Fuel Processing Technology 118 (2014) 296301

Contents lists available at ScienceDirect

Fuel Processing Technology

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

Synthesis of biodiesel from Nigella sativa seed oil using

surfactant-Brnsted acidic-combined ionic liquid as catalyst
Behzad Aghabarari a,, Nasim Dorostkar b, M.V. Martinez-Huerta c
a
b
c

Department of Chemistry, Faculty of Science, Islamic Azad University, Shahrekord Branch, P.O.Box 166, Shahrekord, Iran
Department of Chemistry, Isfahan University of Technology, Isfahan 8415683111, Iran
Institute of Catalysis and Petrochemistry, CSIC, Marie Curie 2, 28049 Madrid, Spain

a r t i c l e

i n f o

Article history:
Received 4 April 2013
Received in revised form 3 October 2013
Accepted 4 October 2013
Available online xxxx
Keywords:
Biodiesel
Nigella sativa
Surfactant
Acid catalyst
Ionic liquid

a b s t r a c t
Two acidic ionic liquids based on 1-benzyl-1H-imidazole have been synthesized and characterized by FT-IR, 1H
NMR, 13C NMR and CHNS analyses. The ionic liquids have been used for transesterication of Nigella sativa
seed oil as newer sources of oil with methanol. We determined relative fatty acid content, iodine and
saponication values of seed oil and estimated cetane number of produced biodiesel based on the chemical
composition of oil. Also, the effect of reaction temperature, type and amount of catalyst, molar ratio and reaction
time were investigated. The results show that the ILH2 ionic liquid has the higher catalytic activity under the
optimized reaction conditions. Thus, this ionic liquid is able to catalyze the transesterication of N. sativa seed
oil to its methyl esters in 6 h with yields of more than 93%. The catalytic activity of ILH2 for the transesterication
of other vegetable oils and alcohols has also been studied.
2013 Elsevier B.V. All rights reserved.

1. Introduction
Biodiesel has gained considerable attention as an alternative fuel
during the past decade due to environmental problems and depletion
of fossil fuels. Indeed, numerous studies have shown the benets of
these alternative fuels [13].
Biodiesel is now mainly produced by transesterication of edible oils
such as canola, palm, safower, soybean and sunower with shortchain alcohols (methanol or ethanol) in the presence of various
catalysts. However, the consumption of edible oils for biodiesel
production has led to food versus fuel problem. Moreover, edible oils'
feedstock costs are far expensive to be used as fuel because 70%80%
of the total cost of biodiesel production is from the raw materials.
Implementation of the biodiesel industry must have a plentiful supply
of raw materials. Therefore, production of biodiesel will only be possible
by using from non-edible oils in an effective way to overcome both
economic and ethical problems [38].
To date, more than 350 oil-bearing crops have been discovered but
the potential of converting these non-edible oils into biodiesel must
be well examined. For example, cetan number (CN), which is a measure
of the ignition quality of diesel fuel during combustion ignition,
provides information about the ignition delay (ID) time of a diesel fuel
upon injection into the combustion chamber. This is one of the most
important parameters considered during the selection of methyl esters
for use as biodiesel [1,3,7].
Corresponding author. Tel.: +98 3813361041; fax: +98 3813361043.
E-mail address: behzad@ch.iut.ac.ir (B. Aghabarari).
0378-3820/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fuproc.2013.10.003

Nigella sativa with oil content greater than 35%, commonly known as
black seed, belongs to the botanical family of Ranunculaceae. It is native
to Southwest Asia, but it is cultivated in different parts of the world
including Southern Europe, Northern Africa and Asia Minor. It has
been used in many Middle Eastern countries as a natural remedy for
2000 years ago but the use of N. sativa seed oil in large doses and
prolonged use might be harmful due to the presence of some toxic
components such as glucoside in its oil [913]. However, the production
of biodiesel by using N. sativa seed oil as new feedstock can be interesting.
Transesterication reactions can be alkali-catalyzed, acid-catalyzed
or enzyme-catalyzed. The feedstock often contains large amounts of
free fatty acids which would remarkably decrease the effect of base
catalysts. In the presence of basic catalysts, the free fatty acid content
of the oil is saponied by homogeneous alkali catalysts, leading to
depletion of the catalysts as well as to increase purication costs.
Purication of biodiesel and glycerol is easier when enzymes are used
as catalysts but it is not appropriate for industrial scale because enzymes
have high cost and unstable activities [2,14,15]. These problems can be
avoided by the use of homogenous or heterogeneous acid catalysts.
The use of solid acid catalysts eliminates many of the technological
and environmental problems versus homogeneous acid catalysts,
although the process is much slower due to the fact that three phases
are present in the reaction mixture, thus leading to a lower diffusion
coefcient for the heavier molecules to the surface of the solid catalysts.
Several researchers have investigated the use of co-solvents such as
dimethyl ether (DME), tetrahydrofuran (THF), dimethyl sulfoxide
(DMSO) and n-hexane [1519] and phase-transfer catalysts [2023]
to overcome this problem. Gang et al. [20] used both Brnsted and

B. Aghabarari et al. / Fuel Processing Technology 118 (2014) 296301

Lewis acids bound to surfactant molecules as catalyst. They proposed

that the surfactant moiety of the catalyst increases the interaction
between the hydrophobic feed stocks and its active acid sites. Ghesti
et al. [21] reported the synthesis, characterisation and use of cerium
(III) tris dodecylsulfate trihydrate [Ce(OSO3C12H25)33H2O] as a
combined Lewis acidsurfactant catalyst for the production of biodiesel.
These authors obtained high conversions (91%) for soybean oil
transesterication and oleic acid esterication in the presence of this
catalyst at 100 C in only 46 h and attributed its high catalytic activity
to its chemical composition.
The use of ionic liquids as catalysts or solvents for the esterication of
fatty acids or transesterication of vegetable oils and animal fats, as well
as other chemical reactions, has increased signicantly in recent years.
Indeed, ionic liquids, especially those functionalised with Lewis and
Brnsted acid sites, have found numerous applications [2329]. Also,
ionic liquids as phase transfer catalyst able to improve mass transfer
between polar methanol phase and non-polar oil phase to increase rate
of transesterication reaction. For example, Yi Zhang et al. [23] have
used tetrabutylammonium hydroxide and tetrabutylammonium acetate
as base catalysts to produce biodiesel from soybean oil. All results
showed that the rate of reaction was greatly enhanced by using these
phase transfer catalysts in the transesterication of soybean oil.
Herein we report the synthesis and characterisation of new highly
Brnsted acidic ionic liquids (Scheme 1) and their use for the
transesterication of N. sativa seed oil for biodiesel production. We
have also investigated the effect of the saturation degree of the oil and
the alkyl chain of the alcohols on the catalytic activity of these ionic
liquids in the transesterication reaction.
2. Experimental
2.1. Chemicals and instruments
All chemicals (AR grade) were commercially available and used
without further purication. Elemental analyses were performed
using a Leco CHNS-932 analyser. IR spectra were recorded using a
Jasco FT/IR-680 plus spectrophotometer for KBr pellets. NMR spectra
in DMSO-d6 were obtained using a 100 MHz Bruker instrument, with
TMS as internal standard. UVvis spectra were obtained with a Jasco
UVvis spectrophotometer. The products obtained in each experiment
were analyzed using a Chrompack GC Model CP9001 equipped with a
Varian Capillary Column (50 m, 0.25 mm, 0.25 m) and FID detector.
The biodiesel yield, dened as the amount of fatty acid methyl esters
(FAMEs) formed during the transesterication, was quantied using
tricaprylin as internal standard.
2.2. Synthesis of the ionic liquids
2.2.1. Synthesis of 1-benzyl-1H-imidazole
In a three-neck round bottom ask equipped with condenser,
150 mL THF with 20.73 g (150 mmol) K2CO3 was stirred at 60 C for
20 min. Then 6.81 g (100 mmol) of 1H-imidazole was added to the
suspension and the mixture was reuxed for 2 h. Subsequently,
17.10 g (100 mmol) of benzyl bromide was added dropwise over a

297

period of 60 min, and then the mixture was reuxed for 24 h. The
solution was cooled to room temperature and about 50 mL of water
was added. The aqueous layer was removed and extracted three times
with dichloromethane. The combined organic layers were added to
the THF solution, then dried over anhydrous sodium sulfate and the
solvent was removed under vacuum.
FT-IR (KBr, cm1): 3441, 3127, 3041, 2975, 1610, 1556, 1498, 1456,
1425, 1374, 757, and 698.
1
H NMR (400 MHz, DMSO-d6) (ppm): 7.81 (s, 1H, NCHN), 7.42
6.91 (m, 7H, ImH and ArH), and 5.49 (s, 2H, NCH2), Anal. calcd for
C10H10N2 (M.W = 158.20): C, 75.92; H, 6.37; N, 17.71; found: C, 75.61;
H, 6.33; and N, 17.54%.
2.2.2. Synthesis of 1-benzyl-3-butyl-1H-imidazolium bromide (ILB1)
1-Benzylimidazole (2.37 g, 15 mmol), was dissolved in 60 mL
acetonitrile in a three-neck round bottom ask and 2.06 g (15 mmol) of
1-bromobutane was added dropwise and the mixture was reuxed for
72 h. After cooling and ltration, the resulting IL was recrystallized twice
in ethyl acetate (100 mL) and then dried under vacuum at 70 C for 12 h.
FT-IR (KBr, cm1): 3454, 3120, 3033, 2918, 2850, 1616, 1558, 1457,
1425, 1376, 1192, 1011, 753, 703, and 452.
1
H NMR (400MHz, DMSO-d6) (ppm): 8.81 (s, 1H, NCHN), 7.55
7.28 (m, 7H, BImH and ArH), 5.54 (s, 2H, NCH2), 4.50 (t, 2H, NCH2),
1.91 (pent, 2H, NCH2*CH2), 1.30 (pent, 2H, NCH2CH2*CH2),
and 0.83 (t, 3H,CH3), Anal. calcd. for C14H19BrN2 (M.W = 295.22):
C, 56.96; H, 6.49; and N, 9.49; found: C, 56.31; H, 6.38; and N, 9.61.
2.2.3. Synthesis of 3-butyl-6-sulfo-1-(4-sulfobenzyl)-1H-imidazolium
hydrogen sulfate (ILB2)
To the 10 g concentrated H2SO4 (98%) that previously cooled in an
ice bath, ILB1 (2.95 g, 10 mmol) was added slowly and mixed at this
temperature for 8 h. After this time, the mixture was stirred for 24 h at
80 C to form ILB2. Upon completion, the reaction mixture was cooled
in an ice bath and then the solid product separated and dried under
high vacuum at 70 C for 4 h.
FT-IR (KBr, cm1): 3455, 3125, 3034, 2921, 2850, 1615, 1560, 1489,
1465, 1428, 1377, 1342, 1221, 1192, 1061, 1009, 855, 765, 719, 700, 619,
588, and 423.
1
H NMR (400 MHz, DMSO-d6) (ppm):8.78 (s, 1H, NCHN), 7.66
7.35 (m, 7H, BImH and ArH), 5.75 (s, 2H, CH2), 4.54 (t, 2H, NCH2),
1.90 (pent, 2H, NCH2*CH2), 1.21 (m, 26H, CH2(13)), 0.86 (t, 3H,CH3),
13
C NMR (400 MHz, DMSO-d6) (ppm): 143.18, 138.15, 136.25,
129.91, 128.86, 126.73, 121.62, 51.08, 47.75, 32.63, 31.94, 29.58, 29.41,
29.34, 29.18, 28.93, 28.57, 26.25, 22.54, and 14.37, Anal. calcd. for
C14H20N2O7S2 (M.W = 392.45): C 42.85; H 5.14; N 7.14; and S 16.34
found: C 42.91; H 5.08; N 7.12; and S 16.19.
2.2.4. Synthesis of 1-benzyl-3-hexadecyl-1H-imidazolium bromide (ILH1)
Compound ILH1 was prepared following the same procedure as for
ILB1 except that we used 4.58 g (15 mmol) 1-bromohexadecane for
synthesis of ILH1.
FT-IR (KBr, cm1): 3454, 3121, 3038, 2919, 2850, 1616, 1559, 1458,
1428, 1376, 1194, 1015, 763, 703, and 454.

Scheme 1. Synthesis of ionic liquids.

298

B. Aghabarari et al. / Fuel Processing Technology 118 (2014) 296301

1
H NMR (400 MHz, DMSO-d6) (ppm): 8.81 (s, 1H, NCHN), 7.55
7.28 (m, 7H, BImH and ArH), 5.74 (s, 2H, NCH2), 4.50 (t, 2H, NCH2),
1.91 (pent, 2H, NCH2*CH2), 1.21 (m, 26H, CH2(13)), and 0.83 (t, 3H,
CH3), Anal. calcd. for C26H43BrN2 (M.W = 463.54): C, 67.37; H, 9.35;
and N, 6.04; found: C, 67.14; H, 9.39; and N, 6.11.

2.2.5. Synthesis of 3-hexadecyl-6-sulfo-1-(4-sulfobenzyl)-1H-imidazolium

hydrogen sulfate (ILH2)
Compound ILH2 was prepared by the similar procedures in ILB2
except that we used 10 mmol of ILH1 for the synthesis of ILH2.
FT-IR (KBr, cm1): 3455, 3127, 3030, 2923, 2852, 1615, 1562, 1489,
1465, 1428, 1377, 1342, 1224, 1192, 1065, 1012, 852, 765, 722, 702, 616,
585, and 426.
1
H NMR (400 MHz, DMSO-d6) (ppm):8.78 (s, 1H, NCHN), 7.66
7.35 (m, 7H, BImH and ArH), 5.75 (s, 2H, CH2), 4.54 (t, 2H, NCH2),
1.90 (pent, 2H, NCH2*CH2), 1.21 (m, 26H, CH2(13)), and 0.86 (t, 3H,
CH3), 13C NMR (400 MHz, DMSO-d6) (ppm): 143.18, 138.15, 136.25,
129.91, 128.86, 126.73, 121.62, 51.08, 47.75, 32.63, 31.94, 29.58, 29.41,
29.34, 29.18, 28.93, 28.57, 26.25, 22.54, and 14.37, Anal. calcd. for
C26H44N2O7S2 (M.W = 560.77): C, 55.69; H, 7.91; N, 5.00; and S, 11.44
found: C, 55.01; H, 7.98; N, 5.12; and S, 11.21.
2.2.6. The Hammett acidity of Brnsted acidic ionic liquids
For determination of H0 values of Brnsted acidic ionic liquids, similar
procedure described by Zhao et al. [29] was used. Dichloromethane
solutions of the ionic liquids (5 103 molL1) were prepared from
dried dichloromethane and 4-nitroaniline (1.5 104 molL1) was
used as basic indicator.
2.2.7. Oil extraction and physicochemical composition of N. sativa seed oil
N. sativa was collected from Isfahan (center of Iran), and its seeds
were dried at room temperature in the absence of sunlight and then
crushed with mortar. Fat components were extracted with hexane
using a Soxhlet apparatus at about 60 C until the extraction was
completed. The oil content was determined by the difference in weight
of the dried kernel sample before and after the extraction. The chemical
composition of the N. sativa seed oil (Table 1) was determined by GC of
the methyl esters on a Chrompack GC Model CP9001 equipped with a
Varian Capillary Column (50 m, 0.25 mm, 0.25 m) and FID detector.
Initial temperature: 150 C (15 min); ramp: 3 C/min; and nal
temperature: 210 C (15 min). The molecular weights of N. sativa seed
oil and biodiesel were 872.53 g and 292.1 g, respectively.
Also AOCS ofcial methods [30] were used to evaluate iodine
(method number: Cd 3d-63) and saponication (method number: Cd
3-25) numbers of N. sativa seed oil.
3. General procedure for biodiesel synthesis
The transesterication reaction, for the synthesis of fatty acid methyl
ester from N. sativa seed oil (2 mmol, 1.75 g) with methanol (12 mmol,
0.38 g), was carried out in a round-bottomed ask tted with a reux
condenser that charged with 5% catalyst loading with respect to mmol
of oil. The reaction was typically allowed to proceed for 5 h with

Table 1
Chemical composition of Nigella sativa seed oil.
Fatty acid

MW(gmol1)

Composition (wt.%)

Palmitic acid (C16:0)

Stearic acid (C18:0)
Oleic acid (C18:1)
Linoleic acid (C18:2)
-Linolenic acid (C18:3)
Arachidic acid C20:0
Eicosenoic acid C20:1
Behenic acid C22:0

256.43
284.48
282.47
280.45
278.44
312.53
310.51
340.58

18.8
4.6
23.1
50.3
0.2
0.6
0.2
2.2

The chemical composition of oil was determined by GC.

vigorous agitation at the desired temperature. After completion of the

reaction, the alcohol was distilled off under vacuum, then the residue
was centrifuged for 15 min to complete phase separation. Three phases
were formed, with the upper layer containing biodiesel, the middle
layer glycerol and the lower layer catalyst. After separation, the ionic
liquid was washed with n-hexane and dried under vacuum at 70 C
for 4 h. The collected product was analyzed quantitatively by GC using
tricaprylin as internal standard. The yield of fatty acid methyl ester
was dened as the ratio of the weight of fatty acid methyl esters, as
determined by GC, to the weight of fatty acid methyl esters theoretically
produced upon transesterication of the oil.
4. Results and discussion
4.1. Estimation of the cetane numbers of the biodiesel produced from the N.
sativa seed oil
Biodiesel has different physical and chemical properties compared
with diesel fuel and the quality of biodiesel fuel can be inuenced by
different factors. Accordingly, the properties of the various individual
fatty esters that comprise biodiesel determine the biodiesel properties
such as cetane number [4,7]. High cetane number implies good cold
start properties and reduces the formation of gaseous and particulate
exhaust emissions due to incomplete combustion. The cetane number
of biodiesel identied by ASTM D613 is 47 min and EN ISO 5165 is
51 min. Among the non-edible oil, Pongamia glabra methyl ester has
the lowest cetane number of 45.39 while rice bran methyl ester has
the highest cetane number of 73.6 [3,31]. Some studies show that the
fuel properties such as cetane number, iodine number and oxidation
stability are mainly determined by the degree of unsaturation of
fatty acid in raw oils [4,7,3134]. Azam et al. [34] calculated the
saponication number (SN) and the iodine value (IV) of biodiesel
relative to its content of fatty acid methyl esters and then used these
values to estimate the cetane number of seed oils of some plants. The
cetane number (CN) is calculated as:
CN1 46:3 5458=SN0:225  IV:

The iodine number (IV) is an index of the number of double bonds in

biodiesel which determines the unsaturation degree of the biodiesel
limited to 120 (mg I2/100 g) in the USA (ASTM D6751-2003) and
European biodiesel standard (EN 14214-2005). The saponication
number (SN) is dened as the number of mg of KOH required to
neutralize 1 g of oil. The experimental result showed that the iodine
number and saponication number of N. sativa seed oil were 110
and 198, respectively. These values were similar to those reported
previously [3537].
The cetane number was tted linearly with degree of unsaturation
(DU) by Wang Li-bing et al. [7] and the cetane number decreased with
the degree of unsaturation and follows the equation:
CN2 0:1209  DU 65:0958:

In this study, the cetane numbers of the biodiesel produced from the
N. sativa seed oil are estimated by using the last two equations (Table 2).
According to the physicochemical characterization and the estimated
cetane numbers, the biodiesel produced from the N. sativa seed oil can
meet the USA biodiesel standard and can be developed as potential
energy plant.
4.2. The effect of temperature and catalyst
N. sativa seed oil was transesteried with methanol in the
temperature range of 4575 C, in steps of 15 C, for 5 h (Table 3).
The molar ratio of methanol (MEA) to N. sativa seed oil (NSO) was
6:1 and the ionic liquids (5%, based on mmol of oil) was used as

B. Aghabarari et al. / Fuel Processing Technology 118 (2014) 296301

Table 2
Fuel properties produced from Nigella sativa seed oil.

299

Table 4
Calculation and comparison of H0 values of different ionic liquids in CH2Cl2.

Entry

Fuel properties

Unit

Calculated value

Entry

Ionic liquid

Amaxa

[I] (%)

[IH+] (%)

H0

1
2
3
4
5

Iodine value (IV)a

Saponication number (SN)b
Degree of unsaturation (DU)c
Cetane number (CN1)d
Cetane number (CN2)e

(g of I2/100 g of oil)
(mg of KOH/g of oil)

112.5
201.8
124.5
48.0
50.0

1
2
3

Blank
ILB2
ILH2

2.28
0.99
0.93

100
43.4
40.8

0
56.6
59.2

0.87
0.83

(min)
(min)

Iodine value (IV) is calculated as: IV = (254 D Ai) / MWi, [34].

Saponication number (SN) is calculated as: SN = (560 Ai) / MWi, [34].
c
Degree of unsaturation (DU) is calculated as: DU = (monounsaturated Cn: 1,
%) + 2 (polyunsaturated Cn: 2, %)+ 3 (polyunsaturated Cn: 3, %)+ 4 (polyunsaturated
Cn: 4, %), [7].
d
Cetane number (CN1) is calculated as: CN1 = 46.3 + 5458 / SN 0.225 IV, [34].
e
Cetane number (CN2)is calculated as: CN2 = 0.1209 DU + 65.0958, [7].

H0 = pK(I)aq + log([I] / [IH+]), 4-nitroaniline (pK(I)aq = 0.99) as basic indicator.

a
The maximal absorbance of the unprotonated form of 4-nitroaniline was observed at
349 nm in CH2Cl2.

 h
i

:
H0 pKIaq log I= IH

From the data presented in Table 4, the acidity of ILB2 (H0 = 0.87) is
a little higher than that of ILH2 (H0 = 0.84). According to the elemental
analysis and Hammett acidity function results, there isn't heavy
difference between acidity of ILB2 and ILH2. However the higher
catalytic activity of ILH2, than that of ILB2, can be related to its surfactant
properties that can increase its interaction with hydrophobic reagents.
The long carbon chains connected to the imidazolium moiety of catalyst
increase the interaction between the hydrophobic feedstock and its
Brnsted acidic sites. Gang et al. [20] used surfactant-combined
catalysts dodecylbenzenesulfonic acid and copper dodecylbenzene
Table 3
Effect of reaction temperature and different ionic liquids on the transesterication of
Nigella sativa seed oil with methanol.
Entry

Catalyst

Temperature (C)

Conversion (wt.%)

1
2
3
4
5
6
7
8
9

H2SO4

45
60
75
45
60
75
45
60
75

23.1
34.7
40.3
51.6
64.8
65.5
64.5
75.3
73.0

ILB2

ILH2

Reaction conditions: amount of catalyst = 5% (based on the mmol of oil), MEA/NSO (molar
ratio) = 6, reaction time = 5 h.

4.3. The effect of molar ratio and amount of catalyst

Fig. 1 showed the results of transesterication of N. sativa seed oil
with methanol over ILH2 catalyst using different methanol (MEA):
N. sativa seed oil (NSO) molar ratios 3:1 to 12:1. The reaction was
carried out at 60 C for a period of 5 h. As shown in Fig. 1, the methyl
ester conversion improved considerably upon increasing the methanol
to N. sativa seed oil (MEA:NSO) molar ratio and reaches to a maximum
at 9:1 ratio. This was in agreement with literature, because the reactions
involved in biodiesel production are reversible and excess of methanol
can increase the rate of the reaction. Further increase in the molar
ratio had little effect and this might be due to dilution of ionic liquid
as the catalyst [19,21,25].
Table 5 shows that the production of methyl esters amplied with
increase in the amount of catalyst from 1 to 7.5% (based on the mmol
of oil), although further increases had little effect on the conversion.
An increase in the amount of catalyst to 7.5% clearly increases the
number of acid sites available, although subsequent increases could
result in some degree of catalyst aggregation, thereby effectively
decreasing the number of acidic sites available [25,26]. The optimal
amount of catalyst was therefore taken to be 7.5%.

100
95
90

Conversion (%)

acid catalyst. Also, H2SO4 was used as an industrial Brnsted acid

catalyst for comparison with the catalysts synthesized in this work.
The conversion of fatty acid methyl esters (FAMEs) was found to
increase with temperature from 45 to 60 C and did not obviously
change when the reaction temperature set at 75 C in any catalytic
system. Furthermore, the transesterication reaction showed a
better conversion when we used ILH2 as a catalyst than using the
other ionic liquid. Two main factors, namely the number of Brnsted
acid sites and surfactant properties of catalysts, are likely to have a
major inuence on the transesterication of vegetable oils with
ILB2 and ILH2. Clearly, catalysts with a higher number of Brnsted
acidic sites are likely to be more efcient in the transesterication
reaction [15,19].
In the present study, the acid strength values (H0) of acidic ionic
liquids were determined by the Hammett method with UVvisible
spectroscopy [29]. This method consists of evaluating the protonation
extent of uncharged indicator bases in a solution, in terms of the
measurable ratio of [I]/[IH+] that could be determined from the
measured absorbance differences of 4-nitroaniline (pK(I)aq = 0.99) as
basic indicator at 349 nm (Amax) in dichloromethane solution, before
([I]) and after addition of Brnsted acidic ILs ([IH+]). The Hammett
acidity function, H0, was calculated by using Eq. (3).

sulfonate for solvent-free esterications of various carboxylic acids

and alcohols. They showed the formation of reverse micelles in
hydrophobic reagents by the TEM images of catalysts. The formation
of reverse micelles in the transesterication reaction can increase
local concentration of the reactants at the surface or in the interior
of the micelle and also stabilize the transition state of the reaction
due to a constructive interaction with the surfactant molecules
[22]. However we choose ILH2 as the best catalyst for biodiesel
producing.

85
80
75
70
65
60
55
50
0

12

15

Molar ratio (MEA/NSO)

Fig. 1. Effect of molar ratio on the transesterication of Nigella sativa seed oil with
methanol.

300

B. Aghabarari et al. / Fuel Processing Technology 118 (2014) 296301

100

Table 5
Effect of amount of catalyst on the tranesterication of Nigella sativa seed oil with
methanol.

90

Amount of catalyst (%)

Conversion (wt.%)

blank
0

1
48.9

2.5
77.4

5
82.6

7.5
89.0

10
86.6

Conversion (%)

80
Entry

Reaction conditions: catalyst = ILH2, MEA/NSO (molar ratio) = 9, reaction temperature =

60 C, reaction time = 5 h.

70
60
50
40
30
20

4.4. The effect of reaction time

10
The effect of the reaction time on the transesterication of N. sativa
seed oil was determined using 7.5% of ILH2, a MEA:NSO molar ratio of
9 and a temperature of 60 C. Fig. 2 shows that the conversion increased
from 40.5% to about 93.2% after 6 h, with little change after this time.
This observation remembers that the transesterication of vegetable
oil is a reversible reaction with an equilibrium time of around 6 h,
which was therefore taken as the ideal time for the transesterication
of N. sativa seed oil with methanol.
4.5. Catalyst recyclability
One of the most important factors in designing a new catalyst could
be the reusability of a catalyst. The catalytic stability of ILH2 was
investigated by performing seven runs under the optimized reaction
conditions determined above (Fig. 3). The catalyst was separated,
washed and dried as described in the Experimental section after each
run. It was revealed that the activity of catalyst remained almost steady
after seven runs and decrease in the conversion was negligible (rst
run = 93.2%, seventh run = 89.4%). In addition to high catalytic activity,
this result indicates that the ILH2 ionic liquid is recyclable and has
desirable properties for the transesterication reaction of N. sativa
seed oil with methanol.
4.6. The effect of the type of alcohol or fatty acid
The result listed in Table 6 exhibited the type of alcohol or fatty acid
that had inuence on the conversion of transesterication over ILH2
catalyst at optimum reaction condition. To investigate the effect of the
length of the alcohol alkyl chain, we studied the transesterication of
N. sativa seed oil with methanol, ethanol and n-butanol under the
optimized reaction conditions. Two main alcohol properties, namely
the miscibility with triglyceride molecule and steric hindrance, have a
major inuence on the conversion of transesterication of N. sativa
seed oil. Clearly, alcohols with longer alkyl chain have higher miscibility

100

Conversion (%)

90
80

0
1

Run
Fig. 3. Catalyst recycling of transesterication of Nigella sativa seed oil with methanol using
ILH2.

with oil but less nucleophilicity property for the attack to the activated
carbonyl group of triglyceride molecule. The result showed that the
use of ethanol instead of methanol had no major effect on the yield of
the reaction, although a further increase in the number of carbon
atoms in the alkyl chain resulted in a decrease in the conversion from
93.2% for methanol to 88.5% for n-butanol, probably the steric hindrance
of alcohol has more inuence on the conversion of reaction.
We also studied the catalytic activity of ILH2 for the transesterication
of other vegetable oils and found that the degree of saturation (DS)
of the fatty acid had an inverse effect on the conversion. Thus, the
transesterication yields for canola oil (DS = 7.7%), N. sativa seed oil
(DS = 25.9%), and palm oil (DS = 46.7%) under the optimized reaction
conditions were 97.7, 93.2% and 85.6%, respectively. The result show
that the oils with a higher degree of saturation are likely to be more
packed and therefore less likely to approach the active site of the catalyst,
Furthermore, methanol would not penetrate well into such a packed
structure.
5. Conclusion
In this study, we have synthesized and characterized two acidic ionic
liquids (ILB2 and ILH2). The experimental results have shown ILH2 to
be more active than ILB2 in the transesterication of N. sativa seed
oil with methanol. Also based on the seed oil properties and the
estimated cetane number, the N. sativa seed oil can be developed as a
biodiesel feed stock. A conversion of more than 93% has been obtained
for the transesterication of this oil with methanol upon varying several
reaction parameters, including temperature, molar ratio, amount of
catalyst and reaction time. Furthermore, satisfactory yields (85.697.7%)
have been obtained for the transesterication of several different alcohols

Table 6
Effect of type of alcohol and oil on the tansesterication reaction.

70
Entry

Vegetable oil

1
2
3
4
5
6
7
8

Canola
Safower
Sunower
Soybean
Nigella sativa
Nigella sativa
Nigella sativa
Palm

60
50
40
30
30

60

90 120 150 180 210 240 270 300 330 360 390

Reaction time (Min)

Fig. 2. Effect of reaction time on the transesterication of Nigella sativa seed oil with
methanol.

Fatty acid composition in

oil (%)
Saturated

Unsaturated

7.7
10.7
11.4
14.1
25.9
25.9
25.9
46.7

92.3
89.3
88.6
85.9
74.1
74.1
74.1
53.3

Alcohol

Conversion (wt.%)

Methanol
Methanol
Methanol
Methanol
Methanol
Ethanol
n-Butanol
Methanol

97.7
96.8
97.0
96.2
93.2
93.3
88.5
85.6

Reaction conditions: catalyst = ILH2, catalyst weight = 7.5% (based on the mmol of oil),
alcohol/NSO (molar ratio) = 9, reaction temperature = 60 C, reaction time = 6 h.

B. Aghabarari et al. / Fuel Processing Technology 118 (2014) 296301

and vegetable oils under the optimized reaction conditions. Therefore,

because of its surfactant character, this catalyst can be a suitable substitute
as an acid catalyst in the transesterication of vegetable oil.
Acknowledgments
We would like to thank the Research Council of Islamic Azad
University, Shahrekord Branch for supporting this work.
References
[1] M. Tariq, S. Ali, N. Khalid, Activity of homogeneous and heterogeneous catalysts,
spectroscopic and chromatographic characterization of biodiesel: a review,
Renewable and Sustainable Energy Reviews 16 (2012) 63036316.
[2] M. Pramanik, M. Nandi, H. Uyama, A. Bhaumik, Organicinorganic hybrid porous
sulfonated zinc phosphonate material: efcient catalyst for biodiesel synthesis at
room temperature, Green Chemistry 14 (2012) 22732281.
[3] A.E. Atabani, A.S. Silitonga, H.C. Ong, T.M.I. Mahlia, H.H. Masjuki, I.A. Badruddin, H. Fayaz,
Non-edible vegetable oils: a critical evaluation of oil extraction, fatty acid compositions,
biodiesel production, characteristics, engine performance and emissions production,
Renewable and Sustainable Energy Reviews 18 (2013) 211245.
[4] C.J. Ruan, W.H. Xing, J.A.T. da Silva, Potential of ve plants growing on unproductive
agricultural lands as biodiesel resources, Renewable Energy 41 (2012) 191199.
[5] X. Yu, Z. Wen, H. Li, S.T. Tu, J. Yan, Transesterication of Pistacia chinensis oil for
biodiesel catalyzed by CaOCeO2 mixed oxides, Fuel 90 (2011) 18681874.
[6] M. Su, R. Yang, M. Li, Biodiesel production from hempseed oil using alkaline earth
metal oxides supporting copper oxide as bi-functional catalysts for transesterication
and selective hydrogenation, Fuel 103 (2013) 398407.
[7] W. Li-bing, Y. Hai-yan, H. Xiao-hui, L. Rui-ying, Inuence of fatty acid composition of
woody biodiesel plants on the fuel properties, Journal of Fuel Chemistry and
Technology 40 (2012) 397404.
[8] G. Corro, U. Pal, N. Tellez, Biodiesel production from Jatropha curcas crude oil using
ZnO/SiO2 photocatalyst for free fatty acids esterication, Applied Catalysis B:
Environmental 129 (2013) 3947.
[9] M. Khader, N. Bresgen, P.M. Eckl, In vitro toxicological properties of thymoquinone,
Food and Chemical Toxicology 47 (2009) 129133.
[10] M.L. Salem, Immunomodulatory and therapeutic properties of the Nigella sativa L.
seed, International Immunopharmacology 5 (2005) 17491770.
[11] H. Hosseinzadeh, M. Tafaghodi, M.J. Mosavi, E. Taghiabadi, Effect of aqueous and
ethanolic extracts of Nigella sativa seeds on milk production in rats, Journal of
Acupuncture and Meridian Studies 6 (2013) 1823.
[12] M. Aqel, R. Shaheen, Effect of the volatile oil of Nigella sativa seeds on the uterine
smooth muscle of rat and guinea pig, Journal of Ethnopharmacology 52 (1996)
2326.
[13] A. Zaoui, Y. Cherrah, N. Mahassini, K. Alaoui, H. Amarouch, M. Hassar, Acute and
chronic toxicity o f Nigella sativa xed oil, Phytomedicine 9 (2002) 6974.
[14] S.K. Das, M.K. Bhunia, A.K. Sinha, A. Bhaumik, Synthesis, characterization, and biofuel
application of mesoporous zirconium oxophosphates, ACS Catalysis 1 (2011)
493501.
[15] M. Zabeti, W.M.A. Wan Daud, M.K. Aroua, Activity of solid catalysts for biodiesel
production: a review, Fuel Processing Technology 90 (2009) 770777.
[16] G. Guan, K. Kusakabe, N. Sakurai, K. Moriyama, Transesterication of vegetable oil to
biodiesel fuel using acid catalysts in the presence of dimethy lether, Fuel 88 (2009)
8186.

301

[17] D.M. Alonso, M.L. Granados, R. Mariscal, A. Douhal, Polarity of the acid chain of esters
and transesterication activity of acid catalysts, Journal of Catalysis 262 (2009) 1826.
[18] B.M.E. Russbueldt, W.F. Hoelderich, New sulfonic acid ion-exchange resins for the
preesterication of different oils and fats with high content of free fatty acids,
Applied Catalysis A: General 362 (2009) 4757.
[19] N.U. Soriano, R. Venditti, D.S. Argyropoulos, Biodiesel synthesis via homogeneous
Lewis acid-catalyzed transesterication, Fuel 88 (2009) 560565.
[20] L. Gang, L. Xinzong, W. Eli, Solvent-free esterication catalyzed by surfactant-combined
catalysts at room temperature, New Journal of Chemistry 3 (2007) 348351.
[21] G.F. Ghesti, J.L.D. Macedo, V.C.I. Parente, J.A. Dias, S.C.L. Dias, Synthesis,
characterization and reactivity of Lewis acid/surfactant cerium trisdodecylsulfate
catalyst for transesterication and esterication reactions, Applied Catalysis A:
General 355 (2009) 139147.
[22] F.C.G. de Mattos, J.A. da S. de Souza, A.B. do A. Cotrim, J.L. de Macedo, J.A. Dias, S.C.L.
Dias, G.F. Ghesti, Lewis acid/surfactant rare earth trisdodecylsulfate catalysts for
biodiesel production from waste cooking oil, Applied Catalysis A: General 423
424 (2012) 16.
[23] Y. Zhang, M. Stanciulescu, M. Ikura, Rapid transesterication of soybean oil with
phase transfer catalysts, Applied Catalysis A: General 366 (2009) 176183.
[24] N.B.A. DaSilveira, M.B. Alves, A.A.M. Lapis, F.M. Nachtigall, M.N. Eberlin, J. Dupont,
P.A.Z. Suarez, 1-n-Butyl-3-methylimidazolium tetrachloro-indate (BMI InCl4) as a
media for the synthesis of biodiesel from vegetable oils, Journal of Catalysis 249
(2007) 154161.
[25] M. Han, W. Yi, Q. Wu, Y. Liu, Y. Hong, D. Wang, Preparation of biodiesel from waste
oils catalyzed by a Brnsted acidic ionic liquid, Bioresource Technology 100 (2009)
23082310.
[26] X. Liang, G. Gong, H. Wu, J. Yang, Highly efcient procedure for the synthesis of
biodiesel from soybean oil using chloroaluminate ionic liquid as catalyst, Fuel 88
(2009) 613616.
[27] X. Li, W. Eli, A green approach for the synthesis of long chain aliphatic acid esters at
room temperature, Journal of Molecular Catalysis A: Chemical 279 (2008) 159164.
[28] L. Zhang, M. Xian, Y. He, L. Li, J. Yang, S. Yu, X. Xu, A Brnsted acidic ionic liquid as an
efcient and environmentally benign catalyst for biodiesel synthesis from free fatty
acids and alcohols, Bioresource Technology 100 (2009) 43684373.
[29] Y. Zhao, J. Long, F. Deng, X. Liu, Z. Li, C. Xia, J. Peng, Catalytic amounts of Brnsted
acidic ionic liquids promoted esterication: study of acidityactivity relationship,
Catalysis Communications 10 (2009) 732736.
[30] AOAC: Association of Offcial Analytical Chemists, Ofcial Methods of Analysis, 1990.
(Washington, DC, USA).
[31] C.E. Papadopoulos, A. Lazaridou, A. Koutsoumba, N. Kokkinos, A. Christoforidis, N.
Nikolaou, Optimization of cotton seed biodiesel quality (critical properties) through
modication of its FAME composition by highly selective homogeneous
hydrogenation, Bioresource Technology 101 (2010) 18121819.
[32] G. Knothe, Dependence of biodiesel fuel properties on the structure of fatty acid
alkyl esters, Fuel Processing Technology 86 (2005) 10591070.
[33] M.J. Ramos, C.M. Fernndez, A. Casas, L. Rodrguez, . Prez, Inuence of fatty acid
composition of raw materials on biodiesel properties, Bioresource Technology 100
(2009) 261268.
[34] M.M. Azam, A. Waris, N.M. Nahar, Prospects and potential of fatty acid methyl esters
of some non-traditional seed oils for use as biodiesel in India, Biomass and
Bioenergy 29 (2005) 293302.
[35] A.M. Gad, M. El-Dakhakhny, M.M. Hassan, Studies on the chemical composition of
Egyptian Nigella sativa L. oil, Planta Medica 11 (1963) 134138.
[36] E.S.M. Abdel-Aal, R.S. Attia, Characterization of black cumin (Nigella sativa) seeds. 2
Proteins, Alexandria Science Exchange (1993) 483496.
[37] S. Cheikh-Rouhou, S. Besbes, B. Hentati, C. Blecker, C. Deroanne, H. Attia, Nigella
sativa L.: Chemical composition and physicochemical characteristics of lipid fraction,
Food Chemistry 101 (2007) 673681.