Research Article 769

Vilppu Kuuluvainen1
Extraction of Spent Bleaching Earth
Päivi Mäki-Arvela1
Kari Eränen1 in the Production of Renewable Diesel
Anton Holappa2
Jarl Hemming1 The extraction of oils based on animal fat and vegetable oil from two types of
Heidi Österholm3 spent bleaching earths, namely from the acidic sepiolite and the nonacidic paly-
Blanka Toukoniitty3 gorskite, was investigated by the Soxhlet method with hexane as a solvent. The
yields of oil were independent of the feedstock, whereas a much lower oil yield
Dmitry Y. Murzin1
was obtained with palygorskite exhibiting also a smaller surface area as compared
1
to sepiolite which provided a higher yield. The glyceride compositions were very
Åbo Akademi University, similar in bleached and extracted oils, while slightly lower melting and crystalliza-
Process Chemistry Centre, tion energies were determined by differential scanning calorimetry for the ex-
Turku, Finland.
tracted oils bleached with acidic clay indicating minor hydrolysis of triglycerides.
2
Åbo Akademi University,
Laboratory of Polymer Keywords: Clay, Differential scanning calorimetry, Oil extraction, Renewable diesel,
Chemistry, Turku, Finland. Spent bleaching earth
3 Received: January 26, 2015; revised: February 12, 2015; accepted: February 16, 2015
Neste Oil, Porvoo, Finland.
DOI: 10.1002/ceat.201500052

1 Introduction
In the production of renewable diesel the feedstock is subjected
to bleaching. The term ‘‘bleaching’’ originates from the food in-
dustry and has been recently adapted to the manufacturing
process of renewable diesel [1]. Three different types of bleach-
ing processes are in general use, namely, heat bleaching, chemi-
cal oxidation, and adsorption. The most common method is
bleaching by adsorption [2]. In the food industry, bleaching
was originally used mainly to reduce the color of fats and oil,
but has been developed to remove undesired or harmful by-
products from the feedstock. In practically every type of oil or
fat used as a feedstock there are a variety of compounds which
have to be removed, e.g., phospholipids, soaps, and heavy met-
als [3].
In the bleaching process, the feedstock is brought into con-
tact with a surface-active substance that adsorbs the contami-
nating compounds and particles [2]. Chemical and physical in-
teractions during the bleaching process where the contaminant
holds onto the sorbent can be described in three different ways:
via chemical interactions occurring through ionic bonds, via
physical attraction described by Van der Waals forces or by
molecular sieving effect when the contaminants are trapped in-
side the pores of the bleaching earth (BE) [1]. The lipid extrac-
tion from hexane onto acid-activated bleaching earth was
studied by Fourier transform infrared spectroscopy (FTIR). Ac-
cording to ref. [4], the lipid adsorption occurs via polar groups
– the oil. The SBE containing oil can cause environmental prob-
Correspondence: Prof. Dmitry Y. Murzin (dmurzin@abo.fi), Åbo
Akademi University, Industrial Chemistry and Reaction Engineering,
Biskopsgatan 8, Turku 20500, Finland.
between the lipid and OH groups and bound water on the
bleaching earth.
In modern bleaching facilities, the most important adsorbent
is bleaching earth or clay [5]. Adsorbents applied for bleaching
can be categorized into three main categories, i.e., activated car-
bon, naturally active BE, and activated BE [3]. Naturally active
clays are used as adsorbents because of their high adsorptive
capacities which are derived from their high specific surface
area. Naturally active clays are most commonly layered sili-
cates, i.e, between the two tetrahedral sheets there is a sand-
wiched octahedral sheet [3].
Activated BEs are usually activated with mineral acids, e.g.,
sulfuric or hydrochloric acid. The activation is done at elevated
temperatures for a few hours [3]. The acid treatment causes al-
terations to the chemical and physicochemical properties and
increases the specific surface area of the BE [5] by removing
the large ions such as K+, Ca2+, Mg2+, and Na+ and replacing
them with H+. The relation between the porosity and the sur-
face chemistry is vital to the effectiveness of the BE [2]. Acti-
vated BE is the most commonly used type of adsorbent for the
purification of animal fats and vegetable oils [3].
Besides clear advantages of feedstock cleaning, the usage of
BE in the bleaching process also causes such problems for the
refineries like oil retention, filtration, and environmental mat-
ters [2]. The spent bleaching earth (SBE) can contain up to
40 % oil by weight. This constitutes a major oil loss and the
SBE is currently disposed as such without any oil recovery [6].
Filtration efficiency is affected by the clay type, but more signif-
icantly by the particle size of the BE. Very fine particles in the
BE cause longer filtration times needed to separate the BE from
lems or at least increase land-fill disposal costs [2]. For the
edible-oil industry, the cost of the oil lost by retention in the
SBE is negligible because of the lowered quality of the oil. In

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770 Research Article

situ biodiesel production starting from the recovered spent oil from the palm tree, namely palm kernel oil and oil from the
from SBE has been recently demonstrated [7, 8]. On the con- pulp (palm oil). The latter one contains palmitic (32–47 %) and
trary, the quality of the oil extracted from the SBE is not an is- oleic (40–52 %) acid [13]. The flow sheet of the production of
sue for the renewable diesel refineries calling for an efficient oil renewable diesel is shown in Fig. 1. According to our knowl-
recovery procedure. edge, extraction of animal fats from SBEs and the content of in-
Adsorption and absorptive capabilities are demanded from organic elements in fresh and extracted oils have not yet been
the BEs. As is well-known, absorption means that molecules in described in the open literature.
the fluid penetrate the bulk of the absorbing solid, whereas the
term adsorption indicates interactions between the molecules fresh bleaching
in the fluid and the solid surface. The major factors contribu- earth
ting to absorption and adsorption processes are the particle-
size distribution, porosity, capillary structure, and the active Hydro- Renewable diesel
feedstock bleaching
surface of the solid. The grain size of the sorbent is also an im- treang
portant factor in the rate of sorption [9]. Filterability issues are
caused by many small BE particles, therefore, a compromise is
extracted bleaching
needed. Spent bleaching extracon earth (EBE)
earth (SBE)
Extraction of vegetable oils from SBEs has been demonstrat-
ed in a few publications [6, 10, 11]. A comparative study of ex-
traction efficiencies from an SBE with different solvents was hexane
demonstrated in [10], in which ethanol gives a higher extrac-
Figure 1. Flowsheet for the production of renewable diesel.
tion efficiency of about 34 % compared to methanol with 21 %
for crude palm oil from an SBE which was delivered from Car-
otino SDN, Malaysia [10]. The reason for this was stated to be
the lower solubility of methanol in crude palm oil in compari- 2 Materials and Methods
son to ethanol. Slightly lower extraction efficiencies of about
28 % were achieved with hexane and petroleum ether being less
2.1 Feedstocks and Adsorbents
polar [10]. Analogous results for the extraction efficiencies of
SBE from a palm oil refinery spent were achieved in ref. [6]. Different feedstocks were used in the current study. Feedstock
On the other hand, only 21 % oil recovery from the SBE deliv- A originated from animal fat and contained 29.2 wt % fatty
ered from an edible oil producer in Taiwan was found with acids of carbon atoms below or equal to 16 carbon atoms,
hexane extraction using 1:4 ratio of hexane to oil in a Soxhlet whereas feedstock B and C involved 44.4 wt % of these fatty
extractor [10]. The reason for the low extraction efficiency in acids. The amount of saturated as well as mono-, di-, and tri-
[10] might have been the high content of saturated fatty acids unsaturated fatty acids in different feedstocks is given in Tab. 1.
in the recovered oil and its high viscosity. Hexane is known to Feedstock B and C contained more saturated fatty acids com-
be a proper solvent to maintain oil quality high [12]. The oil pared to the composition of feedstock A.
quality was, however, better, when extracted with nonpolar
solvents (see above) [11]. When using more polar solvents,
such as methanol or ethanol, the extraction rate can be even Table 1. Fatty acid distribution [%] of different feedstocks.
higher than that for hexane, but in addition to extraction, also
hydrolysis of triglycerides occurs more easily with more polar Feedstock Saturated Mono- Di- Tri-
solvents on acidic clays [6]. Furthermore, the separation of unsaturated unsaturated unsaturated
water, pigments, and phosphorous compounds is more difficult
A 43.1 47.6 8.2 0.9
from the extracted oil in the case when the SBE has been ex-
tracted with, e.g., ethanol [10]. B, C 49.3 39.5 10.3 0
In this context, the extraction kinetics of oil from spent
bleaching was studied, using either palygorskite or sepiolite as
adsorbents. The former one was only treated thermally, where- Two commercially available adsorbents, i.e., sepiolite and
as the latter one was acid-treated. In addition to the investiga- palygorskite, served as adsorbents. Their specific surface areas
tion of oil recovery per se in the current work, also the chemi- were 204 and 146 m2g–1, respectively. Sepiolite was acid-treated
cal composition and content of inorganic elements of the and the pH value of its slurry in deionized water was 2–3,
extracted and bleached oils were compared to those for the whereas thermally treated palygorskite was exhibiting a pH of
fresh ones. Three different feedstocks, composed of either the slurry equal to 8.
100 % animal fat (feedstock A), which is a by-product of the
meat packing industry, or of a mixture of crude palm oil (CPO)
and palm fatty acid distillate (PFAD) (feedstock B and C) were 2.2 Extraction Method for Oil
selected. In the former case, the most common inedible animal
fats are tallow and greases, whereas the feedstocks B and C A conventional Soxhlet extractor was used to extract the ad-
contain palm oil from oil palm (Elaies guineensis) fruits, which sorbed oil from the SBE. Extraction was performed under
can produce two different oils. Two types of oil are obtained reflux conditions with hexane as solvent. Typically, 25 g of SBE

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 Research Article 771

was weighed into the extraction thimble and 100 g of hexane
into the distillation flask. The apparatus was then placed on a
heat source and hexane was heated up to its boiling tempera-
ture. The boiling hexane evaporates to the condenser from
where it drips onto the SBE. When the hexane level reaches the
overflow level in the extractor, the siphon aspirates the hexane-
oil mixture back into the distillation flask below. The circula-
tion of the solvent is carried on through the whole extraction
process with fresh solvent continuously in contact with the
SBE in the extractor. The temperature during extraction varied
in the range of 52–58 C in such a way that at the top of the
thimble the temperature was 57–58 C, in the middle between
53–55 C, and at the bottom 52–54 C. After extraction, the
hexane-oil mixture was allowed to cool down. Hexane was then
evaporated in an evaporator from the hexane-oil mixture and
the remaining oil was weighed.
The BE from which the oil was extracted (EBE) was gathered
from the extraction thimble and weighed; it was then left over-
night in order for the remaining hexane in the EBE to evapo-
rate off. Before the EBE was collected for analysis, it was put in
an oven at 105 C for 16 h.
The extraction was performed twice for every kinetic mea-
surement, in which each point corresponds to a separate exper-
iment and the average percentage denotes the yield for that ex-
traction time. The theoretical oil content of the SBE samples
was calculated from the weight loss obtained from the thermo-
gravimetric analysis (TGA) results by comparing the weight
loss of the SBE with the one of the fresh BE.
50-mL measuring flask and weighed. Tetrahydrofuran served
as eluent. The samples were analyzed by SEC together with the
calibration samples containing sterol.
A 1-mL portion of the dissolved samples was filtered
through a 0.2-mm filter and analyzed. The SEC system
comprised a low-temperature evaporative light-scattering
(LT-ELS) detector (Sedex 85, Sedere LT-ELSD) with degasser
(DGU-14A), a gradient pump (FCV-10ALVP), and a fraction
collector (Pharmacia LKB-Helifrac together with the system
controller (SCL-10AVP). The system was equipped with three
columns, two Jordi Gel DVB 500A (300 ·7.8 mm) and one
Guard column (50 ·7.8 mm). The peaks obtained in the
detector were integrated with an integrator (Shimadzu Class-
VP 8v.6.12 SP5).
2.3.4 Differential Scanning Calorimetry (DSC)
The thermal properties of the feedstocks and extracted oil were
characterized with a DSC Q1000 v9.9 instrument. Samples of
ca. 2 mg in aluminum pans were heated from –90 C to 85 C,
then cooled to –90 C and heated again to 85 C at 10 C min–1.
3 Results and Discussion
3.1 Oil Extraction from SBE
3.1.1 Preliminary Experiments

2.3 Characterization of Fresh, Extracted, and
Bleached Oil
2.3.1 Thermogravimetric Analysis
TGA analyses were performed with a SDT Q600 (V20.9 Build 20)
instrument. The sample was heated with the following temper-
ature program: from 25 C in 10 C min–1 steps to 1000 C. The
purge gas was fed into the system at 100 mL min–1.
The reproducibility tests for extraction of oil within 5 h using
1:4 ratio of SBE to hexane were performed prior to study the
extraction kinetics. The results in Tab. 2 indicate that good
reproducibility in the extraction process could be achieved
and only slight variations in the obtained yields were noted.
The variations in the yields correlated with the SBE amounts.

Table 2. Reproducibility study of extraction kinetics; ratio SBE:hexane 1:4, ex-

2.3.2 Inductively Coupled Plasma-Mass traction time 5 h.
Spectroscopy (ICP-MS)
Experiment m (SBE) [g] m (Hexane) [g] m (oil) [g] Extraction yield [%]
Oil samples were weighed (approx. 0.3 g) into Tef-
lon bombs, 5 mL HNO3 (65 %) and 1 mL H2O2 A1 24.97 99.51 7.72 30.92
(30 %) were added, digested in a microwave oven A2 24.91 101.97 7.90 31.71
(Anton Paar, Multiwave 3000), diluted to 100 mL
A3 25.09 100.44 8.10 32.28
with deionized water, and analyzed by ICP-MS
(PerkinElmer, ELAN 6100 DRC plus). Acids used B1 24.95 100.62 6.58 26.37
were of suprapure grade (Merck).
B2 25.01 100.75 6.49 25.95

B3 25.15 101.73 6.86 27.28

2.3.3 Size-Exclusion Chromatography
C1 25.24 100.08 4.51 17.87

Size-exclusion chromatography (SEC) was applied C2 24.96 101.15 4.29 17.19

to determine the fatty acid composition of the oils. C3 25.11 100.11 4.32 17.20
Five droplets of the oil sample were pipetted into a

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772 Research Article

3.1.2 Extraction Kinetics Table 3. DSC results for the oil sample from different feedstocks.

A comparative plot of extraction Sample Crystallization Combined energy Melting Combined energy
kinetics using different feedstocks temperatures [C] of crystallization [J g–1] temperatures [C] of melting [J g–1]
and adsorbents is presented in Feedstock A 21.4; 4.6 40.9 7.9: 42.0 38.4
Fig. 2. The oil yield depends on the
BE type and the feedstock used in Extracted oil A 21.4; 4.1 30.4 5.1; 41.6 18.3
the refinery. The extractable oil Feedstock B 17.4; –2.8 40.8 –7.6; 40.7 45.5
content in sepiolite is almost 35 %
Extracted oil B 18.9; –3.9 38.4 –7.3; 41.0 43.2
and only 20 % in palygorskite due
to its lower specific surface area Feedstock C 17.3; –2.5 41.8 –7.6; 42.5 54.1
and, therefore, the oil yields from
Extracted oil C 18.0; –2.7 43.5 –7.2; 41.3 56.2
sepiolite are larger. The feedstock
composition influences the extrac-
tion yield which can be correlated
with the melting point of the fatty acids. A comparison be- temperature was measured from the bottom of the thimble, the
tween feedstock A and B curves indicates that a lower melting second measuring point was in the middle, and the third point
point of feedstock B makes it easier for the oil to be extracted was in the upper part of the thimble, while keeping the ther-
than for the feed with a higher melting point (A). The results mometer inside the SBE sample. The temperature range of the
from feedstock A and B are comparable since the same BE is extraction is above 50 C, which is necessary because the melt-
used. In the same way, B and C can be compared because of ing points of the extracted oils are lower as can be seen from
the similar types of feedstock. the results of the DSC analysis (Tab. 3). In theory, the extrac-
The extraction temperature was measured during one ex- tion temperature is high enough to extract all of the oil sorbed
traction from three different points to collect reliable informa- to the SBE.
tion. All points were inside the extraction thimble. First the The extraction efficiencies of feedstock A from the SBE were
compared at 2-h intervals from 1 to 7 h. The theoretical oil
amount of feedstock A samples was calculated to be 36 %
(Tab. 4).
The extraction results in Tab. 5 clearly show that above 90 %
of the oil trapped in the SBE can be extracted within 5 h. The
experiment A4 was performed to determine if there is a differ-

Table 4. Determination of theoretical oil content in different

SBEs by TGA.

Feedstock Weight loss in Weight loss in Oil in SBE

fresh BE [%] SBE [%] [%]

A 85.69 50.00 35.69

B 85.69 50.00 35.69

Figure 2. Extraction yield of oil A (^) and B (¢) with sepiolite C 78 66 12
and oil C with palygorskite (~) in reflux with hexane.

Table 5. Yields of extracted oil from SBE with feed from feedstock A.

Experiment m (SBE) Theoretical m (Hexane) m (SBE)/ m Time m (Oil) Extraction Extracted oil/
[g] amount of oil [g] [g] (hexane) [h] [g] yield [%] theoretical [%]

A1 25.19 8.99 102.31 1/4 7 8.61 34.18 95.74

A2 25.60 9.14 95.20 1/4 7 8.90 34.77 97.37

A3 25.16 8.98 101.77 1/4 5 8.24 32.75 91.73

A4 12.43 4.44 106.02 1/9 5 4.12 33.15 92.84

A5 25.29 9.03 101.22 1/4 3 7.10 28.07 78.63

A6 25.22 9.00 100.39 1/4 3 6.00 23.79 66.64

A7 25.01 8.93 101.18 1/4 1 1.74 6.96 19.49

A8 25.10 8.96 101.70 1/4 1 2.07 8.25 23.10

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 Research Article 773

ence in the yield when the SBE-to-hexane ratio is Table 7. Yields of extracted oil from SBE with feed from feedstock C; ratio SBE:-
altered. Since no significant differences were found, hexane 1:4.
the rest of the experiments were conducted with
the original 1:4 ratio. Experiment m (SBE) m (Hexane) Time m (Oil) Extraction
[g] [g] [h] [g] yield [%]
Analogously to feedstock A, extraction efficien-
cies were also investigated for feedstock B with 2-h C1 25.28 100.17 7 5.14 20.33
intervals from 1 to 9 h; see Tab. 6. The theoretical
C2 25.15 100.24 7 4.71 18.73
oil amount of the B sample was calculated to be
35 % (Tab. 4). The variation in the oil yield is larger C3 25.11 100.46 5 4.99 19.87
than that of the A samples. This was also one rea-
C4 25.05 101.01 5 3.76 15.01
son that all kinetic experiments were performed
twice, in order to obtain more reliable data. C5 25.03 101.15 3 4.48 17.90
The extraction efficiencies of the spent palygor-
C6 25.29 100.50 3 4.16 16.45
skite from feedstock C were studied using the same
principles as for the SBE applied for feedstock A C7 25.18 100.07 1 1.04 4.13
and B. When comparing the results of feedstock C
C8 25.25 100.14 1 1.25 4.95
as indicated in Tab. 7 with those of feedstock B in
Tab. 6, the difference in the extraction yield is ob-
vious. While the oil yield is 20 % at most from paly-
gorskite, almost 35 % can be obtained from sepiolite. This gummed corn oil in a local factory in Saudi Arabia, under re-
means that sepiolite adsorbs more oil from the feed than paly- fluxing hexane with a hexane-to-adsorbent ratio of 5. In [14],
gorskite and subsequently leads to larger oil losses when sepio- an extraction efficiency of only 42 % was then achieved.
lite is used and the oil is not recovered.
The extraction yield of oil achieved with sepiolite in the cur-
rent work was equivalent compared to the work of Lee et al. 3.2 Characterization of Fresh, Extracted,
[6], in which extraction of palm oil from an SBE gave about and Bleached Oils
37 % oil yield within 46 min using hexane as a solvent with the
ratio of SBE to hexane of 8.3 [6] and with the reflux rate of 3.2.1 DSC Results of Fresh and Extracted Oils
150 drops min–1. Unfortunately, the nature of the SBE was not
described in [6]. The extraction rate achieved in the work of The results of the DSC analysis made for the feedstock sample
Lee et al. [6] was higher compared to that attained in the cur- and extracted oil samples from different refineries are summa-
rent work. In addition, the oil yield of 24 % was reported for rized in Tab. 3 and Fig. 3. For feed A (animal fat), a sharp exo-
the extraction of crude palm oil with hexane in four cycles with thermic peak with a positive heat flow at 21 C originates from
the reflux rate of 200 drops min–1, when each cycle lasted for crystallization of the oil sample. The crystallization curve indi-
about 8 min [11]. In addition, no direct comparison of extrac- cates that there are distinct fractions in the oil sample since the
tion rate can be made with the current work and the work of difference between the crystallization temperatures is very
Al-Zahrani et al. [14], who applied a very short extraction time large. The lower crystallization temperature of 4.1 C is much
of 5 min for oil extraction from an SBE used for bleaching de- higher than those recorded for vegetable oil-based oils (Tab. 3,

Table 6. Yields of extracted oil from SBE with feed from feedstock B; ratio SBE:hexane 1:4.

Experiment m (SBE) Theoretical amount of oil m (Hexane) Time m (Oil) Extraction yield Extracted oil/theoretical
[g] [g] [g] [h] [g] [%] [%]

B1 25.16 8.79 101.69 9 8.66 34.42 98.48

B2 25.37 8.87 101.06 9 8.48 33.43 95.63

B3 25.25 8.83 100.70 7 6.82 27.01 77.28

B4 25.09 8.77 100.37 7 7.98 31.81 91.00

B5 25.44 8.89 99.65 5 6.98 27.44 78.50

B6 24.94 8.72 100.16 5 5.93 23.78 68.03

B7 25.14 8.79 100.62 3 4.92 19.57 55.99

B8 25.11 8.78 101.78 3 4.38 17.44 49.91

B9 25.09 8.77 100.53 1 3.04 12.12 34.67

B10 25.11 8.78 100.28 1 1.67 6.65 19.03

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 774 Research Article

a) melting energies were achieved compared to the case, in which

the slightly basic palygorskite was applied as an adsorbent. This
result indicates that slight hydrolysis of oil can occur during
bleaching leading to formation of free fatty acids analogously to
the results of Lee et al. [6], whereas with a nonacidic adsorbent no
changes in the thermal properties of the oil were observed. It
should, however, be pointed out that SEC (see below) is not able
to differentiate between them because of a slight difference in the
molecular mass of free fatty acid or monoglyceride.

3.2.2 Glyceride Analysis from Different Feedstocks

with SEC
b)
SEC results for the oil samples from different feedstock are
summarized in Tab. 8. The SEC results from the feedstock A
demonstrate that the glyceride composition of the oil samples
remains quite similar after extraction and bleaching. The ana-
lyzed samples are very pure in the glyceride composition with
over 90 % of all glycerides being triglycerides. From the glycer-
ide perspective, the extracted oil can certainly be used in the
same way as the bleached oil. The SEC results for the oil sam-
ples from feedstock B (Fig. 4) and C demonstrate correspond-

600

500
c) 1
Feedstock 5
Intensity*103 (a.u.)

400
Extracted oil 4

3 300
Heat flow [mW]

2
200
1 3
0 100
-100 -80 -60 -40 -20 0 20 40 60 80 100 2
-1

-2
0
-3 1000 2000
Temperature [°C] Time [s]
Figure 3. Heat flows of the DSC analysis of the oil samples from Figure 4. SEC-chromatogram of the extracted feedstock B. No-
feedstock (a) A, (b) B and (c) C. tation: 1. Triglyceride, 2. diglyceride and 3. monoglyceride.

Figs. 3 b, c) as expected due to the differences in

Table 8. SEC results for the oil samples from different feedstocks.
their chemical composition. The negative heat
flows giving peaks below 0 mW come from the Sample Area-% of Area-% of Area-% of
melting of the oil sample. The melting curve sup- triglycerides diglycerides monoglycerides
ports the same hypothesis of different fractions in
Feedstock A 93.37 5.21 1.43
the feed as the curve is so fragmented. Analogously
to the differences in crystallization temperatures Feedstock A extracted 95.99 2.32 1.69
compared to those for the vegetable oil-based feed- Feedstock A bleached 93.84 4.79 1.37
stock, feedstock A has a higher melting point for Feedstock B feedstock 73.68 7.87 18.46
the low melting fraction being 5.1 C.
Feedstock B extracted 65.77 8.16 26.07
In addition to the differences in crystallization and
melting temperatures for various feedstocks, there Feedstock B bleached 70.66 7.01 22.32
were also variances in combined energies for crystal- Feedstock C feedstock 73.16 7.25 19.59
lization and melting. When the bleaching process Feedstock C extracted 69.75 7.93 22.31
was performed with acidic adsorbents, such as sepio-
Feedstock C bleached 74.96 6.91 18.13
lite for feedstock A and B, lower crystallization and

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 Research Article 775

ingly that the glyceride composition of the extracted oil is quite
close to the bleached one, which means that the extracted, re-
newable oil can be used in the same way as the bleached oil.
3.2.3 ICP Results of Inorganic Elements in Fresh,
Extracted, and Bleached Oil
The amounts of inorganic elements in the three feedstocks are
listed in Tab. 9. Silicon and phosphorus are two of the unreli-
able elements to be analyzed by the ICP-MS method, moreover,
sulfur is also very difficult to detect due to a high background.
High relative standard deviations (RSD) of these elements also
confirm the analysis problems. Nevertheless, the results indi-
cate that a large amount of the metals is adsorbed on the BE
and merely a small fraction is left in the bleached oil.
The ICP-MS analysis results for the oil samples from animal
fat feedstock (A) demonstrates that 84 % of inorganic elements
remain in the extracted oil (Tab. 9), whereas only 56 % of the
original amount was present in the bleached oil. Especially S,
Ca, Na, P, and Ba contents were increased in the extracted BE,
sepiolite after extraction [15]. When comparing their amounts

Table 9. ICP-MS results for the oil samples from feedstock A, B, and C; during bleaching sepiolite was used as an adsorbent, while paly-
gorskite was used as an adsorbent for C.

Feedstock A Extracted oil Bleached oil

Element Content RSD Content RSD Content RSD
[mg kg–1] [%] [mg kg–1] [%] [mg kg–1] [%]
Potassium (K) 3.47 1.3 0.27 (8) 6.3 0.18 (5) 6.8
Iron (Fe) 3.51 1.2 2.05 (58) 1.3 0.08 (2) 3.9
Calcium (Ca) 11.88 2.7 10.26 (86) 2.3 0.52 (4) 22.0
Sodium (Na) 6.74 1.6 1.94 (29) 2.3 0.31 (5) 9.7
Magnesium (Mg) 0.88 1.2 1.07 (121) 1.3 0.12 (14) 6.9
Silicon (Si) 15.92 4.4 36.65 (230) 1.5 24.65 (155) 1.7
Phosphorus (P) 36.65 2.6 24.56 (67) 7.0 17.44 (48) 3.7
Sulfur (S) 53.94 17.9 34.45 (64) 13.4 32.37 (60) 23.0
Sum (mg kg–1, % of original) 132.99 111.28 (84) 75.67 (56)
Feedstock B Extracted oil Bleached oil
Element Content RSD Content RSD Content RSD
[mg kg–1] [%] [mg kg–1] [%] [mg kg–1] [%]
Potassium (K) 3.68 0.8 0.26 (7) 8.8 0.15 (4) 8.6
Iron (Fe) 6.66 0.4 0.16 (2) 1.8 0.04 (< 1) 6.0
Calcium (Ca) 22.60 0.9 4.11 (18) 4.1 3.08 (14) 2.0
Sodium (Na) 2.86 1.0 0.75 (26) 4.7 0.48 (17) 4.1
Magnesium (Mg) 3.61 1.1 0.32 (9) 2.5 0.08 (2) 8.5
Silicon (Si) 32.51 1.8 25.36 (78) 0.8 21.56 (66) 1.5
Phosphorus (P) 35.79 2.2 15.03 (42) 4.7 14.85 (41) 3.8
Sulfur (S) 44.42 13.0 6.28 (14) 101.3 13.75 (31) 48.3
Sum (mg kg–1, % of original) 152.13 52.27 (34) 53.99 (35.5)
Feedstock C Extracted oil Bleached oil
Element Content RSD Content RSD Content RSD
[mg kg–1] [%] [mg kg–1] [%] [mg kg–1] [%]
Potassium (K) 4.61 0.9 0.13 (3) 8.1 0.16 (3) 15.0
Iron (Fe) 12.27 1.0 0.20 (2) 5.6 0.44 (4) 2.1
Calcium (Ca) 10.79 1.8 10.84 (100) 1.0 5.14 (48) 2.8
Sodium (Na) 3.27 1.3 0.80 (24) 5.0 0.82 (25) 1.9
Magnesium (Mg) 2.71 0.8 0.13 (5) 5.4 0.18 (7) 2.0
Silicon (Si) 15.01 1.0 32.33 (215) 1.1 16.51 (110) 0.5
Phosphorus (P) 25.01 2.3 16.78 (67) 5.5 11.39 (46) 4.7
Sulfur (S) 16.11 29.3 30.62 (190) 19.8 9.88 (61) 65.7
Sum (mg kg–1, % of original) 89.79 91.83 (~100) 55.96 (50)

Chem. Eng. Technol. 2015, 38, No. 5, 769–776 ª 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
776 Research Article

with those present in extracted oil it could be seen that the so- extracted oil bleached with the nonacidic adsorbent palygor-
dium content was very low in extracted oil from feedstock A, skite as compared with the acidic adsorbent palygorskite.
whereas calcium and sulfur levels were quite high also in ex-
tracted oil. On the other hand, some accumulation of magnesi-
um and silicon occurred in extracted oil A during the bleaching Acknowledgment
process. The bleached oil A contained only 46 % of its original
amount of inorganic elements. This work is part of activities of the Process Chemistry Centre,
A direct comparison of retaining minerals can be made be- Åbo Akademi University. The authors are grateful to
tween animal fat and vegetable oil based oils, since in both Mr. L. Silvander for performing EDXA analysis, to Mr. S. Lind-
cases sepiolite was used as an adsorbent. The amount of inor- holm and Mr. P. Ek for ICP-MS analysis.
ganic elements in the fresh feed B from vegetable oils was
slightly higher than that in feed A. The extracted oil B con- The authors have declared no conflict of interest.
tained only 34 % of its original amount of inorganic elements
which is much less than accumulated in extracted animal fat
oil. Furthermore, the bleached oil contained only 36 % of its
original amount of inorganic elements. This result shows that Abbreviations
there is a difference in retaining inorganic elements in animal
fat and vegetable oil based oils. When the feed contains more BE bleaching earth
high-boiling-point fats, it also contains more minerals. CPO crude palm oil
The third feed C, based on a vegetable oil, was bleached with DSC differential scanning calorimetry
a slightly basic palygorskite-type clay. Now the effect of the clay EBE extracted bleaching earth
type, being sepiolite or palygorskite (Tab. 9), can be directly FTIR Fourier transform infrared
compared, since similar types of feeds were used in both cases. ICP-MS inductively coupled plasma/mass spectroscopy
The largest difference in this comparison is the fact that the ex- LT-ELS low-temperature evaporative light-scattering
tracted oil contained about the same amount of minerals as PFAD palm fatty acid distillate
was present in the fresh feed C. Moreover, only 50 % reduction RSD relative standard deviations
of the mineral content was achieved in the bleached oil, where- SBE spent bleaching earth
as the corresponding reduction with sepiolite was 64 %, agree- SEC size-exclusion chromatography
ing also with the results, i.e., the extraction efficiency was lower TGA thermogravimetric analysis
in the case of palygorskite. This result is reasonable since paly-
gorskite was less acidic and exhibited a lower specific surface
area than sepiolite. References
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