Accepted Manuscript

Crude palm oil (CPO) extraction using hot compressed water (HCW)

Mohd Sharizan Md Sarip, Noor Azian Morad, Yoshiyuki Yamashita, Tomoya

Tsuji, Mohd Azizi Che Yunus, Mustafa Kamal Abd Aziz, Hon Loong Lam

PII: S1383-5866(16)30604-9
DOI: http://dx.doi.org/10.1016/j.seppur.2016.06.001
Reference: SEPPUR 13057

To appear in: Separation and Purification Technology

Received Date: 28 March 2016

Revised Date: 31 May 2016
Accepted Date: 1 June 2016

Please cite this article as: M.S.M. Sarip, N.A. Morad, Y. Yamashita, T. Tsuji, M.A.C. Yunus, M.K.A. Aziz, H.L.
Lam, Crude palm oil (CPO) extraction using hot compressed water (HCW), Separation and Purification
Technology (2016), doi: http://dx.doi.org/10.1016/j.seppur.2016.06.001

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 Crude palm oil (CPO) extraction using hot compressed water (HCW)
Mohd Sharizan Md Saripa, Noor Azian Morada,*, Yoshiyuki Yamashitab, Tomoya Tsujia,
Mohd Azizi Che Yunusc, Mustafa Kamal Abd Azizd, Hon Loong Lamd

a
Shizen Conversion and Separation Technology (Shizen ikohza),
Malaysia – Japan International Institute of Technology (MJIIT),
Universiti Teknologi Malaysia, Jalan Sultan Yahya Petra, 54100 Kuala Lumpur, Malaysia
b
Department of Chemical Engineering,
Tokyo University of Agriculture and Technology (TUAT), Koganei, Tokyo 184-8588, Japan
c
Centre of Lipid Engineering Applied Research (CLEAR),
Faculty of Chemical Engineering, Universiti Teknologi Malaysia, UTM Skudai, 81310
Johor Bahru, Johor, Malaysia
d
Department of Chemical & Environmental Engineering
University of Nottingham Malaysia, Jalan Broga, 43500 Semenyih, Selangor Darul Ehsan,
Malaysia

Abstract
Hot compressed water extraction (HCWE) is a promising alternative technology which
has proven to be successful in many applications. In this study, hot compressed water
extraction (HCWE) was applied in the extraction of crude palm oil (CPO) from palm
mesocarp. The operating conditions investigated were pressure of 30, 40 and 50 bar with
varied temperature ranging from 120 to 180oC through semi-batch extraction of 10 mins
interval and total extraction time of 60 mins. The CPO yield, free fatty acids (FFA) content
through HCWE process was analysed. Scanning electron microscopy (SEM) study on various
palm mesocarp fibres undergone HCWE process at various conditions was also performed.
The extracts formed three distinguished layers; oil, oil-water emulsion and water. The
maximum CPO extracted in the oil layer was 0.541 ± 0.005 (g-oil/ g-dried mesocarp) with
averaged FFA of 0.81 ± 0.08% at the optimum operating condition of 160oC and 50 bar. CPO
recovered from the emulsion was 0.159 ± 0.004 g-oil/ g-dried mesocarp giving a total CPO
extracted at 0.700 ± 0.005 g-oil/ g-dried mesocarp. SEM micrographs were used to assist
understanding of the mechanism that took place during the experimental conditions of
HCWE. The time dependence of the compounds was well represented by the second order
mass transfer model. The mechanism of CPO extraction from palm mesocarp using HCWE
was also explained through this study.
Keyword: Hot compressed water extraction, Mass transfer model, crude palm oil (CPO),
mechanism of extraction
1.0 Introduction
In a typical palm oil mill in Malaysia, mechanical screw press system has been utilized
as a CPO extraction method after the sterilization, threshing and digestion processes. This
conventional process contributes to overall oil losses estimated up to 7% or 0.07 (g-oil /g-
dried mesocarp) [1-2]. Various researches throughout the years have proposed improvements
to the process to increase CPO yield which includes aqueous enzymatic extraction [3],
supercritical fluid CO2 extraction [4] and subcritical R134a extraction [5]. The use of these
processes has been proven to increase CPO yield up 0.77 g-oil/g-dried mesocarp [4]
compared to the current palm oil mill with CPO yield at 0.61 g-oil/g-dried mesocarp.
However, most of these solutions ended up at the research scale due to several reasons mainly
related to economical constraint and process sustainability. Thus, it is essential to continue
search and establish possible alternative process to further improve the oil extraction rate
(OER) from 20 to 23 % by the year 2020 in the palm oil mills as initiated by the government
development programs to boost the industry. The national OER indicates the overall milling
efficiency where the output which is CPO is measured against the input of fresh fruit bunches
into all the palm oil mills in Malaysia. The national OER positive increment would generate
additional revenue for the industry at RM 2.2 billion per percent OER per year.
In this study, the practicality of utilising hot compressed water extraction (HCWE) for
possible alternative in CPO extraction process was evaluated. Since 1990s, HCWE was
receiving great deal of attention from numerous researchers for its attractive features as a
green and safe solvent. Although HCWE has never been explored for CPO extraction, it has
already been proven to be an alternative method for other oilseeds extraction such as jojoba
[6] and cottonseed oils [7]. HCW also has been applied in natural products [8-9],
environmental sample, food [10] and microalgae extractions [11]. The positive result on oil
and bioactive extraction from these different sources using HCWE is promising and has
potential to be applied for CPO extraction.
The primary goal of extraction is to enhance the species mass transfer into bulk solvent.
Basically, the extraction of species within plant matrix involves solid-liquid extraction for
multi compounds from its location within the plant matrix to the solvent [12]. The extraction
is explained through mass transfer phenomena with a few steps. The rate-limiting step is
caused by the local driving force which is known as concentration gradient of the plant
matrix to solvent phase [13-14]. The mechanism of extraction of species that includes
dissolution of the species in the solvent may not be the same for species that are not soluble
in the solvent such as CPO in HCW. Moreover, the possibility of having side reactions during
the extraction such as in HCWE condition may change the typical mechanism of species
mass transfer within plant matrix in the solid-liquid extraction.
Hence, the objective of this study was to investigate the effect of HCWE condition for
CPO extraction. The study also includes the HCWE effect on free fatty acid (FFA) content.
Micrographs of scanning electron microscopy (SEM) on the effects of experimental
conditions were used to assist understanding the mechanisms that took place during the
experimental conditions of HCWE. In addition, the mechanism of the HCWE extraction for
CPO is also explained by suitable hypothesis since the solubility of CPO in HCW is very
low. This mechanism is also characterized using mass transfer model to represent the process.
Understanding the mechanism of extraction and identifying possible improvements in HCWE
of CPO from palm mesocarp would be the first step in identifying further research areas to be
made in this alternative method.

2 Material and Method

2.1 Material and sample preparation
Oil palm fresh fruit bunch (FFB) was collected from Felda Mempaga Satu, Bentong,
Pahang, Malaysia. Each FFB was approximately 25 kg in weight with a length of 36 cm and
width of 32 cm. The whole FFB was sterilized within 2 hours of harvesting using an
autoclave (ALP CL-32L, Japan) at 130oC for 40 min. This process was assumed to give same
effect as the palm oil mill sterilization. The softened palm oil mesocarp from the sterilised
fruitlets of the FFB was shredded into 3.5 to 4.0 cm pieces, sealed in plastic containers before
being stored in a freezer at -5oC for further experimental use.
HPLC grade hexane, 98% (Friendemann Schmidt, Australia) was used for solvent
extraction and liquid-liquid extraction. AR grade isopropanol, 99.7 % (QReC, New Zealand),
sodium hydroxide, 0.1 M (R&M Chemical, India) and phenolphthalein solution (Fluka,
Sigma Aldrich, Switzerland) were used for free fatty acids (FFA) analysis. Distilled water
generated from water distiller (Favorit, Thailand) was used as solvent in the HCWE process.

2.2 Hot compressed water extraction (HCWE)

HCWE was done semi-batch wisely using the fabricated equipment in this laboratory as
shown in Figure 1. The fabricated equipment consisted of two vessels with one litre volume
each; the extraction and the cooling vessels were connected by a 3/8 inch stainless steel
pipeline and a fresh water tank of one litre supplies water to the extraction cell. Prior to
extraction experiments, the stored, shredded mesocarp was taken out of the freezer and left to
thaw at room temperature (27oC) for 60 mins. 100 g of the shredded palm mesocarp was
weighed and loaded into a stainless steel mesh cylinder (height = 14 cm, OD = 8 cm) before
being covered and placed into the extraction vessel. 500 ml of distilled water was added into
the vessel. The vessel was then securely covered with a stainless steel lid with several ports
for instrumentations including temperature and pressure sensors. Apart from that, the lid also
has inlet and outlet ports for nitrogen gas, fresh water, extract and a safety vent.
Nitrogen gas was passed through one of the ports of the vessel and bubbled for 2 mins
to purge out air and dissolved oxygen in the water. Excess pressure was relieved through the
venting valve. The temperature was set according to the required experiment ranging from
120 to 180oC. The heating was through an electrical jacket enclosing the extraction vessel
and it took 10 to 15 mins to achieve the set temperature. The total extraction time started once
the set temperature was achieved as indicated by the temperature indicator. After 10 mins of
extraction, the heating was stopped; the extract was rapidly transferred into another pre-
cooled vessel where it was collected within 1 min. 500 ml of fresh water was immediately
pumped into the extraction vessel for the next 10 mins interval of extraction using the same
sample. The procedure was repeated until 60 mins of extraction time at each constant
temperature. All HCWE experiments were at constant pressures of 30, 40 and 50 bar with a
constant stirring at 500 rpm.
The extract was subjected to post treatment process before being analysed. Table 1
summarises the variables studied in HCWE. Two different outputs were analysed and
measured in this study; CPO yield (g-oil/g-dried mesocarp) and free fatty acid, FFA (%).
CPO yield were based on the cumulative value of 60 mins extraction time. Meanwhile, the
FFA was analysed for each 10 mins time interval to evaluate the effect of extraction time
during HCWE process.

2.3 Soxhlet extraction using hexane

Hexane extraction using soxhlet extractor was conducted as a benchmark of CPO

content in the mesocarp in this study using solvent to solid ratio of 15:1 in 8 hours of
extraction time based on earlier study [4]. The CPO yield was obtained after removing
hexane from the extract using rotary evaporator (Buchi, Switzerland) at a vacuum pressure of
320 mbar and water bath temperature of 55oC.

2.4 Post treatment of water extract

 The water extract was subjected to oil and water separation through clarifying and
centrifuging processes. The method was adapted from [15]. The water extract was clarified
using separating funnel where it was left to stand for 60 mins at a constant temperature of
60oC to form three distinguished layers of oil, oil-water emulsion and water. The bottom
layer of water was collected for glucose analysis. The top two layers of oil and oil-water
emulsion were further centrifuged at 7000 rpm for 10 mins to give a distinct oil and oil-water
emulsion layers. This procedure was performed for each batch of extract from 10 to 60 mins.
Thus, for each operating conditions 6 batches of extracts were processed, and the
accumulated CPO was collected and measured before subjected to further analysis.
Water in the oil-water emulsion was removed using rotary evaporator (Buchi,
Switzerland) at a vacuum pressure of 100 mbar and water bath temperature of 70oC. The
remaining dried solid residue was collected, weighted, mixed with hexane up 2 folds of its
weights, stirred for 60 mins and filtered using vacuum filter (45 μm) to extract out the CPO.
Hexane in the filtered mixture was removed using rotary evaporator at a vacuum pressure of
320 mbar and water bath temperature of 55oC. CPO retained in the flask was collected and
weighted.
2.5 Crude palm oil (CPO) yield calculation
The CPO yield was calculated using equation 1.

where Yoil yield is the CPO yield (g-oil/g-dried mesocarp), Voil is the volume of CPO recovered
from extraction (ml), ρoil is the density of CPO (g/ml), and Ws is the mesocarp dry weight
(g).
The mesocarp dry weight was established from the drying curve of this study. The
shredded mesocarp was weighed at 20g each in three separate petri dishes. The mesocarp
samples were dried at 103oC in the electric oven (Memmert, Germany) until a constant
sample weight was achieved. In this drying curve development, the reduction of the weight
was measured and recorded in one hour interval for the first 10 hours and extended to 21
hours for the total moisture removal. The mesocarp dry weight, was calculated using
equation; where is the mesocarp weight (g) and df is the calculated water
removed from the mesocarp.

2.6 Free fatty acid (FFA) analysis

 The FFA analysis was done using MPOB standard titration method [16]. The procedure
assumes FFA to compose solely of palmitic acid using equation 2.

where FFA is the free fatty acid percentage (FFA %), is the volume of sodium
hydroxide (ml) used for titration, is the molarity of sodium hydroxide (M) and is
the weight of the oil (g). FFA analysis was performed on the oil layer for each batch for the
first three batches of extract from 10 to 30 mins.

2.7 Analysis of glucose in the water layer of HCW extract

The concentration of glucose in water was analysed using HPLC 1100 series (Waters,
USA) with Refractive Index (RI) detector (Waters, USA) adapted from Muda (2015). A
Shodex Sugar SP0810 column (NREL, Japan) and mobile phase of deionised water with
flowrate of 0.8 ml/min was used [17]. 2 ml of the water layer was filtered using syringe filter
(Nylon, 0.45 μm). 10 μL of filtered solution was injected into the HPLC. Prior to that, the
calibration curve was developed using glucose standard (Friedmann Schmidt, UK) to
quantify the concentration of the sugar in the sample.
2.8 Microscopic analysis using scanning electron microscope (SEM)
The microscopic analysis was done using scanning electron microscope (SEM) LEO
1455 VPSEM with Oxford Inca EDX (LEO, UK). The mesocarp fibres were coated with gold
using SCD 005 sputter coater (Baltec, UK). The coating was conducted in a vacuum
condition of 0.086 mbar.

2.9 Mass transfer model

In order to provide an appropriate representation of HCWE process, the mass transfer
model was employed in this study. Two mathematical expressions namely first [18] and
second order mass transfer models were compared in this study. Both models were based on
the extraction mechanism which indicated the mass transport of the species from the core of
the sample matrix to the bulk solution [18]. The first order model, assumed that the mass was
transferred at a linear rate whilst the second order, assumed the second degree polynomial
rate. Other assumptions for these models were: (1) the effective surface areas for solid
particles are constant, (2) CPO is evaluated as a single species studied even though it is a
mixture of different species comprising of TAG, DAG, FFA and minor component such as β-
carotene and vitamin-E, (3) constant agitation rate.
 The first order mass transfer model is based on the mass balance for the process with
the assumption that the amount of species transferred is proportional to the concentration
difference as expressed in equation 3 [13] integrated and simplified as equation 4 [9, 18].

where k1 is the first order mass transfer coefficient, is the species concentration in the bulk
liquid at time, t (g-species/g-dried mesocarp) and is the concentration at equilibrium or
maximum concentration of species (CPO) in the palm oil mesocarp (g-species/g-dried
mesocarp). In this study, for first order mass transfer model was obtained through the
solvent extraction as discussed in section 2.3. The value was determined from the slope of

against t plot.

The second order mass transfer model or known as second order rate law was also
proposed in this study. The model was proven to provide an accurate representation in solid
liquid extraction using water or aqueous solution which is similar with HCWE process [19-
21]. The second order kinetic model is expressed as equation 5.

where k2 is the second order extraction rate coefficient (g-dried mesocarp/g-species.min).

for the second order mass transfer model is not a constant parameter unlike Co in first order
mass transfer model and is determined through integration of the experimental data
throughout the duration of experiment. Therefore, is assumed as maximum concentration
achieved at a specific condition and may vary for each experimental condition. This model
can be integrated from to at times t=0 to t respectively to be written as equation 6
and linearized into equation 7.

The initial rate of extraction h (g-species/g-dried mesocarp.min) can be expressed as equation

8 when t and Ct approach 0.
Equations 7 and 8 can be rearranged as equation 9.

The value, and were determined from the y intercept and slope of against t plot.

The differential equation of the model was solved using Matlab R2012b (MathWorks,
Inc, USA). The predictive capability for both models were evaluated based on the average
absolute relative deviation, AARD (%) using equation 11.

where n is the no of experimental data, is the experimental data, and is the predicted
data. The goodness of the model fit to the experimental data was evaluated using r2. The
lower value of AARD (%) indicated better predictive capability of the model while r2 value
near to unity indicated lower deviation between predicted and experimental data.

2.10 Statistical analysis

The analysis of variance (ANOVA) was conducted to demonstrate the significant effect
of the HCWE parameter to CPO yield and FFA. One way ANOVA analysis was used to
demonstrate the effect of constant pressure at varied temperature and constant temperature at
varied pressure. Two ways ANOVA was used to evaluate the overall effect both pressure
and temperature simultaneously. The parameter was considered to give statistically
significant different to the process if p value of was obtained based on the 99 %
confidence level. The higher f value would represent high significant effect to the process.
The R software version 3.1.2 was used for this analysis.

3.0 Results and discussion

3.1 Effect of temperature and pressure on the CPO yield using HCWE
From the developed drying curve of palm mesocarp, the averaged water removed, df
was 0.254 g-water/g-sample and would be used for calculations throughout this study. After
clarifying process, the water extract forms three distinguished layers of solution. The top
most is the oil followed by the oil-water emulsion and water layers. The oil layer which is
CPO is bright orange in colour. The oil-water emulsion is murky brown as a result of
dispersed oil droplets and tiny solid residue in water whilst the water layer is almost clear but
still consists of a small amount of tiny specs of oil droplets and particles. The one way
ANOVA is conducted to study the effect of temperature and pressures on the CPO yield
using HCWE is tabulated in Table 2.
As indicated in Table 2, the statistically significant effect of temperature can be
observed at p value of , and for constant pressure of
30, 40 and 50 bar respectively. Meanwhile, the statistically insignificant effect of pressure
can be observed at constant temperature of 120, 140 ad 180 oC at p value of 0.07, 0.13 and
0.09 respectively. However, the statistically significant effect of pressure can be observed at
160oC with the p value of 0.01. Based on the two way ANOVA analysis, the statistically
significant effect of temperature was observed as determined by
but pressure has no significant effect as determined by
. This confirmed that pressure has minimal effect on the
CPO yield in HCWE.
The effect of temperature on CPO yield at constant pressure of 30, 40 and 50 bar is
shown in Figure 2. It should be noted that CPO yield is referring to the cumulative oil layer
for 60 mins of total extraction time. At 30 bar, the CPO yield increases significantly by 17.21
% from 0.456 to 0.533 ± 0.006 (g-oil / g-dried mesocarp) from the temperatures of 120 to
160oC. Above 160oC, the CPO yield decreases gradually to 0.483 ± 0.006 (g-oil / g-dried
mesocarp) at the temperature of 180oC at the same pressure. At this temperature, the
maximum CPO yield is obtained in all studied pressure. It was observed that HCWE at 50 bar
gives the maximum yield of 0.541 ± 0.005 (g-oil/ g-dried mesocarp) at 160oC. A significant
drop in CPO yield can be observed for HCWE between 0.489 to 0.431 ± 0.005 (g-oil/g-dried
mesocarp) for all pressures at the temperature of 180oC.
In the parenchyma cells of fresh mesocarp, the lipid bodies which store neutral lipids
or oil and protein bodies are completely encased within cell walls and middle lamella or
intercellular junctions [22-23]. The introduction of sterilization of FFB as the pre-treatment
process in palm oil mills promotes the degradation of some middle lamella and cell walls
[22]. In this study, the pre-treatment of FFB bunch through autoclaving has similar effect as
sterilization where the lipid bodies and minor component in exposed mesocarp was released
into the fibre from its encasement. However, sterilization is insufficient to totally degrade and
rupture the structural component of the cell walls which mainly consist of 42.8 % of
cellulose, 33.1% of hemicelluloses and 20.49 % of lignin [22, 24]. Figure 3(a) shows SEM
micrograph of sterilised palm mesocarp fibres. The large number of intact or unruptured cells
supports earlier findings of insufficient cell wall rupture during sterilisation process. This
causes some of the lipid bodies together with the minor components to be inbound in the fibre
or its original structure and mechanical extraction method using screw press system will not
be able to extract such trapped CPO in within the cell walls [25].

The HCWE of the pre-treated mesocarp in this study further ensures complete
disintegration of the cell walls containing lipid bodies. The HCWE condition is conducive for
hydrolysis of hemicellulose and cellulose from the fibres to produce glucose which can start
at a low temperature of 120oC. This phenomena was confirmed through the glucose
concentration analysis of water layer extract as shown in Figure 2. It was found that glucose
concentration in the water layer was at 1.08 ± 0.06 mg-glucose/g-dried mesocarp at 120oC
and 50 bar. The sugar concentration increases with temperature to above 2.00 mg-glucose / g-
dried mesocarp at temperature of 160oC. The hydrolysis of hemicellulose and cellulose
weakens the fibre structure and facilitates the entrainment of CPO from the core matrix into
the HCW. This is interesting since the mechanism of extraction through entrainment of
species into bulk solvent takes place for immiscible liquids like oil-water unlike in most
extraction of species which is soluble in the bulk solvent. However, it may be possible that oil
is slightly soluble in water at elevated temperatures.

SEM micrographs in Figures 3b, c, d and e indicate that as the temperature of HCWE
process at 50 bar was increased from 120, 140, 160 to 180 oC respectively the number of
ruptured cell walls also increased. Concurrently, hydrolysis of hemicellulose and cellulose
into glucose increases with increasing temperature as shown in Figure 3. Glucose
concentration in the water layer was at 1.34 ± 0.08 and 2.18 ± 0.07 mg-glucose/g-dried
mesocarp at 140 and 160oC respectively. When the temperature was increased from 120 to
160oC, cellulosic hydrolysis process was rapidly increased and produces higher concentration
of glucose at 2.18 ± 0.07 mg/g-dried mesocarp and releasing oil at 0.541 ± 0.005 (g-oil/ g-
dried mesocarp) as CPO yield. The CPO yield increases with temperature in conjunction
with increased glucose concentration signifies more cell walls ruptured during HCWE from
120 to 160oC displaying ruptured cells as observed in the micrographs. The pore structures
shown in the micrographs indicated that the oil in the ruptured cells was entrained into HCW
leaving tiny craters at the matrix site. As the temperature was increased to 180 oC (Figure 3e),
more severe cell rupture and disintegration of fibres was observed leaving no intact cells.

The mechanism observed in HCWE which involves rupturing of cell walls is similar
to those observed in the aqueous enzymatic process. However, during aqueous enzymatic
process of CPO from oil palm, hydrolysis of hemicellulose and cellulose occur with the
assistance of an enzyme and known as enzymatic hydrolysis [3, 22].

The changes of physico-chemical properties of both species and solvent at high

temperature and pressure also contribute to extraction efficiency. On the chemical properties
aspect, according to Shinoda (1977), the iceberg formation caused by hydrogen bonding in
water molecule is weakened as the temperature increases [26]. These would disrupt the strong
interactions or adhesive energy between oil and active sites on the sample matrix thus
promoting desorption of the oil and improve its mass transfer mechanism [27]. The weakened
hydrogen bonding at 160oC resulted in increased of CPO yield. Physical properties of water
as solvent at elevated temperature and pressure plays a major role in improving mass transfer
effects. The viscosity of water decreases as temperature increases which exhibit better
penetration of solvent into matrix particles [27]. The viscosity of water decreases from 890.3
to 183.4 μPa.s for temperature of 25 and 150 oC respectively at constant pressure of 50 bar
[28]. In addition, surface tension of water is also decreased as the temperature increases from
71.98 to 48.75 mN/m at the temperature of 25 and 150oC respectively [29]. A decrease of
surface tension of water will facilitate better contact between water and oil which allow water
cavities formation outside the sample matrix [27]. The reduced surface tension of water also
resulted in easier dislodging of the oil globules within the palm mesocarp fibres to be
entrained into the bulk water as solvent.

Figure 4 shows CPO yield at various temperature in HCWE at 50 bar. A significant

amount of CPO was also recovered from the oil-water emulsion layer through the procedure
described in Section 2.4. It was found that the oil-water emulsion layer contained 0.159 ±
0.004 g-oil/ g-dried mesocarp or 23% of the total CPO extracted through HCWE as shown in
Figure 5. It is also important to note that almost similar amount of CPO was detected in the
oil-water emulsion layer at all HCWE condition with variation of 0.006 (g-oil/g-dried
mesocarp) in oil content with reduced amount noted at 160 oC and above. The constant
amount of CPO detected in the oil-water emulsion layer for this study could also be attributed
to the constant solvent:sample ratio at 5ml:1g during HCWE.
As the temperature increases above 160oC the decreasing of CPO yield is probably
caused by the possible oil degradation which converts oil into undesirable by-product. The
increased in solid residue was also contributed from the by-product of fibre disintegration
during hydrolysis. This can be observed by the formation of high solid residue at 0.538 ±
0.004 g-solid/g-dried mesocarp compared to 0.378 ± 0.004 g-solid/g-dried mesocarp at 180
and 160oC respectively. The solid residue increased drastically at above 160 to 180oC by 42
% in comparison to only 28 % increment at lower temperatures from 140 to 160 oC.
During HCWE, at high temperatures possible reactions that may occur includes TAGs
hydrolysis [30-34] and other form of decomposition such as polymerization of TAG [35].
Above 160oC at 50 bar, physical changes were noted on the overall appearance of the
mesocarp fiber, extracts and solid residue. The experimental procedure which removed the
extracts at 10 mins interval to be replenished with fresh water also exposed the palm
mesocarp fibres at high temperature even though for a minute to cause the fibres to be burnt
and disintegrated. This can be observed by the production of waste fibre, darkened oil
accompanied by burning odour possibly due to cellulosic conversion. It is possible that due to
the experimental circumstances, during these short intervals without HCW in the extraction
vessel at above 160oC, the remaining CPO in the exposed mesocarp fibre may form
polymeric substances which may react with the burnt fibre resulting in tar like solid residue.
This solid residue was a result of accumulated formation at every 10mins intervals during the
short 1min exposure in the absence of HCW and for each semi-batch process of 60 mins,
such reaction may take place 5 times of a total of 5 mins. Therefore, the semi-batch procedure
may not be suitable to be performed at high temperature and improved procedure to minimise
these effects is required.
In another study, it was demonstrated that thermal hydrolysis of wheat straw using
HCW indicated a rapid increase of reducing sugar from 170oC and achieving its optimum
condition at 190oC with 30 mins of reaction [36]. Apart from that, the phenomena of the
compound degradation was especially pronounced in thermal labile extracts as confirmed in
most HCWE process at high temperatures such as 6-gingerol and 6-shogaol extraction from
ginger [9], catechin extraction from Areca catechu seeds [20] and metabolites extraction from
Angelica roots [37]. Therefore, CPO extraction using HCW should not exceed the
temperature above 160oC at 10 mins intervals.
Besides that, based on ANOVA analysis as observed in Table 2, the limited significant
different is observed on pressure change at only 160oC. This is probably due to the limited
effect of pressure on the physico-chemical properties such as viscosity and surface tension of
water from 30 to 50 bar [38].

3.2 Effect of temperature and pressure on the free fatty acid (FFA) content in CPO using
HCWE
 According to Malaysian Standard, CPO can be classified into two grades that are
special quality (SQ) with FFA below 2.5% and standard (STD) grade where the FFA is below
5% [40]. FFA is a measure of independent fatty acids. CPO is largely comprises of 93%
triglycerides (TAGs) and 6% of diglycerides (DAGs) naturally consist of FFA at lower
percentage [41]. FFA can be increased through triglycerides and diglyceride hydrolysis either
by enzymatic hydrolysis by microbial lipases or thermal hydrolysis [32-34]. To deactivate the
naturally occurring enzyme lipase, the sterilization process on FFBs at 130oC is carried out in
palm oil mills [41].
Thermal hydrolysis is a concern in HCWE process since it operates at high temperature
of up to 180oC and this condition may be conducive for TAGs hydrolysis. Therefore, this
study investigated the effect of operating conditions during HCWE on FFA increment in the
extracted CPO. The FFA value and one way ANOVA test at different temperatures and
constant pressure of 30, 40 and 50 bar in the first 10 mins of HCWE process is tabulated in
Table 3.
The results indicated that the temperature and pressure conditions of 120 to 180 oC and
30 to 50 bar respectively has shown no statistically significant effect to FFA % in the oil
extracted using HCWE in this study. This is based on the higher p value of above 0.01 as
tabulated in Table 3. One way ANOVA analysis at constant temperature gave similar results
as for constant pressure analysis, therefore data is not included in Table 3. Table 3 also shows
that HCWE process is very effective in producing high quality CPO with an average FFA of
0.54 ± 0.08 % under these conditions. This finding is supported by Eller et al (2011) in their
study in which FFA remains fairly constant at 0.5 % for 300oC and reaction time of 5.7 min
indicating hydrolysis did not occur at these conditions. However, hydrolysis took place at
350oC for pressures between 10 to 40 bar increasing FFA to about 2.0 % and from 40 to 50
bar, a further significant increase of 0.5 % FFA was observed at this temperature. This was
reported in another previous study where it was found that thermal hydrolysis will only take
place at very high temperature of 300oC and pressure of above 40 bar [32].
Not limited to that, further study using HCW hydrolysis for vegetable oil such as
coconut, soybean and linseed oils observed that the hydrolysis reaction occurred in the
temperature range of 260 to 280oC for 20 mins of reaction time [34]. The hydrolysis of corn
oil using HCW however, showed that the reaction started at a lower temperature of 220oC but
at prolonged reaction time of 40 mins [30]. This indicates that apart from temperature,
reaction time is also a contributing factor for FFA increment. The finding of this work also
show similar pattern on the effect of time at various temperatures and pressures as illustrated
in Figure 5. The FFA was analysed at 10 mins intervals for each 10, 20 and a maximum time
of 30 mins CPO batches where approximately 90 to 91 % of the CPO was extracted. At
higher extraction times of 40 and 60 mins the reduced CPO yield makes it difficult to conduct
FFA analysis.
The extraction time gave significant effect to the FFA based on
. As the extraction time was increased from 10 to 30 mins, FFA was
increased by 160 % from 0.57 to 1.49 ± 0.05% for HCWE operated at 120oC and 30 bar as
shown in Figure 5(a). Similar trend can be observed for the other temperatures and pressures
with an average increment of 206 % from 10 to 30 mins as shown in Figure 5(b) and 5(c). In
general, the findings of this work indicated that prolonged exposure to high temperature will
increase the FFA content even though the temperature did not exceed 180 oC.
The finding of this work is supported by other studies. In one study it was found that
longer heat exposure of sunflower oil enhanced thermal hydrolysis of TAG which resulted in
increased FFA as demonstrated by Alenezi et al (2010). The conversion process started after
5 mins at 270oC and reached 71% of fatty acid conversion after 26 min of reaction [31]. In
another study, the thermal hydrolysis of various vegetable oils also demonstrated the
significant effect of time in HCW process at the optimum time of 20 mins for temperatures
above 260oC [34].
However, the increment of FFA in this study was insignificant to affect the oil quality
since the HCWE process extracted 54 % in the first 10 minutes and about 91 % of total
recovered CPO after 30 minutes of extraction time with an average FFA of 0.81 ± 0.08%.
Thus, CPO extracted from palm mesocarp using HCW at temperatures and pressures between
120 to 180oC and 30 to 50 bar respectively within 30 mins of extraction time qualifies for the
SQ grade CPO.

3.3 Comparison between HCWE and other extraction methods when applied to palm
mesocarp
Comparison of oil extracted using HCWE with other extraction methods is tabulated in
Table 4. Hexane was used as a benchmark for CPO yield in this study using the same
mesocarp sample. It may be noted that the use of different mesocarp samples for other
methods of extraction from other studies will to a certain extent contribute to discrepancy in
comparison of CPO yield. Therefore, it should be cautioned that the comparison here is use
as a rough guide on the different methods of extraction when applied to palm mesocarp.
 The CPO yield from the oil layer obtained from HCWE is relatively low compared to
the other methods at 0.541 ± 0.005 g-oil/g-dried mesocarp. However, CPO recovered from
the emulsion contributes another 0.159 ± 0.004 g-oil/g-dried mesocarp giving a total CPO
extracted through HCWE 0.700 ± 0.005 g-oil/g-dried mesocarp. This value is lower for about
5% compare with solvent (hexane) extraction which obtained a CPO yield of 0.757±0.005 g-
oil/g-dried mesocarp. The CPO yield obtained from the solvent (hexane) extraction is also
used for Co in the calculation of first order mass transfer model. Based on the literature, the
higher CPO yield were obtained through supercritical CO 2 at 0.76 g-oil/g-dried mesocarp [4]
followed by aqueous enzymatic extraction at 0.71 g-oil/g-dried mesocarp. Using subcritical
R134a on palm mesocarp extraction gave 0.66 g-oil/g-dried mesocarp whilst the current
commercial mechanical screw press widely use in palm oil mills is at 0.62 g-oil/g-dried
mesocarp.
The lower oil yield recovered in the oil layer through HCWE is mainly attributed to the
formation of the oil water emulsion layer. As discussed earlier in section 3.1, an average 23
% of CPO is in the oil-water emulsion. Thus, the maximum CPO yield using HCWE process
is at 0.70 g-oil/g-dried mesocarp. Apart from oil losses from oil-water emulsion, small
amount of oil was trapped in the water layer as tiny oil globules. Oil losses in emulsion and
water layers contribute significantly to CPO recovery. The complete recovery method for oil
collection which is not the scope in this study needs to be established to improve the CPO
yield using HCWE. Hence, HCWE may be an alternative method in palm mesocarp
extraction.
The averaged FFA content of 0.850 in the CPO extracted using HCW is slightly higher
compared with supercritical CO2 and hexane extraction at 0.612 and 0.790, respectively.
Therefore, HCWE is capable of producing the special quality (SQ) grade CPO with FFA
below 2.5 % compared to the commercial standard (STD) grade CPO with FFA of 3.53 [42].

3.4 Mass transfer modelling for CPO yield in HCWE process

In a typical extraction process for plants, seed, or rhizome, the extraction mechanisms
are governed by the mass transport phenomena principle which represents the transfer of
species mass from the solid matrixes into solution or solvent [43]. This mechanism can be
described by two distinguished models namely diffusivity and mass transfer. In this study, the
mass transfer model were chosen based on the physical process characteristic with the
existence of the constants agitation speed [13]. Not limited to that, mass transfer model is the
best method to obtain the compound concentration versus time correlation whilst the used of
the diffusivity model would require more input parameters that has to be estimated [13].
The first and second order mass transfer models were employed to demonstrate the
extraction curve for CPO using HCWE process. The value of the r2 and AARD are used to
evaluate the goodness of the fit in representing the experimental data. Table 5 shows the mass
transfer model coefficient, AARD and r2 values for both models in CPO extraction using
HCW. The second order mass transfer model exhibit a good fitting performance with AARD
values ranging from 0.75 to 6.27 % and r2 value of between 0.942 to 0.999 for the conditions
studied. Meanwhile, for the same operating conditions studied, the first order mass transfer
model displayed poor fitting performance with AARD values of between 16.95 to 46.69 %
and r2 values of between 0.746 to 0.931. This indicates that CPO extraction using HCW
process follows the second order mass transfer model. Meanwhile, the first order mass
transfer model gave a high deviation and therefore is not suitable to be used to represent this
process. In fact, the first order mass transfer model suggests that extraction rate is constant
over the duration of extraction which is too simplistic an assumption and is not representative
in most application of solid-liquid extraction process.
The cumulative CPO yield extracted predicted using second order mass transfer model
compared with experimental data at different temperature and pressure is shown in Figure 6.
It is observed from that Figure that at 30 bar and 120oC, the CPO yield was 35.8 % (w/w)
within 20 mins of extraction time after which the rate of extraction gradually decreases with
only 9 % (w/w) increment in yield at 50 mins of extraction time. The cumulative CPO
extracted was found to be almost constant from 50 to 60 mins of extraction time indicating
minimal amount of oil being extracted in the last 10 mins of the process. It can also be
observed that at the temperature of 160 oC at all pressures studied, the extraction rates were
relatively higher compared to other temperatures. At 160oC and 30 bar, the oil was effectively
being extracted at 43 % (w/w) in 20 mins of extraction time. Reduced rate of oil extracted at
10 % (w/w) over the next 20 mins duration from 20 to 40 mins of extraction time was
observed, after which the CPO yield remains fairly constant from 40 to 60 mins. Meanwhile,
pressure does not seem to affect the CPO yield or the rate of extraction at all temperatures.
The second order mass transfer model describes four subsequent steps in a typical
extraction process which involves desorption of the species into matrix active site, diffusion
of the solvent into matrix, dissolution of the species into the bulk solvent and species mass
transfer from the matrix into the solvent [44-45]. However, when the model was applied to
the extraction of CPO from palm mesocarp using HCWE, some adjustments in the
mechanism as supported by the findings is proposed even though the model fits very well.
During HCWE in this study, the first step; 1) desorption of the CPO into matrix fibre occurs
simultaneously with the hydrolysis of lignocellulosic cell walls to weaken the fibre structure
which facilitates CPO to migrate into the matrix active site. Hence, simultaneous reaction
and desorption occurs here. The second step; 2) diffusion of the solvent into matrix took
place when HCW further diffuse and penetrates the weakened and loosened fibres. Another
adjustment in the mechanism also is observed in the third step; 3) dissolution of the species
into the bulk solvent. Due to CPO being insoluble in HCW this step is replaced by the
entrainment of CPO from the matrix into the HCW as solvent. However, there may be slight
dissolution of CPO in HCW at elevated temperatures during the process. In this step,
agitation helps to partially solubilise CPO in HCW to form the heterogeneous mixture. The
final step, 4) species mass transfer from the matrix into the solvent is applicable where the
phenomena in step 3) is facilitating the entrainment of CPO from the solid matrix into the
HCW.
During the first step of CPO extraction from palm mesocarp using HCWE, the reaction
is rapid but continuous throughout the extraction duration. The role of the reaction in this
case is facilitating the extraction process and under controlled conditions the reaction is mild
enough to break the cell walls therefore assisting the release of CPO into the fibre matrix. In
the first 20 mins, the main contribution for the highest extraction rate is the higher
concentration difference of CPO between sample matrix and bulk solvent (HCW). This is
typically observed in all types of solid-liquid extraction in the second order mass transfer
model equation [13, 27]. As the extraction time increases from 30 mins and above, the
concentration gradient of CPO between HCW and sample matrix gradually decreases since
most of the oil has been entrained in earlier batches. This exhibits the lower extraction rate
recorded in this stage of extraction process for all operating conditions. The second order
mass transfer model describes that the amount of species mass transfer is proportional to the
concentration gradient and interfacial area with the second degree polynomial rate [13]. This
model has taken into consideration of the varying concentration gradient over time therefore
giving a good representation of the extraction process.
In summary, for CPO extraction from palm mesocarp using HCWE process, the
mechanism of extraction was described as:
1) Simultaneous reaction of lignocellulosic cell walls/fibres and desorption of the species
into matrix fibre
2) Diffusion of the solvent into matrix, the weakened and loosened fibres enables further
diffusion and penetration of solvent into matrix
3) Entrainment of CPO from the matrix into bulk solvent
4) Species mass transfer from the matrix into the solvent

Conclusion
Temperature between 120 to 180oC gives significant effect to CPO yield (g-oil/ g-dried
mesocarp) in HCWE but pressure does not give significant effect. The maximum CPO yield
in the oil layer was 0.541 ± 0.005 with a further 0.1592 recovered from the emulsion layer
giving a total CPO yield of 0.700 g-oil/ g-dried mesocarp was obtained at 50 bar and 160oC.
Under these conditions the averaged FFA content in the HCWE extracted CPO was 0.807 ±
0.076 % which qualifies it for the SQ grade oil. A different mechanism for extraction of CPO
from palm mesocarp using HCWE where the hydrolysis of cell wall facilitates the
entrainment of the CPO from matrix core into the HCW was unveiled in this study. The
mechanism of extraction was described as: 1) simultaneous reaction of lignocellulosic cell
walls/fibres and desorption of the species into matrix fibre, 2) diffusion of the solvent into
matrix, 3) entrainment of CPO from the matrix into bulk solvent, and 4) species mass
transfer from the matrix into the solvent.
CPO extraction from palm mesocarp using HCWE is well described by the second
order mass transfer model. HCWE is a potential process in CPO SQ grade production but
further work is required to identify other valuable minor components present in the CPO.
Improved design which includes recovery/reduced CPO losses in oil-water emulsion and
used water treatment has to be further looked into.

Acknowledgements
The research is funded by Universiti Teknologi Malaysia (UTM) under University Grant
(GUP) grant no. Q.K130000.2543.06H91. The financial assistance from Universiti Malaysia
Perlis (UniMAP), Malaysian Ministry of Higher Education (MoHE) and Malaysian-Japan
International Institute of Technology (MJIIT) are greatly appreciated. The help and assistance
from En. Nasir, the Plantation Manager from Felda Mempaga Satu, Bentong, Pahang for
fresh fruit bunch supply is greatly acknowledged.

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 Pump I-3
I-2

Figure 1: Schematic diagram of the fabricated HCW extractor

0.6 3.5

0.5 3.0

mg-glucose/g-dried mesocarp
2.5
(g oil/dried mesocarp)

0.4 30 bar
40 bar
CPO yield,

2.0

Glucose,
50 bar
0.3 Glucose at 50 bar
1.5
0.2
1.0

0.1 0.5
Hemi-cellulose Glucose
0 0.0
120 130 140 150 160 170 180
o
Temperature, C
Figure 2: Effect of temperature on CPO yield at different pressures of 30, 40 and 50 bar and
glucose concentration in water layer extract at 50 bar using HCWE
 a) Intact cell

b) c)

Ruptured cell

Intact cell Pore structure

d) Intact cell e)
=
d)
Pore structure

Figure 3: SEM micrograph of palm oil mesocarp (a) after autoclave and after HCWE at b)
120oC, c) 140oC, d) 160oC, e) 180oC at constant pressure of 50 bar
 0.8 0.8
0.7 0.7
CPO in emulsion
g-oil /g-dried mesocarp

g-solid/ g-dried mesocarp

0.6 0.6
CPO yield,

Solid residue,
0.5 0.5
CPO yield (oil layer)
0.4 0.4
0.3 Solid residue 0.3
rrrrreresidue
0.2 0.2
0.1 0.1
0 0
120 140 160 180
Temperature, oC

Figure 4: Effect of temperature on CPO yield, CPO content in the oil-water emulsion and
solid residue formation at 50 bar

2.5 2.5 2.5

a. 30 bar b. 40 bar c. 50 bar
2.0 bar
Free Fatty Acid, %

2.0 2.0
Free Fatty Acid,%
Free Fatty Acid , %

1.5 1.5 1.5

1.0 1.0 1.0

0.5 0.5 0.5

0.0 0.0 0.0

10 15 20 25 30 10 15 20 25 30 10 15 20 25 30
Time, mins Time, mins Time, mins
120 oC, 140 oC, 160 oC, 180 oC
Figure 5: Effect of time at different temperatures and pressures to the FFA (%) in CPO
extracted using HCWE
 0.6
(a)

g-oil/g-dried mesocarp
CPO yield, 0.4

0.2

0
0 10 20 30 40 50 60
Time,mins
0.6
(b)
g-oil/g-dried mesocarp

0.4
CPO yield,

0.2

0
0 10 20 30 40 50 60
Time,mins
0.6
g-oil/g-dried mesocarp

(c)
CPO yield,

0.4

0.2

0
0 10 20 30 40 50 60
Time, mins
Second order model at 120°C Second order model at 140°C
Second order model at 160°C Second order model at 180°C
Experimental Data at 120°C Experimental Data at 140°C
Experimental Data at 160°C Experimental Data at 180°C
Figure 6: Comparison of CPO yield with time at different temperatures and constant
pressures of a) 30 bar b) 40 bar and c) 50 bar using HCWE (experimental data versus second
order mass transfer model prediction)
 Table 1: HCWE process conditions

Type Parameter Value

Temperature 120-180oC
Variables
Pressure 30, 40 and 50 bar
Stirrer speed 500 rpm
Solvent to sample ratio 5:1 (ml:g)
Constant
Extraction interval 10 min
Total extraction time 60 min

Table 2: One way ANOVA for CPO yield at constant pressure and temperature
Pressure, Temperature, ANOVA test
o
bar C f statistic p value

Constant 30 120 - 180 105.6

Pressure
40 120 - 180 28.9

50 120 - 180 279.4

30 – 50 120 6.15 0.07

Constant 30 – 50 140 3.72 0.13

temperature
30 – 50 160 28.53 0.01

30 – 50 180 4.47 0.09

Table 3: FFA value and one way ANOVA test at different temperatures and constant pressure
of 30, 40 and 50 bar in the first 10 mins of HCWE process
Pressure, Temperature, FFA ANOVA test
o
bar C % f statistic p value

120 0.57 ± 0.05

30 bar 140 0.42 ± 0.05 6.55

160 0.51 ± 0.05

180 0.47 ± 0.05

 120 0.48 ± 0.10

40 bar 140 0.38 ± 0.10 1.15

160 0.46 ± 0.10

180 0.42 ± 0.10

120 0.56 ± 0.08

50 bar 140 0.54 ± 0.08 0.32

160 0.59 ± 0.08

180 0.56 ± 0.08

Table 4: Comparison of palm mesocarp extraction using HCWE and other extraction methods
CPO yield FFA
Extraction method Reference
(g-oil/g-dried mesocarp) (%)

HCWE at 160oC and 50 bar

– Oil layer 0.541 ± 0.005 0.81 ± 0.08

This work
– emulsion layer 0.159 ± 0.004 0.99 ± 0.01

– Total 0.700 ± 0.005 0.85 ± 0.05

Soxhlet (Hexane) extraction 0.757 ± 0.005 0.790 ± 0.12 This work

Supercritical fluid CO2 extraction 0.77 0.61 [4]

Aqueous enzymatic extraction 0.71 NA [3]

Subcritical R134a extraction 0.66 NA [5]

Commercial CPO 0.611 3.53 [42]

1
Estimated based on mill data. NA = Not available.

Table 5: First and second order mass transfer coefficient, AARD and r 2 value
 1st Order mass transfer model 2nd Order mass transfer model

k2 Ceq
h
Temperature Pressure k1 AARD
AARD
(g-dried (g-oil/g-
(%) (g-oil/g-dried
(oC) (bar) (min-1) mesocarp/ dried (%)
mesocarp.min)
g-oil.min) mesocarp)

120 30 0.0139 31.433 0.815 0.1291 0.5739 0.0425 4.565 0.988

140 30 0.0102 46.693 0.849 0.1549 0.5556 0.0478 2.884 0.996

160 30 0.0265 16.954 0.746 0.1236 0.6647 0.0546 6.277 0.979

180 30 0.0157 27.696 0.863 0.1193 0.6102 0.0443 3.124 0.993

120 40 0.0138 32.283 0.826 0.1368 0.5696 0.0443 3.394 0.991

140 40 0.0183 17.609 0.826 0.0536 0.7217 0.0279 7.376 0.942

160 40 0.0159 35.874 0.751 0.1945 0.6049 0.0712 4.027 0.992

180 40 0.0127 41.344 0.863 0.2047 0.5617 0.0646 1.552 0.998

120 50 0.0156 29.842 0.761 0.2604 0.5289 0.0729 2.816 0.996

140 50 0.0154 27.898 0.920 0.1058 0.6132 0.0398 1.927 0.995

160 50 0.0157 36.651 0.850 0.1132 0.6741 0.0514 3.527 0.989

180 50 0.0099 43.075 0.931 0.1246 0.5432 0.0367 1.186 0.999

 0.6 3.5

0.5 3.0

mg-glucose/g-dried mesocarp
2.5
(g oil/dried mesocarp)

0.4 30 bar
40 bar
CPO yield,

2.0

Glucose,
50 bar
0.3 Glucose at 50 bar
1.5
0.2
1.0

0.1 0.5
Hemi-cellulose Glucose
0 0.0
120 130 140 150 160 170 180
Temperature, oC
Highlights:

1. Hot compressed water extraction for CPO is proposed

2. Extraction of CPO is through entrainment since it is insoluble in water
3. The hydrolysis of cell wall facilitates the entrainment of the CPO from matrix core
4. Process can be described by second order mass transfer model.