J.

of Supercritical Fluids 95 (2014) 512–518

Contents lists available at ScienceDirect

The Journal of Supercritical Fluids

journal homepage: www.elsevier.com/locate/supflu

Extraction of oil from uncrushed olives using supercritical fluid

extraction method
Awni Al-Otoom a,∗ , Sameer Al-Asheh b , Mamdouh Allawzi a , Khalid Mahshi a ,
Nahawand Alzenati a , Bader Banat a , Bdour Alnimr a
a
Department of Chemical Engineering, Jordan University of Science and Technology, P.O. Box 3030, Irbid 22110, Jordan
b
Department of Chemical Engineering, American University of Sharjah, P.O. Box 26666, Sharjah, United Arab Emirates

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
Olive oil is considered among the important edible oils. Olive oil
is mainly used in cooking, and it is also used as a cosmetic mate-
rial as well as in physiotherapy. Old Egyptians, Greek, and Romans
mixed olive oil with flower to produce medications and cosmet-
ics. Olive oil contains many chemicals like fatty acid, polyphenols,
and vitamins (E, K, and A) [1]. In Jordan, olive trees are considered
the most important fruit trees, they are found almost all over the
country where around one million trees are planted annually. Olive
trees occupy not less than 110,000 ha being harvested between
September and November with an oil content of (15–33 wt%), val-
ued at 30 million USD in 2009 [2].
There are several methods of oil extraction from olive trees.
Main methods of extraction include the traditional press, the selec-
tive filtration – Sinolea process, and the decanters method. Pressing
is the oldest method in the olive oil extraction processes. It involves
applying pressure to stacked filter mats, smeared with olive pastes
generated by crushing, that alternate with metal disks; a central
spike allows the extracted oil and water (olive juice) to the next
step of separation. The machinery; however, is cumbersome since
∗ Corresponding author. Tel.: +962 27201000; fax: +962 27201074.
E-mail address: awni otoom@just.edu.jo (A. Al-Otoom).
this process requires more labor than other extraction methods.
The pressing process is not continuous, and the filter mats can eas-
ily become contaminated. Selective filtration or Sinolea process is
the opposite of the press system since no pressure is applied to the
paste. It depends on the machine which has stainless steel blades
that dip into the paste. Only oil adheres to the metal plates, and the
adhering oil then drips off the blades into a separate container while
the solids and water are left behind. Because of the lack of pressure,
these olive oil extraction processes produce light oil with unique
quality and value. In Decanters’ process (two-phase or three-phase
process) olive paste or olive juice containing both water and oil are
allowed to remain in containers until the oil, with a lower spe-
cific gravity, rises to the top naturally. The oil is then decanted
away from the remaining water and solid material. This natural
separation takes considerable time, and not only the contact of oil
with enzymes may breakdown the products, but also this ferment-
ing fruit water may produce defective oil. Modern decanters are
large horizontal centrifuges that separate the oil from the solids and
water in the same process as in a decantation tank, just faster. The
savings in time increase the efficiency of the system, but decrease
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
the olives, screening, and centrifugation. Therefore, a need for new
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

2.3. HPLC analysis

HPLC analysis was performed to qualitatively determine the

main components found in the extracted olive oil using the method
employed in this study. The analysis was performed at a wave-
length of 280 nm with acetone as the carrier phase.

2.4. Experimental procedure

Olives were dried to 50 ◦ C for 24 h before extraction in order

to remove water content from olives, to prevent emulsion effect
and to accurately calculate the oil extraction yield. Approximately
50 g of dried uncrushed olives were introduced into the basket of
the extraction vessel. The extraction vessel including the basket of
olives is purged with CO2 for 2 min to remove any moisture or impu-
rities from the pump filter. After purging, the exit valve is closed
and the water batch is heated to the required temperature using
the thermostat, and then pressure is set to the desired value using
the control panel of the SF10 pump. Time is recorded upon reach-
ing the desired temperature and pressure, where the extraction can
take place.
At the end of the extraction process, the exit valve is opened
partially to depressurize the system till the system pressure attains Fig. 2. HPLC analysis of the extracted oil using the SCFE method employed in this
the atmospheric pressure. Then, the extraction vessel is opened and study.
the extracted oil was collected in two steps. The first step involved
washing the extracted olive with 40 ml of acetone twice each time Table 1
for a very short period of time (1 min) in order to remove any traces Major components of the extracted olive oil using HPLC.
of the extracted oil on the pulp surface. This procedure was tested Retention time Identified chemical Chemical formula
for unextracted olives and showed that acetone does not perform (min)
any solvent extraction in the 1 min washing time. After washing 15.2 Squalene C30 H50
with acetone, the products (acetone and the extracted olive oil) 17.2 Methyldopa C10 H13 NO4
are then heated at 50 ◦ C until constant mass or complete evapora- 21.1 Palmitic acid C16 H32 O2
tion of the acetone. This constant mass represents the mass of the 22.8 Methyl 13-octadecenoate C19 H38 O2
23.3 6-Octadeceoic acid C18 H34 O2
extracted oil. This evaporation process was at 50 ◦ C, the same tem- 27.4 Bis(2-ethylhexyl)phthalate C24 H38 O4
perature in which fresh olives were dried at. The extracted olives 28.9 Oleic acid, 3-hydroxyprpyl ester C21 H40 O3
were dried again at 50 ◦ C once more after the extraction process, 31.6 Olean-12-en-28-oic acid, C28 H48 O2
and then the dry olives are weighed in order to calculate the change 2,3,23-trihydroxy-, methyl ester
37.7 9,19-Cycloanostan-3-ol,24-methylene. C31 H52 O
in mass between fresh olives and extracted olives. This difference
shall equal the amount of extracted oil in order to close the mass
balance. The percentage yield is then calculated by dividing the
process. Since, there are three independent variables; namely pres-
mass of the oil extracted to the total mass of original olives used in
sure (10 and 24 MPa), temperature (60 and 45 ◦ C), and extraction
each experiment.
time (150 and 15 min); this leads to 23 designs. Such values were
It is important to point out here that most of the oil was removed
selected based on critical condition of CO2 and kinetics of the pro-
from the olive fruit using the SCFE method before using the acetone
cess. Through the use of factorial design, the operating variables
removal step. Acetone was used in this experimental procedure in
influencing the yield can be quantified.
order to accurately calculate the mass of the extracted oil. However,
In the factorial design analysis, the operating variables such as
on industrial SCFE this step would not be necessary.
pressure, temperature, and extraction time were designated as X1 ,
X2 , and X3 ; while yield, as response variable, was designated as
3. Results and discussion Y. A 23 complete factorial design was performed with the values
of these operating variables shown in Table 2. As mentioned pre-
HPLC analysis for the extracted oil was performed to determine viously, this results in eight tests with all possible combinations
a qualitative description of the contents of the extracted oil using
the method employed in this study. The results are presented in
Fig. 2 and summarized in Table 1. Table 2
Two-level factorial design for the olive oil SCFE.

Test # Pressure (psi)a X1 Temperature (◦ C)X2 Time (min)X3 Yield (%)Y1

3.1. Experimental design analysis
1 +1 +1 +1 12.37
The factorial design test involves initially the determination of 2 +1 +1 −1 4.64
3 +1 −1 +1 8.42
an experimental outcome to be examined. The experimental out- 4 +1 −1 −1 4.16
come is the variable that the operating parameter will influence 5 −1 +1 +1 12
and represent a measure of process performance; this is often 6 −1 +1 −1 4.3
referred as response variable. The experimental outcome for this 7 −1 −1 +1 6.8
8 −1 −1 −1 1.7
work is the yield for oil production from olive using CO2 super-
critical extraction. Traditionally, in two-level factorial design the a
24 MPa, 60 ◦ C and 150 min represent the +1 for X1 , X2 and X3 , respectively; while
10 MPa, 45 ◦ C and 15 min represent the −1 for X1 , X2 and X3 , respectively.
response variable is at two levels of each operating variable in the
 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.
of X1 , X2 , and X3 . The response variable Y was measured for each
of these tests as shown in Table 2. These tests were performed
randomly to avoid any time trend or other types of influences on
the experiments. Results of this analysis are used to determine
the most significant parameters affecting the extraction process,
as discussed below. In addition, it is used in the modeling of the
results.
3.2. Effect of SCFE process parameters
The effects of pressure, temperature, and time, as independent
variables, on the oil yield during CO2 super critical extraction were
considered at ranges of temperature and pressure beyond the crit-
ical points.
3.2.1. Effect of extraction temperature
Effect of extraction temperature was investigated in the range
of 45–60 ◦ C at constant pressure and contact time of 24 MPa and
150 min, respectively. The results are shown in Fig. 3. It is seen
that olive oil yield increases with increasing the temperature, such
trend could be due to the increase of oil vapor pressure in the pores
of the olives which enhances the mass transfer phenomena. The
fact that density of CO2 decreases with the increase in temperature
results in a decrease in CO2 solvency power, but in this case the
effect of increasing the oil vapor pressure may be predominant. It
is expected that the olive pores contain liquid oil and the oil vapor
while the CO2 surrounds the external surface of the pores. Increas-
ing the oil vapor may increase the resistance toward the diffusion of
CO2 . At high pressure, the external force applied by CO2 overcomes
the internal vapor pressure resistance, leading to an increase in
the pressure inside the pores which cause the pore to expand and
finally explode, and bring the trapped oil into the CO2 (Fig. 4).
The increase in yield with temperature could also be explained
in terms of the increase in the rate of diffusion of CO2 within the
particles and the decrease in the viscosity with increasing the tem-
perature. Increasing the temperature has also an effect on the oil,
since the oil viscosity and density decrease with increasing the
temperature which facilitates the transfer of oil into the SC phase.
Similar results were also obtained by Bimakr et al. [19], for extrac-
tion of bioactive flavonoid compounds from spearmint leaves. The
authors claimed that the increase in the system temperature leads
to an increase in the molecules speed and their corresponding
kinetic energy; so that the diffusion rate of the CO2 will increase,
and the extraction process will become more efficient, and thus the
yield increases.
515
Fig. 4. Rupture of the olives after SCFE of uncrushed olives.
3.2.2. Effect of extraction pressure
The effect of pressure was studied at a constant temperature of
60 ◦ C and a constant time of 150 min, in which the pressure was in
the range 10–24 MPa. The results are shown in Fig. 5. Two regions
can be noticed, the first one where the yield decreases with increas-
ing the pressure from 10 to 17 MPa. At the beginning of this region
the high temperature results in a high oil vapor pressure within
the pores while the surrounding relatively low pressure results in
a small resistance which allows the oil to move out. Increasing the
pressure around the pores may increase the resistance which leads
to entrapment of the oil within the pores preventing it from leach-
ing into the CO2 ; and thus a decrease in the yield. Similar results
were obtained by Bimakr et al. [19] for extraction of bioactive
flavonoid compounds from spearmint leaves over pressure range
from 20 to 30 MPa. De Souzaa et al. [20] also found that increas-
ing pressure, after certain pressure range, leads to a decrease in
the oil yield during their extraction process of Candeia (Eremanthus
erythropappus) oil using supercritical carbon dioxide. In the second
region, the yield starts to increase with increasing the pressure from
17 to 24 MPa. Such trend could be due to the fact that with increas-
ing pressure the CO2 diffuses rapidly into the pores regardless of
the vapor pressure; also with increasing the pressure the solubil-
ity of oil in CO2 increases because of the increase in CO2 density
(Fig. 5). In addition, at high pressure and constant temperature, the
density of CO2 will increase so as the solvency power leading to an
increase of the oil yield. Such finding was concluded by Salgın et al.
Fig. 5. Effect of pressure on oil yield using CO2 SCE. Contact time: 150 min; temper-
ature: 60 ◦ C.
516 A. Al-Otoom et al. / J. of Supercritical Fluids 95 (2014) 512–518
Fig. 6. Effect of SCFE time on oil yield using CO2 SCF. Pressure: 24 MPa; temperature:
60 ◦ C.
[21] over pressure range 20–60 MPa for the extraction of sunflower
oil using CO2 supercritical fluid.
3.2.3. Effect of extraction time
The effect of time was studied over periods of 15–150 min at
constant pressure and temperature of 24 MPa and 60 ◦ C, respec-
tively, as shown in Fig. 6. It is seen that increasing the contact time
increases the yield. This is also found by de Souzaa et al. [20]. Such
trend is due to intimate contact between the CO2 and the vegetative
material, which leads to better opportunity for the oil to transfer
into the super critical phase (CO2 ).
3.3. Modeling of the experimental results
3.3.1. Factorial design model
The factorial design yielded results pertaining to the main oper-
ating parameters and interaction parameters.
Eq. (1) is used to represent the parameters in a dimensionless
form:
Value of operating variable − 0.5 × (upper limit + lower limit)
Xi =
(Upper limit − lower limit) × 0.5
(1)
The complete factorial model that can be used to fit the data in
Table 2 is
E(Y ) = ˇ0 + ˇ1 X1 + ˇ2 X2 + ˇ3 X3 + ˇ12 X1 X2 + ˇ13 X1 X3
+ ˇ23 X2 X3 + ˇ123 X1 X2 X3
where the parameters ˇi are responsible for the influence of the
operating variable Xi on the response Y, while ˇij and ˇijk are param-
eters responsible for the possible interactions among the operating
variables i, j and k, and the effect of this interaction on the response.
Values of the parameters displayed in Eq. (2) can be obtained from
the least square estimates:
−1
T
ˆ = (X X) T
ˇ X Y
The matrix X represents the matrix of the operating variables at
different runs. The elements of the columns of X associated with
the interaction terms X1 X2 , X1 X2 X3 are the products of the corre-
sponding elements in the columns associated with X1 , X2 and X3 .
The matrix XT X is an 8 × 8-symmetrical-square matrix with diag-
onal elements each equals to 8, and off-diagonal elements each
equal to zero. Therefore, (XT X)−1 is also 8 × 8-symmetrical-square
matrix with diagonal elements each equal to 1/8, and off-diagonal
elements each equal to zero. Because XT X is a diagonal matrix, each
of the parameter estimates in Eq. (2) can be calculated indepen-
dently of the other parameters. That is, the parameter estimates are
mutually uncorrelated. Further, since the variances of the parame-
ˆ are the diagonal elements of (XT X)−1  2 , where
ter estimates, V (ˇ)
 2 is the estimate of pure error variance, it is clear that a 23 design
produces parameter estimates equal variances, namely  2 /8.
Accordingly, calculation of the parameters in Eq. (2) resulted in
the following fitted model:
Ŷ = 6.793 + 0.5939X1 + 1.534X2 + 3.104X3 − 0.416X1 X2
− 0.096X1 X3 + 0.753X2 X3 + 0.103X1 X2 X3 (4)
It is obvious that interactions exist among the operating variables
and that the parameters do not operate independently on the
response (they are not additive).
One of the features of factorial design analysis is the direct esti-
mation of the main effects and interaction effects. The main effect
can be estimated from the difference between the average high-
and low-factor-level responses:
 
{Response at high Xi } − {Response at low Xi }
Main effect of Xi =
{Half the number of factorial runs}
In this case, all the data in the experiment (Table 2) should be used
to estimate each main effect and interaction effect, and each of
these can be estimated independently of the other effects. This fea-
ture of 2n effect is referred as hidden replication, giving maximum
information per experimental run [22]. A Summary of the calcula-
tion procedure is shown in Table 3 for the response variable Y. It
is important to mention that the factorial design model used the
experimental results based on the highest and the lowest values of
the operating parameters, i.e. the eight data points in Table 2.
Thus, according to the calculations displayed in Table 3, the
effect of increasing pressure 10–24 MPa, averaged over all levels
of temperature and contact time, is to increase yield by 1.1%. Also,
the effect of increasing the temperature 45–60 ◦ C is to increase the
yield by 3%. The effect of increasing the contact time from 15 to
150 min is to increase the yield by 6%. Thus, it can be concluded
that contact time is the most contributing parameter to the yield
followed by temperature and then pressure.
The importance of each term in Eq. (4) on the correspond-
ing response can be assessed by giving a confidence interval for
each parameter. Accordingly, if the confidence interval for a given
parameter contains the point zero, it means that the term associ-
ated with such parameter is not important and can be excluded
from the model. The confidence interval for the least squares
parameter estimates is given by [23]:
1/2
ˆ i ± t,˛ [V (ˇ
ˇ ˆ i )] (6)
(2)
where t,˛ is student’s statistics,  is the degrees of freedom associ-
ated with the pure variance,  2 , and ˛ is the probability limit. The
pooled variance, p2 , can be used as an estimate of the pure error
variance and is given by
l
i=1
(mi − 1)i2
p2 = l (7)
i=1
(mi − 1)
(3)
where l is the total number of replicates available in the data set,
mi is the number of data points in the ith set of replicates and i2 is
the estimate of the pure error variance in the set of replicates. The
i
term i=1
(mi − 1) represents the degrees of freedom associated
i 2
with p2 . The sample variance i=1
((y − Ȳ ) /(n − 1)) can be used
as estimate of the variance i2 .
Replicates for some runs for the purpose of statistical analyses
are shown in Table 4 along with calculation of standard deviation
(i.e.  i ). As seen, the resulting degrees of freedom is  = 6; thus,
for 95% confidence interval, the t,˛ is 2.447. Since V (ˇ ˆ i ) of each
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 .

Y1 (%) Main operating variables Dummy factors

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 .

interval for each parameter in each response variable is ˇ ± 0.534.

Applying such value of confidence interval, Eq. (4) reduces to
∧
Y = 6.793 + 0.5939X1 + 1.534X2 + 3.104X3 + 0.753X2 X3 (8)

The interaction effect is obvious on the yield; it can be concluded

that all three variables and interactions between X2 (temperature)
and X3 (extraction residence time), have significant effects on the
yield as response variable (Y). While other interactions between X1
and X3 and between X1 and X2 are not significant. Such conclusions
are drawn at 95% confidence level.

Fig. 7. JMP statistical screening analysis of model parameters.

3.3.2. Driving force experimental model
A model that represents the believed driving force behind the
propensity of SCFE of olive oil is also developed in this investiga- with their combinations and their effect on the yield can be repre-
tion. The driving forces are represented by the differences between sented by Eq. (10):
the operating pressure and the critical pressure and between
the operating temperature and the critical temperature; namely, Yield = Constant + A × (T − Tc ) + B × (P − Pc )2 + C × t (10)
(P − Pc ) and (T − Tc ), respectively. Additionally, the contact time was
included in the model. The suggested model can be described in Eq. Nonlinear least square technique was used to determine the
(9): parameters displayed in Eq. (10). This lead to Eq. (11):

Yield = A × (T − Tc )a + B × (P − Pc )b + C × t c (9) Yield = −0.647 + 0.154 × (T − Tc ) + 1.91 × 10−7

× (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.

Test # Y (%) Degree of freedom Standard

(mi − 1) deviation,  i

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
Fig. 9. Error estimation of the parameters of the driving force model using JMP
program.
Fig. 8 shows the relation between the yield obtained from the
experiments and the yield as calculated using Eq. (11). The corre-
lation coefficient (R) indicates an agreement of the model to the
experimental data.
The outcome shows that the pressure driving force and hence
mass transfer of CO2 has the most significant effect on the extrac-
tion yield of olive oil. The JMP program provides sensitive analysis
for the model parameters by providing an error determination for
each parameter, as well as the t-ratio as shown in Fig. 9.
4. Conclusions
The following conclusion remarks can be drawn from this work:
(1) SCFE of uncrushed olives can be a viable process; thus reducing
the cost of operation and increasing the separation propensity
between solids and the extracted oil.
(2) The yield was found to be mostly affected by the SCFE residence
time, followed by lower degree by the operating temperature
and lastly by the operating pressure. The maximum value of
the oil yield obtained was 12.37% at 24 MPa, 60 ◦ C and 150 min.
Therefore, the process condition of 10 MPa, 60 ◦ C and 150 min
are considered the optimum due to highest yield and a rela-
tively low cost.
Acknowledgment
The authors would like to acknowledge the support from the
university of Science and Technology in Jordan to complete this
work.
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