate- the opposite of the press system since no pressure is applied to the
rial as well as in physiotherapy. Old Egyptians, Greek, and Romans paste. It depends on the machine which has stainless steel blades
mixed olive oil with flower to produce medications and cosmet- that dip into the paste. Only oil adheres to the metal plates, and the
ics. Olive oil contains many chemicals like fatty acid, polyphenols, adhering oil then drips off the blades into a separate container while
and vitamins (E, K, and A) [1]. In Jordan, olive trees are considered the solids and water are left behind. Because of the lack of pressure,
the most important fruit trees, they are found almost all over the these olive oil extraction processes produce light oil with unique
country where around one million trees are planted annually. Olive quality and value. In Decanters’ process (two-phase or three-phase
trees occupy not less than 110,000 ha being harvested between process) olive paste or olive juice containing both water and oil are
September and November with an oil content of (15–33 wt%), val- allowed to remain in containers until the oil, with a lower spe-
ued at 30 million USD in 2009 [2]. cific gravity, rises to the top naturally. The oil is then decanted
There are several methods of oil extraction from olive trees. away from the remaining water and solid material. This natural
Main methods of extraction include the traditional press, the selec- separation takes considerable time, and not only the contact of oil
tive filtration – Sinolea process, and the decanters method. Pressing with enzymes may breakdown the products, but also this ferment-
is the oldest method in the olive oil extraction processes. It involves ing fruit water may produce defective oil. Modern decanters are
applying pressure to stacked filter mats, smeared with olive pastes large horizontal centrifuges that separate the oil from the solids and
generated by crushing, that alternate with metal disks; a central water in the same process as in a decantation tank, just faster. The
spike allows the extracted oil and water (olive juice) to the next savings in time increase the efficiency of the system, but decrease
step of separation. The machinery; however, is cumbersome since the contact time with the fermenting fruit water.
In Jordan, olive oil is generally separated from olive by mechan-
ical means. This requires a complex mechanism involving crushing
∗ Corresponding author. Tel.: +962 27201000; fax: +962 27201074. the olives, screening, and centrifugation. Therefore, a need for new
E-mail address: awni otoom@just.edu.jo (A. Al-Otoom). separation processes has emerged to provide an easier, cheaper,
http://dx.doi.org/10.1016/j.supflu.2014.10.023
0896-8446/© 2014 Elsevier B.V. All rights reserved.
A. Al-Otoom et al. / J. of Supercritical Fluids 95 (2014) 512–518 513
simpler or more efficient separation process than the traditional SCFE was performed on crushed olives from some countries like
processes. Among such extraction techniques is the suggested Portugal and Spain. Results have indicated that SCFE of olive oil
method of direct supercritical extraction system of olive fruit in does not alter the nutrition value of the olive oil [17]. It has also
which a supercritical fluid, normally CO2 , is used for the extraction been shown that SCFE results in a yield of 80% relative to hexan
process. soxhlet extraction with the smallest particle size [18].
The ability of supercritical fluid (SCF) to dissolve solid material The present work represents a preliminary investigation aimed
was first reported by Hannay and Hogarth in 1897 [3]; however, to establish the propensity of extracting oil from Jordanian olive
but the application of supercritical fluid extraction (SCFE) in indus- fruits using SCFE CO2 solvent, without the commonly needed size
trial process such as decaffeination [4], food industry [4], and reduction of the olive fruit. It is believed that avoiding crushing
wastewater treatment [5] has been relatively recently explored. of the olive fruit will not only reduce the power consumption and
Supercritical fluid extraction (SCFE) has many advantages among operation cost of olive extraction process, but it will also increase
other separation methods as it yields extremely clean and abso- the separation capability between olive fruit and the oil. In addition,
lutely solvent free extracts. Also, unlike traditional methods, it avoiding size reduction is believed to reduce the contamination of
greatly reduces or eliminates the oxidation rate of the components. olive oil with impurities from size reduction machineries. More-
In addition, the used solvent, for example carbon dioxide, is pre- over, the suggested process will largely reduce the effluent of
ferred since it is nonflammable, nontoxic, naturally abundant and wastewater, resulted by the traditional extraction methods, that
less expensive compared to most of the conventional solvents [6]. contains chemical pollutants which require further investment for
The CO2 supercritical extraction process eliminates the need for wastewater treatment. This study will also present the effect of
potentially harmful solvents like hexane that is often used in the operating pressure, operating temperature, and the extraction time
manufacture of absolute oils, avoiding unnecessary environmen- on the yield of extraction of uncrushed olives.
tal pollution and potential human bodily harm. Fortunately, CO2
can penetrate the solid sample faster than liquid solvents due to its 2. Materials and methods
fluidity property, and complete separation of CO2 always results
in a pure extract. However, the SCFE process exhibits high operat- 2.1. Materials
ing pressures which lead to relatively high operating cost as well
as the need for specialized equipment and dissolves non-polar or Nabali Olives were collected from the campus of Jordan Uni-
slightly polar compounds [6]. SCF is being used to extract oil from versity of Science and Technology at three different periods. The
black pepper [7], peach [8], jojoba [9], avocado [10], grape seeds general analysis of the olive oil using GC (GC–MS method using
[11], Lavender [12], Lutein [13], and many other fruits or medicinal Varian 450-GC, British) indicated that it contains fatty acid, ester,
herbs. SCFE was even performed on trees leaves including those of phenols and vitamins in addition to other components that exist
olive trees [14] in minor quantities. Carbon dioxide was used as the supercritical
SCFE has been demonstrated earlier that it can be a competi- solvent. It was supplied with 99% purity. Also acetone (99.9%, w/w,
tive with conventional solvent extraction [15] since it omits the supplied from ACROS ORGANICS) was used as a washing solvent.
need for solvent distillation. Extraction of oil from black pepper
using supercritical extraction technique has been investigated by
2.2. Experimental apparatus
Perakis et al. [7]. According to the authors, as supercritical car-
bon dioxide (SC-CO2 ) flows through the void spaces of the feed
The extraction apparatus is installed as shown in Fig. 1; it con-
black pepper, solute (oil) gets dissolved in it. The extraction pro-
sists of a 300 cm3 stainless steel extract unit (H = 15 cm, D = 4.5 cm)
cess is primarily divided into two distinct stages; initial constant
which is inserted into a glass water bath where its temperature
extraction rate stage, where the easily accessible solute available
is controlled by a thermostat in order to raise the temperature
on the external surface of the feed particles gets extracted. In this
above the critical temperature. A 99% CO2 is supplied from an exter-
stage, solubility of the solute controls the extraction rate. The sec-
nal cylinder (pressure is 5.4 MPa). Two needle valves are used to
ond stage is the falling extraction rate, where the easily accessible
isolate the extraction cell in order to perform the batch experi-
oil gets depleted and the diffusion mechanism controls the extrac-
ments. SFT-10 supercritical carbon dioxide pump is used to increase
tion process. The transition from a constant rate regime to a falling
the pressure beyond the critical pressure. A risk assessment for
rate regime depends on the initial oil content in the solid sub-
proposed experimental procedure was obtained. The apparatus
strate as well as the cell structure of the natural material. The
was tested at a high pressure reaching 27 MPa without any leak
extraction of black pepper essential oil was carried up in the tem-
detected, and safety steps were considered during the experimental
perature range of (303–323) K and pressure range of (15–30) MPa
test.
[7].
SCFE was also used in association with other preparation of
substrates such as freeze drying. Ye and Lai [16] have used the
freeze drying method for onion powder to extraction the important
organosulfur-containing compounds.
Peach contains 50wt% of oil, so it is considered as an important
source of oil for food and nutraceuticals supplements industries.
Extraction of oil from peach was studied by Sanchez-Vicente et al.
[8] using supercritical carbon dioxide at temperatures of 40 and
51 ◦ C and pressures of 15 and 20 MPa. At optimum cell size and
optimum flow rate of the solvent, the yield was 70% of that obtained
by extraction in liquid hexane, which means that the yield of SCFE is
lower than that of conventional extraction. The addition of a small
amount of a liquid co-solvent such as ethanol (5 mol%) enhanced
significantly the extraction of polar compound. Depressurization
Fig. 1. Experimental setup for the SCFE experiments for olive oil. (1) CO2 cylinder,
after extraction allowed complete separation of the oil and gaseous (2) SFE pump (SF-10), (3) needle valve, (4) pressure gage, (5) extraction cell, (6)
carbon dioxide. water bath, (7) thermostat, (8) trap.
514 A. Al-Otoom et al. / J. of Supercritical Fluids 95 (2014) 512–518
Fig. 3. Effect of temperature on oil yield using CO2 SCE. Contact time: 150 min;
pressure: 24 MPa.
3.2.3. Effect of extraction time In this case, all the data in the experiment (Table 2) should be used
The effect of time was studied over periods of 15–150 min at to estimate each main effect and interaction effect, and each of
constant pressure and temperature of 24 MPa and 60 ◦ C, respec- these can be estimated independently of the other effects. This fea-
tively, as shown in Fig. 6. It is seen that increasing the contact time ture of 2n effect is referred as hidden replication, giving maximum
increases the yield. This is also found by de Souzaa et al. [20]. Such information per experimental run [22]. A Summary of the calcula-
trend is due to intimate contact between the CO2 and the vegetative tion procedure is shown in Table 3 for the response variable Y. It
material, which leads to better opportunity for the oil to transfer is important to mention that the factorial design model used the
into the super critical phase (CO2 ). experimental results based on the highest and the lowest values of
the operating parameters, i.e. the eight data points in Table 2.
3.3. Modeling of the experimental results Thus, according to the calculations displayed in Table 3, the
effect of increasing pressure 10–24 MPa, averaged over all levels
3.3.1. Factorial design model of temperature and contact time, is to increase yield by 1.1%. Also,
The factorial design yielded results pertaining to the main oper- the effect of increasing the temperature 45–60 ◦ C is to increase the
ating parameters and interaction parameters. yield by 3%. The effect of increasing the contact time from 15 to
Eq. (1) is used to represent the parameters in a dimensionless 150 min is to increase the yield by 6%. Thus, it can be concluded
form: that contact time is the most contributing parameter to the yield
followed by temperature and then pressure.
Value of operating variable − 0.5 × (upper limit + lower limit)
Xi = The importance of each term in Eq. (4) on the correspond-
(Upper limit − lower limit) × 0.5
ing response can be assessed by giving a confidence interval for
(1)
each parameter. Accordingly, if the confidence interval for a given
parameter contains the point zero, it means that the term associ-
The complete factorial model that can be used to fit the data in ated with such parameter is not important and can be excluded
Table 2 is from the model. The confidence interval for the least squares
parameter estimates is given by [23]:
E(Y ) = ˇ0 + ˇ1 X1 + ˇ2 X2 + ˇ3 X3 + ˇ12 X1 X2 + ˇ13 X1 X3
1/2
ˆ i ± t,˛ [V (ˇ
ˇ ˆ i )] (6)
+ ˇ23 X2 X3 + ˇ123 X1 X2 X3 (2)
where the parameters ˇi are responsible for the influence of the where t,˛ is student’s statistics, is the degrees of freedom associ-
operating variable Xi on the response Y, while ˇij and ˇijk are param- ated with the pure variance, 2 , and ˛ is the probability limit. The
eters responsible for the possible interactions among the operating pooled variance, p2 , can be used as an estimate of the pure error
variables i, j and k, and the effect of this interaction on the response. variance and is given by
Values of the parameters displayed in Eq. (2) can be obtained from l
i=1
(mi − 1)i2
the least square estimates: p2 = l (7)
−1 i=1
(mi − 1)
T
ˆ = (X X) T
ˇ X Y (3)
where l is the total number of replicates available in the data set,
The matrix X represents the matrix of the operating variables at mi is the number of data points in the ith set of replicates and i2 is
different runs. The elements of the columns of X associated with the estimate of the pure error variance in the set of replicates. The
the interaction terms X1 X2 , X1 X2 X3 are the products of the corre- i
term i=1
(mi − 1) represents the degrees of freedom associated
sponding elements in the columns associated with X1 , X2 and X3 . i 2
The matrix XT X is an 8 × 8-symmetrical-square matrix with diag- with p2 . The sample variance i=1
((y − Ȳ ) /(n − 1)) can be used
onal elements each equals to 8, and off-diagonal elements each as estimate of the variance i2 .
equal to zero. Therefore, (XT X)−1 is also 8 × 8-symmetrical-square Replicates for some runs for the purpose of statistical analyses
matrix with diagonal elements each equal to 1/8, and off-diagonal are shown in Table 4 along with calculation of standard deviation
elements each equal to zero. Because XT X is a diagonal matrix, each (i.e. i ). As seen, the resulting degrees of freedom is = 6; thus,
of the parameter estimates in Eq. (2) can be calculated indepen- for 95% confidence interval, the t,˛ is 2.447. Since V (ˇ ˆ i ) of each
dently of the other parameters. That is, the parameter estimates are parameter estimate in Eq. (6) is 2 /23 , then the 95% confidence
A. Al-Otoom et al. / J. of Supercritical Fluids 95 (2014) 512–518 517
Table 3
Calculations and results for main effects and interaction effects for the response variables Y1 , Y2 and Y3 .
X1 X2 X3 X1 X2 X1 X3 X2 X3 X1 X2 X3
12.37 +1 +1 +1 +1 +1 +1 +1
6.64 +1 +1 −1 +1 −1 −1 −1
8.42 +1 −1 +1 −1 +1 −1 −1
4.16 +1 −1 −1 −1 −1 +1 +1
12.0 −1 +1 +1 −1 −1 +1 −1
4.30 −1 +1 −1 −1 +1 −1 +1
6.80 −1 −1 +1 +1 −1 −1 +1
a
1.70 −1 −1 −1 +1 +1 +1 −1
+Y 29.45 33.31 39.59 25.51 26.79 30.18 27.58
− Yb 24.8 21.04 14.76 28.84 27.56 24.16 26.76
Difference effect for Y1 1.186 3.068 6.208 −0.831 −0.191 1.506 0.206
a
+ corresponds to the sum of the responses at high Xi .
b
− corresponds to the sums of the responses at low Xi .
× (P − Pc )2 + 0.0393 × t (11)
All the results obtained in this study were utilized in this model.
The statistical analysis using JMP programming results are shown where T is the operating temperature in ◦ C,
and Tc is the critical
in Fig. 7. Such diagram shows the analysis for the effect of dif- temperature in ◦ C, P is the operating pressure in psi, Pc is the critical
ferent variables and their combinations on the yield. It is noticed pressure in psi, and t is the extraction time in minutes.
that the most significant parameters are; time, T − Tc and (P − Pc )2 ,
the remaining combinations do not have significant contributions.
Therefore, the most appropriate model that includes the variables
Table 4
Experimental results of replicates.
12.14
1 1 0.325
12.60
4.40
2 1 0.332
4.87
4.00
4 1 0.163
4.23
11.14
5 1 1.209
12.85
7.50
7 1 0.99
6.10
1.72
8 1 0.035
1.67
Pooled variance, 2 p 0.382 Fig. 8. Actual yield versus predicted yield calculated from the driving force experi-
mental model.
518 A. Al-Otoom et al. / J. of Supercritical Fluids 95 (2014) 512–518
[3] (a) M.A. McHugh, V.J. Krukonis, Supercritical Fluid Extraction: Principles and
Practice, 2nd ed., Butterworth-Heinemann, Boston, 1994;
(b) M.P. Hulya Peker, J.S. Srinvasan, B.J. McCoy, Caffeine extraction rates from
coffee beans with supercritical carbon dioxide, J. AIChE 38 (1992) 761–769.
[4] S. Mohamed, G.A. Mansoori, The Use of Supercritical Fluid Extraction Tech-
nology in Food Processing. Featured Article – Food Technology Magazine, The
World Markets Research Centre, London, UK, 2002.
[5] D. Ghonsagi, S. Gupta, K.M. Dooley, F. Knopf, Measurement and modeling of
supercritical carbon dioxide extraction of phenol from water, J. Supercritical
Fig. 9. Error estimation of the parameters of the driving force model using JMP Fluids 4 (1991) 53–59.
program. [6] I. Norhuda, K. Jusoff, Supercritical carbon dioxide (SC-CO2 ) as a clean technology
for palm kernel oil extraction, J. Biochemical Technology 3 (2009) 75–78.
[7] C. Perakis, V. Louli, K. Magoulas, Supercritical fluid extraction of black pepper
Fig. 8 shows the relation between the yield obtained from the oil, J. Food Engineering 71 (2004) 386–393.
[8] Y. Sanchez-Vicente, A. Cabanas, J. Renuncio, C. Pando, Supercritical fluid extrac-
experiments and the yield as calculated using Eq. (11). The corre-
tion of peach (Prunus persica) seed oil using carbon dioxide and ethanol, J.
lation coefficient (R) indicates an agreement of the model to the Supercritical Fluids 49 (2009) 167–173.
experimental data. [9] U. Salgın, Extraction of jojoba seed oil using supercritical CO2 + ethanol mix-
The outcome shows that the pressure driving force and hence ture in green and high-tech separation process, J. Supercritical Fluids 39 (2007)
330–337.
mass transfer of CO2 has the most significant effect on the extrac- [10] B. Botha, R. McCrindle, Supercritical Fluid Extraction of Avocado Oil, South
tion yield of olive oil. The JMP program provides sensitive analysis African Avocado Growers’ Association Yearbook, 2003.
for the model parameters by providing an error determination for [11] C.P. Passos, R.M. Silvaa, F.A. Da Silvaa, M.A. Coimbrab, C.M. Silvaa, Supercritical
fluid extraction of grape seed (Vitis vinifera L.) oil. Effect of the operating con-
each parameter, as well as the t-ratio as shown in Fig. 9. ditions upon oil composition and antioxidant capacity, Chemical Engineering
J. 160 (2010) 634–640.
4. Conclusions [12] S.M. Ghoreishi, H. Kamali, H.S. Ghaziaskar, A.A. Dadkhah, Optimization of super-
critical extraction of linalyl acetate from lavender via Box–Behnken design,
Chemical Engineering Technology 35 (9) (2012) 1641–1648.
The following conclusion remarks can be drawn from this work: [13] D. Ruen-ngam, A. Shotipruk, P. Pavasant, S. Machmudah, M. Goto, Selective
extraction of lutein from alcohol treated chlorella vulgaris by supercritical CO2 ,
Chemical Engineering Technology 35 (2012) 255–260.
(1) SCFE of uncrushed olives can be a viable process; thus reducing [14] F. Le Floch, M.T. Tena, A. Ros, Supercritical fluid extraction of phenol compounds
the cost of operation and increasing the separation propensity from olive leaves, Talanta 46 (1998) 1123–1130.
between solids and the extracted oil. [15] A.M. Gomez, C.P. Lopez, E.M. Ossa, Recovery of grape seed oil by liquid and
supercritical carbon dioxide extraction: a comparison with conventional sol-
(2) The yield was found to be mostly affected by the SCFE residence vent extraction, Chemical Engineering J. 61 (1996) 227–231.
time, followed by lower degree by the operating temperature [16] C.-L. Ye, Y.-F. Lai, Supercritical CO2 extraction optimization of onion oil using
and lastly by the operating pressure. The maximum value of response surface methodology, Chemical Engineering Technology 35 (2012)
646–652.
the oil yield obtained was 12.37% at 24 MPa, 60 ◦ C and 150 min.
[17] P. Simões, P. Carmelo, J.P.J. Pereira, J.A. Lopes, M. Nunes da Ponte, Quality assess-
Therefore, the process condition of 10 MPa, 60 ◦ C and 150 min ment of refined olive oils by gas extraction, J. Supercritical Fluids 13 (1998)
are considered the optimum due to highest yield and a rela- 337–341.
tively low cost. [18] A. De Lucas, J. Rincon, I. Gracia, Influence of operating variables on yield and
quality parameters of olive husk oil extracted with supercritical carbon dioxide,
J. American Oil Chemical Society 80 (2002) 181–188.
Acknowledgment [19] M. Bimakr, R.A. Rahman, F.S. Taip, L.T. Chuan, A. Ganjloo, J. Selamat, A. Hamid,
Supercritical carbon dioxide (SC-CO) extraction of catechin, epicatechin, 2 Rutin
and Luteolin from Spearmint (Mentha spicata L.) leaves, World Applied Sciences
The authors would like to acknowledge the support from the J. 5 (2008) 410–417.
university of Science and Technology in Jordan to complete this [20] A. Teixeira de Souzaa, T.L. Benazzia, M.B. Gringsa, V. Cabrala, E. Antônio da Sil-
work. vac, L. Cardozo-Filhoa, C.O.A. Antunesb, Supercritical extraction process and
phase equilibrium of Candeia (Eremanthus erythropappus) oil using supercriti-
cal carbon dioxide, J. Supercritical Fluids 47 (2) (2008) 182–187.
References [21] U. Salgın, O. Döker, A. Çalımlı, Extraction of sunflower oil with supercritical
CO2 : experiments and modeling, J. Supercritical Fluids 38 (2006) 326–331.
[1] J. Tous, L. Ferguson, Mediterranean Fruits, ASHS Press, Arlington, VA, 1996. [22] T.D. Murphy Jr., Design and analysis of industrial experiments, Chemical Engi-
[2] Jordan Ministry of Planning, Report on export strategies for Jordanian neering 84 (1977) 168–183.
olive oil, Jordan 2002, 2002, Available from: http://www.competitiveness. [23] D.C. Montgomery, G.C. Runger, Applied Statistics and Probability for Engineers,
gov.jo/files/olive.pdf 4th ed., John Wiley & Sons Incorporated, United States of America, 2007.