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A Study of Residual Oils Recovered from Spent Bleaching Earth: Their

Characteristics and Applications

Article  in  American Journal of Applied Sciences · October 2006

DOI: 10.3844/ajassp.2006.2063.2067 · Source: DOAJ

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American Journal of Applied Sciences 3 (10): 2063-2067, 2006
ISSN 1546-9239
© 2006 Science Publications

A Study of Residual Oils Recovered from Spent Bleaching Earth:

Their Characteristics and Applications

Loh Soh Kheang, Cheng Sit Foon, Choo Yuen May and Ma Ah Ngan
Malaysian Palm Oil Board, P. O. Box 10620, 50720 Kuala Lumpur, Malaysia

Abstract: This study described the extraction of residual oils of spent bleaching earth (SBE) from
palm oil refining industry, the properties and applications of residual oils obtained there from. Residual
oils of SBE (acid-activated, WAC and neutral, NC) were recovered via solvent and supercritical-fluid
(SC-CO2) extraction. The yields of residual oils recovered from WAC were higher than those from NC
using solvent and SC-CO2 extraction respectively. Both the residual oils recovered from WAC and NC
had fatty acids composition (FAC) similar to that of crude palm oil. These oils exhibited poor qualities
in terms of free fatty acids (FFA) content and peroxide value (PV). As the residual oils had very high
FFA value (more than 10%), they were no longer suitable for food applications. Alternatively, these
oils can be converted to their respective methyl esters for biofuel and other non-food applications as
they were thermally and chemically stable with induction period of up to 29 h in Rancimat test. The
methyl esters conversion via esterification and transesterification gave optimum yields of more than
80%. The methyl esters obtained have comparable fuel properties as petroleum diesel; hence, they can
be used as diesel substitute.

Key words: Residual oil, spent bleaching earth, extraction, methyl esters, biodiesel

INTRODUCTION extracted oil form SBE. Theoretically non-polar solvent

such as hexane allows the use of extracted oil in foods.
Pre-treatment of crude palm oil in refinery which To obtain oil with better quality, the extraction has to
involves degumming and bleaching generates plenty of be carried out on fresh SBE and under nitrogen
spent bleaching earth (SBE). It is estimated that about protection.
600,000 metric tones or more of bleaching earth are Aqueous extraction was another inexpensive
utilized worldwide in the refining process based on the method to recover oil that retained in SBE. The types of
worldwide production of more than 60 million tones of aqueous extraction were steam blowing through SBE,
oils[1]. The SBE serves as by-product, which contains circulating hot water through the cake, boiling of SBE
high percentage of oil[2]. Disposal of SBE by in water containing soda and salt. The quality of oil
incineration, inclusion in animal feeds, land filling recovered was poor and only suitable for technical
method or concrete manufacturing is generally purpose.
practiced. Large quantity of SBE is disposed off in The oil was also recovered via supercritical-fluid
landfills, causing fire and pollution hazards due to the extraction[8]. Extraction of SBE via supercritical fluid
substantial oil content in the earth. The oil in SBE technology is a clean and environmental friendly
would be wasted if it were not recovered and causes technology, utilising non-hazardous carbon dioxide
loss of oil in the long run. (SC-CO2) as solvent for extraction of oil. Overall good
The oil was commonly recovered by solvent quality of oil can be recovered by this method.
extraction[2-7]. Depending on the applications of the The loss of oils in SBE is a cause for concern from
extracted oil, several non-polar or polar solvents can be the palm oil industry as the oil can be used for
considered as extracting medium. Polar solvents such as industrial purposes. The oil retained in SBE should be
acetone, methylethyl ketone, methylene chloride, recovered and re-used as raw materials for industrial
perchloroethylene, isopropyl alcohol, chloroform applications to save cost in the oil processing industry.
extract polar components, coloured bodies together One possible approach is to convert the oil into fatty
with the oil from SBE while non-polar solvents such as acid alkyl esters. There existed a process to treat SBE in
petroleum benzene, petroleum ether, toluene, xylene, organic (alcohol) phase at high temperature (110-
hexane, flugen extract the non-polar fractions mainly 270°C) and moderate pressure to simultaneously
triglycerides as well as other useful non-polar recover the oil and convert it into alkyl esters of C1 to
components. The type of solvent used and the method C8 carbon atoms[1]. The oil was converted in situ to
of oil extraction could determine the quality of the alkyl esters using methanol and used as oleochemical
Corresponding Author: Loh Soh Kheang, Malaysian Palm Oil Board (MPOB). P. O. Box 10620, 50720 Kuala Lumpur,
Malaysia
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 Am. J. Appl. Sci., 3 (10): 2063-2067, 2006

feedstock. The alkyl esters especially methyl esters are filtrate was pumped dry before subjected to the
very useful ingredients for non-food applications. transesterification process.
In this study, the residual oil of SBE was The resin-treated WAC residual oil (FFA 1.5%,
recovered by solvent extraction and supercritical-fluid 193 g), methanol (96 mL) and NaOH (0.031M) were
extraction and the oil was then converted to methyl refluxed in a round bottom flask at 80ºC for 30 minutes.
esters of C14 to C18 using an modified approach from At the end of reaction, the reaction mixture was left
the established process[9,10] designated for conversion of settling in a separating funnel. The upper layer
methyl esters from pure palm oil. containing methyl esters/methanol was separated from
the lower layer containing glycerol/methanol. The
MATERIALS AND METHODS esters layer was washed excessively with water and
pumped dry for fuel characterization. The yield of
Materials: Two types of spent bleaching earth (SBE), methyl esters obtained was 84%.
i.e. acid-activated, WAC and neutral, NC were obtained
from Malaysian local palm oil refinery. All solvents Esterification/transesterification of residual oil of
used were of analytical grades: hexane, methanol, SBE (NC)[10]: Residual oil of NC (FFA 12.6%, 200 g)
ethanol, petroleum ether were purchased from Merck, and RH resin (20 g) were mixed with methanol (100
Germany. The catalysts used for conversion of residual mL) in a round bottom flask. The reaction mixture was
oil to methyl esters i.e. sulphonated ion exchange (RH refluxed for 3 hours at 80ºC, filtered by suction and the
resin) and sodium hydroxide (NaOH) were purchased residue resin was rinsed several times with
commercially. methanol/petroleum ether b.p. 60-80ºC to remove any
oil trapped in the resin. The filtrate was pumped dry
Solvent extraction of residual oil from SBE (reflux before subjected to the transesterification process.
condition): The SBE (WAC) (800 g) was packed in a The resin-treated NC residual oil (FFA 0.4%, 195
thimber inside a soxhlet extractor. Hexane (3 L) was g), methanol (99 mL) and NaOH (0.026M) were
poured into a 5 L round bottom flask as extracting refluxed in a round bottom flask at 80ºC for 10 minutes.
medium. The extraction was continued for 2 days until At the end of reaction, the reaction mixture was left
the extracted hexane was colourless. Removal of settling in a separating funnel. The upper layer
hexane under reduced pressure left a yellow residual oil containing methyl esters/methanol was separated from
(30%), which was then subjected to esterification the lower layer containing glycerol/methanol. The
process. The residual oil of SBE (NC) was obtained in a esters layer was washed excessively with water and
similar manner to give 21% of yellow residual oil. The pumped dry for fuel characterization. The yield of
percentage yield of residual oil recovered from SBE methyl esters obtained was 82%.
(WAC & NC) was based on the weight of SBE used for
the extraction process. Analysis: The physicochemical characteristics of the
residual oil from SBE such as FFA, peroxide value
Solvent extraction of residual oil from SBE (room (PV), phosphorus, iron, copper, carotene content and
temperature): The SBE (WAC & NC) (800 g) was total vitamin E were determined via PORIM Test
soaked at room temperature (30ºC) separately with Methods (1995)[11]. All the above measurements were
hexane (3 L) in two 5 L flasks for 2 days. The mixture done in triplicate and the mean values were reported.
was stirred at regular interval. At the end of extraction, The fatty acid compositions (FAC) were
hexane was removed under reduced pressure to give determined using gas-liquid chromatography, with
residual oil yields of 29% for WAC and 20% for NC. reference to the AOCS Ce 1-62 (97)[12] standard
method. The reaction mixture of methyl esters were
Supercritical fluid (SC-CO2) extraction of residual conducted using gas chromatography (GC) with a BPX
oil from SBE: The same amounts of SBE (WAC & 5 capillary column with programmed temperature as
NC) as above were subjected to SC-CO2 extraction. follow; oven temperature: 100ºC, initial temperature:
The oil yields were 27% for WAC and 20% for NC. 100ºC, final temperature: 350ºC, injector temperature:
254ºC, detector temperature: 360ºC, rate: 10ºC min-1,
Esterification/transesterification of residual oil of carrier gas: Helium at 2.0 mL min-1.
SBE (WAC)[10]: Residual oil of WAC with free fatty Viscosity measurements of the methyl esters were
acids (FFA) of 11.45% (200 g) and RH resin (20 g) performed using Automated Multi Range Viscometer
were mixed with methanol (100 mL) in a round bottom HVM472 (Walter Herzog, Germany) at 40°C according
flask. The reaction mixture was refluxed for 3 hours at to ASTM[13] test method D445. All measurements of
80ºC, filtered by suction and the residue resin was viscosity were performed in duplicate and the mean
rinsed several times with methanol/petroleum ether b.p. values were reported. The pour point measurements
60-80ºC to remove any oil trapped in the resin. The were performed using an automatic pour point/cloud

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 Am. J. Appl. Sci., 3 (10): 2063-2067, 2006

point measuring apparatus (ISL CPP 97-2 Analyzer) agricultural chemicals, emulsifiers, soap, candle and
according to ASTM test method D97. The density other oleochemicals.
measurements were conducted using a digital density For this study, the residual oils exhibited FFA of
meter according to ASTM test method D4052. Petronas 11.5 and 12.6%. To get rid of the high FFA in oil, the
Research & Scientific Services Sdn. Bhd. Malaysia esterification step using RH resin (preferably 10% by
performed the rest of the measurement for fuel weight i.e. ratio of oil to RH resin 10:1) must be
characteristics of methyl esters. accomplished to convert most of the FFA in oil to
The oxidative stability of methyl esters was methyl esters[9,10]. This could avoid formation of soap
performed using the Model 743 Rancimat (Metrohm that gave complication during the transesterification
AG, Switzerland). Samples of 3g were analyzed under process, which convert the triglycerides to methyl
constant airflow of 10 L/h and the temperature of the esters. The conversion of triglycerides and remaining
heating blocks at 110ºC. All determinations of FFA (less than 5%) to methyl esters using small
induction periods were performed in duplicate and the quantity of NaOH was more than 98% (monitored by
mean values were reported. GC). Table 2 shows the composition of methyl esters
derived from residual oils of SBE (WAC and NC).
RESULTS AND DISCUSSION
60
The residual oils obtained from different types of

FFA (%)
SBE were characterized. Residual oils recovered from 40
SBE via SC-CO2 extraction were light yellow in color 20
whereas with hexane, the oils were darker in color for
both types of SBE used. It is interesting to find that no 0
iron and copper was detected in the residual oils 0 1 2 3 4
recovered via SC-CO2. This observation reveals that the
residual oils recovered by SC-CO2 have less impurity. Catalyst Concentration (weight %
Table 1 shows the better quality of the residual oils based on oil)
recovered via SC-CO2 than oils recovered via hexane Fig. 1: Correlation of FFA and catalyst concentration in
by lower PV value and total phosphorus content. The the esterification process. Reaction time: 3 hrs
FFA values of residual oils remain the same for both
types of extraction method used.
60
It was found that the recovery of residual oils from
FFA (%)

SBE (WAC) was higher than that of SBE (NC) via both 40
solvent and SC-CO2 extractions respectively. This 20
might be due to the higher capacity of oil retention by 0
SBE (WAC) during the physical refining process.
Extraction of SBE by solvent at both room temperature 0 30 60 90 120 150 180
and elevated temperature (reflux condition) gave Reaction Time (minutes)
comparable yields of residual oils. The percentage
yields of residual oils recovered in this study were Fig. 2: Correlation of FFA and reaction time in the
comparable to that reported by other workers[1,6] esterification process. Ratio of oil to catalyst:
corresponding to 20 up to 40% of residual oil yields. 10:3
The extraction of SBE by both the extraction
methods yielded residual oils with FAC that When the FFA of residual oils increased to 44.8%
corresponded fully with the expected values for crude due to the exposure of the earth to air for a couple of
palm oil. The insignificant difference in the FAC months, the conversion of the residual oils to their
between crude palm oil and the residual oil of SBE corresponding methyl esters could still be possible.
confirms that the refining process has no effect on the However, the amount of RH resin used and reaction
fatty acid or triglyceride composition of the oil and the time for the esterification process could be different.
bleaching earth does not alter the chemical properties of Investigation was done to find the optimum condition
the oil. for the conversion of residual oil with 44.8% of FFA
content. To determine the optimum treat level of RH
Conversion of residual oil of SBE to methyl esters: resin required, the esterification time was fixed at three
Due to the high FFA content of residual oils recovered hours and the amount of RH resin used varied from 1
from both types of SBE, their applications in foods are wt% to 4 wt% based on the amount of residual oil used
limited. However, these residual oils can be used in for esterification. A small quantity of reaction mixture
non-food applications such as converting them to was taken and checked on its FFA content at the end of
methyl esters as biofuels. Other possible applications the reaction. It was found that the ratio of oil to RH
include bio-lubricants, grease, plasticisers, detergents, resin most effectively used to reduce FFA to below 5%
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 Am. J. Appl. Sci., 3 (10): 2063-2067, 2006

Table 1: Characteristics of residual oils of SBE (WAC & NC)

Characteristics of residual oil Solvent extraction SC-CO2 extraction

WAC NC WAC NC
FFA (%) 11.5 12.6 11.5 12.6
PV (meq/kg) 3.1 3.4 2.8 2.2
Phosphorus (ppm) 19.3 18.7 18.1 15.8
Fe (ppm) 0.22 1.24 N.Da N.D
Cu (ppm) 0.32 0.38 N.D N.D
Carotene Content
-Carotene (ppm) 3 6 7 7
Total Vitamin E (ppm) 0 0 0 38.8
Fatty Acid Composition, FAC
(wt% as methyl esters)
C14:0 1.1 1.0 1.2 1.3
C16:0 45.2 44.4 44.5 43.6
C18:0 4.9 4.7 5.1 4.9
C18:1 37.9 39.4 38.6 39.7
C18:2 10.9 10.5 10.6 10.5
Oil Recovery (%) 30 21 27 20
a
Note: Not detected

Table 2: Composition of methyl esters derived from residual oils of SBE

Composition WAC Methyl Esters (%) NC Methyl Esters (%)
Esters 99.5 98.9
Monoglycerides 0.45 1.00
Diglycerides 0.05 0.10
Triglycerides 0.00 0.00
Fatty Acid Composition, FAC
(wt% as methyl esters)
C14:0 0.9 0.8
C16:0 44.8 43.8
C18:0 5.1 4.9
C18:1 38.6 39.3
C18:2 10.6 11.2

Table 3: Fuel properties of methyl esters derived from residual oils of SBE
Properties WAC Methyl Esters NC Methyl Esters Malaysian Diesel
Density at 25°C (kg/L) 0.9051 0.8853 0.8310
ASTM D4052
Viscosity @ 40ºC (cSt) 3.7 3.7 4.0
ASTM D445
Sulfur Content (wt%) 0.04 0.04 0.10
IP 242
Pour Point (ºC) 16 15 15
ASTM D97
Flash Point (ºC) 172 164 98
ASTM D93
Gross Heat of Combustion (kJ/kg) 38,080 39,470 45,800
ASTM D240

is 10:3 as shown in Fig. 1. Using this optimum ratio, The methyl esters obtained have relatively high
the esterification process was monitored to find the induction periods; i.e. 14.6 hours for WAC methyl
optimum reaction time required to lower FFA to below
5%. A small quantity of reaction mixture was taken at esters and 29.4 hours for NC methyl esters, determined
half an hour time interval and checked on its FFA via Rancimat test (pr EN 14112)[14] at 120ºC. The
content. Fig. 2 shows the subsequent reduction trend of Rancimat stability test determines the acceptance of
FFA of residual oil from 44.8 to 5.6%. methyl esters as biodiesel; a minimum of 6 hours is
required for the methyl esters to be used as automotive
Fuel characterisation: Table 3 shows the fuel
properties of methyl esters derived from residual oils of diesel fuel. The Rancimat results thus indicate that the
SBE. From the results, it is shown that the methyl esters methyl esters derived from residual oil of SBE are of
obtained have comparable fuel properties as petroleum good thermal stability and within the acceptable range
diesel. Hence, these methyl esters may be used as a for use as a biodiesel.
diesel substitute.

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 Am. J. Appl. Sci., 3 (10): 2063-2067, 2006

CONCLUSION 6. Aziz, A.R., S. Harcharan, E.M. Elkanzi, L.S. Lam

and S.H. Liew, 2001. Feasibility study of oil
The study shows that solvent and SC-CO2 recovery from used bleaching earth using waste
extractions could quantitatively recover the residual oils solvents. Porim Intl. Palm Oil Cong. (PIPOC)
of SBE. The residual oils with various concentration of
Proc., pp: 126-133.
FFA content can be converted to methyl esters for non-
food applications and as diesel substitute. 7. Chanrai, N.G. and S.G. Burde, 2004. Recovery of
oil from spent bleaching earth. US Patent No.
ACKNOWLEDGEMENTS 6,780,321 B2.
8. Waldmann, C. and R. Eggers, 1991. De-oiling
The authors wish to thank Tan Sri Datuk Director- contaminated bleaching clay by high-pressure
General of MPOB for his support and permission to extraction. J. Amer. Oil Chem. Soc., 68: 922-930.
publish this study. Thanks are also due to the staff of 9. Choo, Y.M., A.S.H. Ong, K.Y. Cheah and A.
Processing Research Laboratory for their technical
Bakar, 1988. Production of alkyl esters from oils
assistance.
and fats. Australian Patent PI 1105/88.
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