Residual Oil Recovery Using Bio-Ethanol from

Spent Bleaching Clay and Its Characterization

Mustafa Kamal Abdul Aziz
Department of Chemical and
Environmental Engineering,
University of Nottingham Malaysia,
Broga Road, 43500 Semenyih,
Selangor, Malaysia
clear.utm@gmail.com
Noor Azian Morad
Center of Lipids Engineering and
Applied Research (CLEAR),
Malaysia-Japan International
Institute of Technology (MJIIT),
Universiti Teknologi Malaysia,
54100 Kuala Lumpur, Malaysia
azian.morad@gmail.com
Noor Baini Nabila Muhamad
Center of Lipids Engineering and
Applied Research (CLEAR),
Malaysia-Japan International
Institute of Technology (MJIIT),
Universiti Teknologi Malaysia,
54100 Kuala Lumpur, Malaysia
baininabila@gmail.com

Takayuki Okayama Ryota Kose

Division of Natural Resources and
Ecomaterials, Institute of
Agriculture, Tokyo University of
Agriculture and Technology, Tokyo
183-8509, Japan
okayama@cc.tuat.ac.jp
Division of Natural Resources and
Ecomaterials, Institute of
Agriculture, Tokyo University of
Agriculture and Technology, Tokyo
183-8509, Japan
kose@cc.tuat.ac.jp

Abstract Residual oil from oil palm refining waste, spent
bleaching clay (SBC) was recovered through a pilot plant scale
up solvent extraction process. To develop a green extraction and
sustainable approach for recovery of oil, bio-ethanol was used as
a solvent instead of hexane. The SBC was extracted in a round-
bottomed jacketed vessel subjected to heat and two different
pressures. Two consecutive separation processes was applied in
this study, fractional crystallization followed by evaporation. The
yields of residual oils extracted slightly under vacuum pressure
were higher by 64% than those from the extraction at
atmospheric pressure. The residual oil recovered by evaporation
exhibited inferior qualities in term of free fatty acid (FFA). In
contrast, the oil recovered by fractional crystallization shows
superior FFA content to that of crude palm oil (CPO) which was
suitable for food applications.
Keywordsspent bleaching clay;residual oil; bio-ethanol;
solvent extractino; pilot plant
I. INTRODUCTION
SBC offers revenue of RM 90 million to the palm oil
processing industry [1]. Several processes have been
developed to strip residual oil from the clay matrix based on
treatment of the clay with dilute caustic solution or extraction
of the oil using organic solvent [3] especially hexane as
reported by other workers [2], [4], [5] and [6]. Hexane is
widely used since it is cheap and easily vaporized despite the
fact that it can be hazardous to human health and environment.
The use of hexane has become the common issues in the
environmental debate therefore, an alternative green solvent is
required to replace the use of hexane. In the present pilot
scale-up study, the residual oil of SBC was recovered using
bio-ethanol as an extracting medium. The extracted oil was
then separated from the solvent by cold and hot temperature
treatments which are the fractional crystallization and
evaporation, respectively. The characteristics of the extracted
oil were analysed before deciding on its appropriate
applications depending on its suitability.

In refining palm oil, bleaching earth is used to remove

colour, phospholipids, oxidized products, metals and residual
gums from the oil [1]. The Spent Bleaching Clay (SBC),
containing 30 - 40% oil, is generally disposed untreated. The
disposal of SBC in landfills may cause fire and pollution
hazards due to the substantial oil content in the clay. This
disposal constituted a significant economic waste and an
environmental burden [2]. Annual production of CPO is 15.9
million tonnes (2006). Based on that, approximately 0.8% of
bleaching clays which is 120,000 tonnes are used in palm oil
refining. The potential residual oils in SBC (based on 30% of
oil absorbed in SBC) that can be recovered are estimated to be
approximately 36,000 tonnes. Recovery of residual oil from
II. MATERIALS AND METHODOLOGY
A. SBC and Solvent Preparation
Spent Bleaching Clay (SBC) used in this study was
obtained from Malaysian local palm oil refinery operated by
Sime Darby Jomalina Sdn. Bhd. Bio-ethanol 99.8% (Mass
Tumor Resources) was used for the extraction process. The
ratio of solid to solvent (wt/v) is 1:10. The SBC was packed in
a stainless steel mesh cylinder with 26 m aperture size as
shown in Fig. 1(a). Each packed mesh contains 500 g of SBC
samples.

,(((
B. Pilot Plant Solvent Extaction
The extraction was performed in CLEAR (Centre of Lipid
Engineering and Applied Research) pilot scale round-bottomed
mineral oil jacketed vessel connected to a condenser as shown
in Fig. 1(b). Bio-ethanol (20 L) was poured into the 50 L round
bottom vessel as extracting medium. The packed clay (2 kg)
samples were soaked in the solvent and the vessel opening was
tightly closed. The extraction was performed at two different
pressure conditions (91.32 kPa and 101.32 kPa) with set boiler
temperature of 90C. The process was carried out for 5 hours
duration. For extraction process at 91.32 kPa reflux solvent is
being recycled back into the extraction vessel. Upon
completion, the SBC was removed from the extraction vessel
and taken out from the stainless steel mesh cylinder. The
experiments were carried out in triplicates.
b mbar pressure. The percentage yield of extracted oil known as
Fig. 1(a) Stainless steel wire mesh cylinder (b) Round-
bottomed mineral oil jacketed vessel connected to a condenser
in CLEAR.
To obtain the initial oil content in the SBC, 100 g of
samples was soaked in 1 L of bio-ethanol in a 2 L round
bottom flask. The extraction was carried out with continuous
stirring for 5 hours at 90 rpm. The extractant was filtered by
suction to separate the extracts and the SBC powder. The
solvent was then removed by means of a rotary evaporator. The
experiments were carried out in triplicates.The oil obtained
(Wlse) is used as a benchmark for deoiling efficiency.
C. Fractional Crystallization and Evaporation
Incubation: The extractant was filled up in a plastic
container of 20 L and stored at -25C in a deep freezer for 12
hours to growth the crystal of wax.
Crystallization: After 12 hours the mixture was loaded to
to a water jacketed crystallizer as shown in Fig. 2(a). The
vessel internal consists of five layers of stainless steel mesh
screen as shown in Fig. 2 (b). The water jacketed crystallizer
vessel was maintained at 5C cooling water. The light gold
solid known as gold fingers (GF) in this study was allowed
to settle on the screen by gravity force. The percentage yield
was calculated by the following expression:

 
where, WGF and WSBC are the weights of the separated solid
and the weight of the SBC used for the extraction process,
respectively.
a
Fig. 2(a) Crystallization water jacketed vessel (b) Five
layers of stainless steel mesh screen with 26 m aperture size.
Evaporation: To recover the remaining oils in the filtrate
from crystallizer vessel, the solvent was then separated using
rotary vacuum evaporation at 60C bath temperature and 175
black wax (BW) in this study was determined as (2):


where, WBW is the weight of the residual oil recovered from
the evaporator.
The percentage of deoiling efficiency was determined as (3):
 the extraction process. At lower pressure, the bio-ethanol
  molecules vibrate vigorously as it is near its boiling point.
Where, Wpse and Wlse are the weight of the total oil extracted
using pilot plant scale extraction and the weight of the total oil
extracted using lab scale extraction, respectively.
D. Analysis of the Characteristic of the Extracted Oils
The characteristic of SBC residual oil recovered by pilot
plant experiment such as FFA, carotene content,
saponification value and kinematic viscosity were determined
via AOCS Ca 5a-40, AOCS Cd 3.2 and ASTM D445 method
respectively. All the above measurements were performed by
SGS Laboratory Services (M).
III. RESULTS AND DISCUSSION
To develop a green extraction and sustainable approach for
recovery of oil, bio-ethanol was used as a solvent. Different
from industrial ethanol synthesized from petroleum, bio-
ethanol is the fermentation product of glucose from renewable
biomass (edible starch and non-edible cellulose, etc.), thus,
bio-ethanol is safe, clean, green and sustainable [8].
The concept of this pilot plant scale extraction with reflux
at 91.32 kPa corresponds to a typical percolations process
used in the extraction of plant matrix such as soxhlet
extraction. In extraction under reflux, the plant material is
immersed in a solvent in a round-bottomed flask, which is
connected to a condenser. The solvent is heated until it reaches
its boiling point. As the vapour is condensed, the solvent is
recycled back to the flask [9]. In this experiment, vacuum
pressure was exerted to achieve the reflux. However, the
reflux does not occur at atmospheric condition therefore the
extraction process corresponds to soaking in hot ethanol below
its boiling point.
A. Effects of Pressure in Pilot Plant Scale Up Extraction
The concentration of oil in the solvent extracted at two
different pressures in the pilot plant is shown in Table I.
Pressure is observed to markedly influence the amount of oil
extracted from the SBC. The oil extracted varies from 22.0 to
27.89% and 12.94 to 16.65% for extraction 91.325kPa and
101.325kPa, respectively. The deoiling efficiencies for
extraction with pilot plant at 91.325 kPa are 59.4% and 36.2%
at 101.325 kPa. This shows that extraction performed under
slight vacuum give a higher efficiency. Increased extraction
yield during vacuum extraction was due to the expanded
volume of bio-ethanol surrounding the SBC particles allowing
more intermolecular interaction between bio-ethanol and oil
molecules. The comparison from the different condition of the
extraction is shown in Fig. 3. Extraction under vacuum
condition corresponds to percolations condition which gives
good mixing created through turbulence due to reflux during
This vibration created bubbles particularly around the SBC
bed thus increased the contact between the solid matrix and
the solvent which enhanced the solubility of the oil in the
solvent. This condition gives higher efficiency compared to
the static soaking condition at atmospheric extraction.
However, overall the extraction efficiency is still low and
this is attributed to the confinement of the sample within the
stainless steel mesh which restricts the mass transfer of oil into
the solvent. This can be improve by packing the SBC samples
into smaller stainless steel mesh container of 50g each for
better mass transfer and interaction between samples and
solvent. Further improvement can be made through better
mixing by having higher reflux through reduced pressure to
higher vaccum. Incorparating mechanical agitator in the
system can facilitate mass transfer process during extraction.
The percentage yields of residual oils recovered in this
study were comparable to that reported by other workers [2],
[3], [4] and [10] equivalent to 15 up to 40% of residual oil
yields. It is expected that improved extraction conditions using
bio-ethanol will further improve the current deoiling
efficiency values.
B. Yield of Gold Finger and Black Wax
It can be observed from Table II, that the GF yield ranges
from 9.0 to 24.6% and the BW yield ranges from 3.29 to
6.5%. GF yield is very much affected by the percentage of
total oil yield i.e. directly proportional. Whereas the BW yield
is not influence by the percentage of total oil yield and is
constant at 4.78% 0.84 as shown in Fig. 4. The relationship
between percentage of total oil yield and gold finger is also
illustrated in the Fig. with linear regression.
TABLE I. Summary of the extraction conditions for the
different pressure.
Pressure Batch Clay to Total (%)AVG (%)MAD
(kPa) solvent yield
ratio (%)
(kg/L)
1 27.89
91.325 2 1:10 25.20 25.03 2.02
3 22.00
1 12.94
101.325 2 1:10 16.65 15.27 1.56
3 16.23
AVG average
MAD mean absolute deviation
 C. Characterisation of Residual Oils Extracted
Pabs (kPa) 91.325 Pabs (kPa) 101.325
The results in Table III, shows that the FFA of GF
Co (kg/kg) Mean [0.25]
recovered by means of fractional crystallisation (cold
Mean [0.15] temperature treatment) is much lower than that of BW
Concentration of oil in solvent,

0.45 which was recovered by means of rotary evaporation

0.40 0.42 (hot temperature treatment). This increase in FFA values
0.35 is attributable to the hydrolysis of some of the
0.30 triglycerides, catalyzed by the acidic sites of the
(kg/kg)

0.25 bleaching clay [10]. In addition, the FFA of GF which is

0.20 1.23% is also lower than the FFA content of crude palm
0.15
Increase yield by 64% when oil (CPO) which is 3 5%. Due to this low FFA content
0.10 decrease pressure by !0%
0.05 in GF, it may have potential in foods application in spite
0.00 of its low carotene value compared to that of CPO. As
for BW, the possible applications except for foods
0 1 2 3 4
include coating material, lubricants, plasticiser, and
Batch emulsifier. Futhermore, the dark color of BW dictates
that the colored matter (i.e., carotenoid and chlorophyll
Fig. 3. Effect of extractiom pressure on the yield of SBC pigments) that was removed by the SBC in the refining
residual oil. process is concentrated in BW instead of concentrated in
GF. This was further approved by the measurement of
TABLE II. The results of GF and BW
carotene content. BW reported to have 103.1 ppm
carotene content which was higher than the carotene
Total GF BW BW(%)AVG BW (%)MAD content of GF which was only 3.3 ppm.
yield (%) (%)
(%) TABLE III. Characteristic of extracted residual oils of SBC
27.89 24.6 3.29 Characteristic GF BW CPO
25.20 20.0 5.20
FFA, % 1.23 25.19 3-5
22.00 15.5 6.50
4.78 0.84
12.94 9.0 3.94 Saponification value
16.65 11.5 5.15 198 202.3 194 to 205
(mgKOH/g)
16.23 11.65 4.58
Kinematic viscosity at
66.07 77.89 45.34 at 40C
AVG average 30C (mm2/s)
MAD mean absolute deviation
Carotene (ppm) 3.3 103.1 474 to 689

GF (%) BW (%)
IV. CONCLUSION
Percetange of GF and BW

30
25 y = 1.004x - 4.858 The extraction of residual oils of SBC in pilot plant scale
R = 0.964 solvent extraction using bio-ethanol as a green and sustanaible
20 method requires further improvement on the process design to
yield, %

15 increase the extraction efficiency. It was observed that the

10 percentage of oil yields was affected by the pressure. At 91.325
5 kPa the oil yield was 25.03% 2.02 and at 101.325 kPa the oil
yield was 15.27% 1.56. The characteristic of GF and BW
0 shows suitability for food and non-food application,
10 15 20 25 30 respectively.
Total oil yield, % ACKNOWLEDGMENT
Authors would like to acknowledge Ministry of
Agriculture and Agro-Based Industries (MOA) for the
Fig. 4. The relationship of GF and BW yield to the percentage Technofund Grant (Project No-tf0310c113) to finance this
of total oil yield. research study. Individuals who have contributed to this work
are also gratefully acknowledged.
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