chemical engineering research and design 1 1 7 ( 2 0 1 7 ) 584592

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Chemical Engineering Research and Design

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

Synthesis of biodiesel via transesterication of

tung oil catalyzed by new Brnsted acidic ionic
liquid

Jinbei Yang a,b , Yaoyao Feng a , Ting Zeng a , Xiaoting Guo a , Ling Li a ,
Ruoyu Hong a , Ting Qiu a,
aSchool of Chemical Engineering, Fuzhou University, Fuzhou 350108, Fujian, China
bSchool of Ocean Science and Biochemistry Engineering, Fuqing Branch of Fujian Normal University, Fuzhou
350300, Fujian, China

a r t i c l e i n f o a b s t r a c t

Article history: Two new Brnsted acidic ionic liquids were prepared and characterized by NMR and FTIR.
Received 29 June 2016 Their catalytic activities for the synthesis of biodiesel fuel via transesterication of tung oil
Received in revised form 14 with methanol were evaluated and compared to that of two imidazole-based ionic liquids for
September 2016 the rst time. Among them, [Ps-N-Ch(Me)2 ][p-TSA] exhibited the highest catalytic activity
Accepted 30 September 2016 and was chosen as catalyst for further research. A study on optimizing the reaction con-
Available online 25 November 2016 ditions was performed by orthogonal experiment based on the single factor experiment. It
was found that the ranking of the signicance of factors on the biodiesel yield is as follows:
Keywords: molar ratio of methanol to oil > reaction temperature > reaction time > catalyst dosage. The
Brnsted acidic ionic liquid maximum biodiesel yield reaches 98.98% under the optimal reaction conditions at a molar
Transesterication ratio of methanol to oil of 21:1, a reaction temperature of 120 C, a reaction time of 2 h and a
Catalyst catalyst dosage of 5.0 wt.%. Moreover, the reusability experiment exhibits that the catalyst
Biodiesel can be reused ve times with negligible loss of the activity. The rened biodiesel meets the
Tung oil biodiesel standard ASTM D6751-07, which can be used as fuel in diesel engines.
2016 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction
With the rapid growth in fossil fuel consumption and global warming
emissions, there is an urgent need to explore for green and renewable
energy resources (Jothiramalingam and Wang, 2009; Teo et al., 2016).
One way to solve these problems is to increase the use of bio-based fuels
(Aghabarari et al., 2014). Biodiesel, mainly derived from triglycerides
(vegetable oils or animal fats) by transesterication with low molec-
ular weight alcohols, is an attractive alternative to petroleum diesel
fuel because of its well-known advantages, such as nontoxicity, deriva-
tion from renewable feedstocks, and biodegradability (Elsheikh, 2014;
Aarthy et al., 2014; Fauzi and Amin, 2012). In addition, biodiesel, free of
sulfur and aromatics compounds, is therefore considered to be much
more renewable and cleaner than petroleum diesel, which could sig-
nicantly reduce the emissions of SOx , carbon monoxide and unburnt
hydrocarbons (Wu et al., 2007; Hu et al., 2008). Nevertheless, the major
obstacle to the commercialization of biodiesel is the high cost of edi-
ble vegetable oils and insufcient supply as compared to petroleum
diesel (Murugesan et al., 2009; Anuar and Abdullah, 2016), especially
in developing countries, such as China, Malaysia, Philippines, while
the price of biodiesel and demand for vegetable oils can be greatly
reduced if non-edible vegetable oils are used instead of edible vegetable
oils (Banapurmath et al., 2008; Agarwal, 2007). Tung oil, a non-edible
woody vegetable oils, is much suitable for biodiesel production in China
(Huang et al., 2015). Tung trees grow widely in southern China, and its
seed has oil content as high as 3040% approximately (Liu et al., 2015).
Hence, it is of great signicance to explore tung oil as an alternative
feedstock for biodiesel production.
Currently, alkali or acid were used as catalyst to prepare biodiesel,
which have high catalytic activity under mild conditions (Liu et al.,

Corresponding author.
E-mail address: tingqiu@fzu.edu.cn (T. Qiu).
http://dx.doi.org/10.1016/j.cherd.2016.09.038
0263-8762/ 2016 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
 chemical engineering research and design 1 1 7 ( 2 0 1 7 ) 584592 585

Fig 1 Structures of four Brnsted acidic ionic liquids.

2016; Zheng et al., 2006; Ahmed et al., 2015; Kumar et al., 2011). However,
the alkali catalysts, either NaOH or KOH, require vigorous anhydrous
conditions and low amount of free fatty acids (FFAs) in the feedstock
oil to avoid saponication reaction (Shahbazi et al., 2012; Cai et al.,
2015; Chung, 2010). The most commonly used acids such as sulfuric and
sulfonic acids are less sensitive to FFAs content but their application
has led to signicant equipment corrosion and environmental related
problems (Xie et al., 2011; Panchal et al., 2016). Therefore, it becomes
increasingly necessary to develop clean and environmentally friendly
catalysts for manufacturing biodiesel.
In recent years, ionic liquids (ILs), a kind of environmentally friendly
Fig. 2 Synthesis route of [Ps-N-Ch(Me)2 ][HSO4 ].
reaction medium and catalyst, have attracted wide attention among
researchers for biodiesel production through transesterication due to
their outstanding properties such as superior thermal stability, non- (Qiu et al., 2015; Wang et al., 2014), and their structures were
volatility and excellent catalytic activity coupled with their excellent outlined in Fig. 1. [Ps-N-Ch(Me)2 ][HSO4 ] was chosen as exam-
tunability and reusability (Li et al., 2014; Ullah et al., 2015; Yang et al., ple for the synthesis presented as follows, and the synthesis
2015; Zhang et al., 2016). The general type imidazole-based salts Brn-
route was shown in Fig. 2.
sted acidic ILs were greatly effective as water-stable catalysts in many
Firstly, 1,3-propanesultone (12.2 g, 0.1 mol) was dissolved
reactions (Aghabarari et al., 2014; Demir et al., 2015; Wu et al., 2015).
in 100 mL ethyl acetate. Then the equimolar amount of N,N-
Unfortunately, the high cost of ILs restricts their large-scale applica-
tion in biodiesel production. Thereby, we focused on developing lower
dimethylcyclohexylamine (12.7 g, 0.1 mol) was added to the
price and more effective functional ILs. solution at cold temperature with vigorous stirring. The solu-
In this paper, two new Brnsted acidic ILs were synthesized based tion was slowly heated up to 40 C and stirred for 8 h. After
on quaternary ammonium salts, which possess many excellent fea- reaction, the solution was ltered and the zwitterion salt
tures relative to the imidazole-based ILs including cheap feedstock and was puried twice with 50 mL ethyl acetate. The zwitterion
simple preparation procedures. The preparation of biodiesel from tung salt was dried in vacuum (0.1 MPa) at 90 C and obtained as
oil using new Brnsted acidic ILs as catalyst was investigated for the rst a white powder (yield 91.0%). Secondly, the zwitterion salt
time, and a study on optimizing the reaction conditions was performed was then dissolved in deionized water and the equimolar
by orthogonal experiment based on the single factor experiment. Fur-
amount of sulfuric acid (98 wt.%) was added slowly at 0 C
thermore, the reuse performance of ILs and the quality of the rened
under vigorous stirring. The solution was slowly heated up
biodiesel were also studied.
to 80 C and stirred for 4 h. After reaction, the water was
removed under vacuum, and the zwitterionic salt ([Ps-N-
2. Experimental
Ch(Me)2 ][HSO4 ]) was puried twice with 50 mL ethyl acetate.
The [Ps-N-Ch(Me)2 ][HSO4 ] was dried in vacuum (0.1 MPa) at
2.1. Materials
90 C and obtained as a light yellow viscous liquid (yield 97.0%).
Tung oil were obtained from Jiangsu, China. The
chemicals including sulfuric acid, ethyl acetate, 1,3- 2.3. Catalysts characterization
propanesulfonate, p-toluenesulfonic acid, methanol,
N,N-dimethylcyclohexylamine, N-methyl-imidazole were The 1 H NMR and 13 C NMR spectral data were recorded
bought from Aladdin and used without further purication. on a Bruker AV500 M spectrometer (Bruker Corporation,
Switzerland) in DMSO-d6 and calibrated with tetramethyl-
2.2. Catalysts preparation silane (TMS) as the internal reference. FT-IR measurements
were carried out using a Nicolet 510P spectrometer within
The two new types of Brnsted acidic ionic liquids used for the frequency range of 4000400 cm1 , using KBr pellets. The
the experiment were prepared by way of a two-step method thermal decomposition temperature was measured by TG
586 chemical engineering research and design 1 1 7 ( 2 0 1 7 ) 584592

Table 1 Physiochemical properties of tung oil.a

Properties Tung oil

Acid value (mg KOH/g) 6.4 0.1

Saponication value (mg KOH/g) 188.2 0.2
Average molecular weigh (g/mol) 926.0 3.6
Density at 313 K (g/cm3 ) 0.927 0.004
Kinematic viscosity at 313 K (mm2 /s) 101.0 1.2
Water content (wt.%) 0.018 0.002

a
Data are means standard deviation.

Table 2 Composition of biodiesel from tung oil obtained

by gas chromatography.
Composition Retention Composition
time (min) (wt.%)

Methyl palmitate (C16 :0) 12.54 2.26

Methyl oleate (C18 :1) 14.93 14.10
Methyl stearate (C18 :0) 15.18 2.26
Methyl eleostearate (C18 :3) 17.06 76.32
Methyl linoleate (C18 :2) 17.77 3.47
Methyl linolenate (C18 :3) 18.03 1.59

analysis using a Netzsch STA449F5 instrument (Netzsch Co.,

Ltd., Gemerny).
Fig. 3 Separation of biodiesel and glycerine in a
separating funnel.
2.4. Transesterication reaction and product analysis

2.4.1. Properties of tung oil
The saponication and acidic value of tung oil was deter-
mined according to the methods of GB/T 5530-2005 and GB/T
5534-2008 (China National Standard). Before transesterica-
tion reaction, the properties of tung oil such as acidity, density
and viscosity were also measured and listed in Table 1.
Moreover, the fatty acid prole of tung oil was analyzed by
gas chromatography (GC2014, Shimadzu Corporation, Japan)
equipped with a ame ionization detector and a TM-5 capil-
lary column (0.32 mm 50 m) with 0.5 m lm thickness. The
oven was operated with programmed temperature, the initial
temperature of 150 C held for 1 min, heat rate of 30 C/min
to 240 C maintained for 2 min, then heat rate of 5 C/min
to 280 C, held for 2 min, and nally with a further rate of
40 C/min to 310 C, kept for 8 min. The temperatures of injec-
tion and FID detector were both 310 C. The composition of
the tung biodiesel was listed in Table 2. The highest peak is
methyl eleostearate, with content of 76.32%.
2.4.2. Transesterication reaction for biodiesel
Solubility test was conducted on the ILs against the other pro-
cess chemicals namely methanol, fatty acid methyl ester, tung
oil and glycerine prior to the experiment. The results show that
the ILs are only soluble with methanol. The transesterication
reaction was performed in a 50 mL cylindrical 316L-stainless
steel reactor, equipped with a thermostat and magnetic stir-
rer to ensure thorough mixing of reactants. A xed amount
of freshly prepared methanol solution containing the respec-
tive ILs was added into the tung oil. The mixture was heated
rapidly to the desired temperature under 1.0 MPa pressure.
Attempt is then made to optimized the variables known to
affect the transesterication reaction such as the ILs type,
catalyst dosage (1.05.0 wt.%), molar ratio of methanol to oil
(9:1, 12:1, 15:1, 18:1, 21:1), reaction temperature (90, 100, 110,
120, 130 C), reaction time (0, 30, 60, 90, 120, 150, 180 min) and
stirring speed (0, 50, 100, 200, 300, 400, 500, 600 rpm).
Upon completing the reaction, the product mixture was
distilled to remove excess methanol. The leftover liquid is
poured into a separating funnel where it quickly formed two
phases completely within 20 min, which was shown in Fig. 3.
The upper phase, which was mainly composed of biodiesel,
was analyzed by GC. The lower phase containing the glycer-
ine and ILs, was washed with hexane and ethyl acetate and
then dried in vacuum for 3 h. The mixture was cooled and
then centrifuged for 30 min after which the ILs was separated
from the glycerine for reuse.
2.4.3. Determination of yield
During the course of the experiment, the catalyst used in our
work is acidic, not alkaline, thus we found that there is no
side reaction, such as saponication, in synthesis biodiesel via
transesterication of tung oil with methanol. In other words,
the conversion of triglyceride is equal to the biodiesel yield.
The biodiesel yield was determined by indirectly measuring
the weight of the glycerine by-product using a method known
as periodic acid oxidation titrate (Pisarello et al., 2010). The
developed method is simple and accurate with high repeata-
bility. Firstly, free glycerine is oxidized to formaldehyde and
formic acid by excess potassium periodate. Secondly, the con-
tent of iodine, which was generated during the oxidation
of potassium iodide with potassium iodate and periodate,
was titrated with standard sodium thiosulfate solution under
acidic conditions. The related reaction was listed as follows:
(1)
KIO4 + 7KI + 4H2 SO4 4I2 + 4K2 SO4 + 4H2 O (2)
KIO3 + 5KI + 3H2 SO4 3I2 + 3K2 SO4 + 3H2 O (3)
 chemical engineering research and design 1 1 7 ( 2 0 1 7 ) 584592
I2 + 2Na2 S2 O3 Na2 S4 O4 + 2NaI
The weight of glycerine in the tested sample can be calcu-
lated by the following equation:
(V0 V) C Mg
wg =
4 1000
where wg is the weight of glycerine, g; Mg is the molecular
weight of glycerine, 92.09 g/mol; V0 is consumption of stan-
dard sodium thiosulfate solution in the titration of blank
solution, mL; V is consumption of standard sodium thiosul-
fate solution in the titration of the tested sample, mL; C is
concentration of standard sodium thiosulfate solution, mol/L.
The total transterication equation can be described as fol-
lows:
The molecular weight of the synthesized biodiesel is
approximately equal to the molecular weight of tung oil accord-
ing to the Eq. (1), which can be illustrated as:
M(CH3 COORn ) = Mt + 4 Mt
where M(CH is the molecular weight of the synthe-
3 COORn )
sized biodiesel, g/mol; Mt is the average molecular weight of
tung oil, g/mol.
Therefore, the biodiesel yield can be calculated using the
following equation:
wg M(CH
wb 3 COORn ) wg Mt
= 100% = (8)
wt wt Mg wt Mg
where  is the biodiesel yield; wb is the sample weight of
biodiesel, g; wt is the sample weight of tung oil, g; wg is the
weight of glycerine, g; Mg is the molecular weight of glycer-
ine, 92.09 g/mol. All samples were performed in triplicate and
mean values were quoted as results.
3. Results and discussion
3.1. Characterization of catalysts
The 1 H NMR and 13 C NMR spectral data of the two new ILs are
listed as follows:
(A) [Ps-N-Ch(Me)2 ][p-TSA]: 1 H NMR spectrum (500 MHz,
DMSO-d6 ) (ppm): 7.84 (d, 4H, Ph-H), 6.30 (s, 6H, 2N-CH3 ),
4.39 (m, 1H), 3.79 (t, 2H), 2.86 (s, 3H), 2.42 (t, 2H), 2.34
(m, 2H), 2.20 (m, 2H), 1.66 (m, 4H), 1.46 (m, 4H). 13 C NMR
spectrum (125 MHz, DMSO-d6 ) (ppm): 144.91, 138.92,
128.78, 125.94, 71.15, 61.14, 60.14, 48.12, 25.69, 25.28, 24.84,
21.24, 18.92.
(B) [Ps-N-Ch(Me)2 ][HSO4 ]: 1 H NMR spectrum (500 MHz, DMSO-
d6 ) (ppm): 6.76 (s, 6H, 2N-CH3 ), 4.11 (m, 1H), 3.78 (t, 2H),
2.42 (t, 2H), 2.33(m, 2H), 1.76 (m, 2H), 1.66 (m, 4H), 1.46 (m,
4H). 13 C NMR spectrum (125 MHz, DMSO-d6 ) (ppm): 71.13,
61.13, 60.18, 48.11, 25.68, 25.28, 24.84, 18.91.
587
(4)
Table 3 Yield of biodiesel reaction for each ILs used.a
Entry Catalysts Yieldb (%)
A [Ps-N-Ch(Me)2 ][p-TSA] 85.21 0.25
B [Ps-N-Ch(Me)2 ][HSO4 ] 73.60 0.16
C [Ps-mim][p-TSA] 76.55 0.35
(5) D [Ps-mim][HSO4 ] 56.48 0.42
a
Catalysts dosage, 3 wt.% (based on the mass of tung oil); the initial
molar ratio of methanol to oil, 15.0; reaction temperature, 110 C;
reaction time, 90 min; stirring speed, 400 rpm.
b
Data are means standard deviation.
Whilst the FT-IR spectral data of the two new ILs are listed
below:
(A) [Ps-N-Ch(Me)2 ][p-TSA]: FT-IR (KBr, cm1 ): 3440, 2940, 2870,
1720, 1450, 1230, 1030, 681, 565.
(B) [Ps-N-Ch(Me)2 ][HSO4 ]: FT-IR (KBr, cm1 ): 3430, 2940, 2870,
1700, 1460, 1230, 1030, 575.
(6)
The structure analysis of the two new ILs using NMR and
FT-IR shows good agreement on the ILs designed structure
(Fig. 1). Moreover, there is no impurity peak in the 1 H NMR
spectra, which demonstrates that the synthesized ILs are of
high purity. In addition, the thermal decomposition tempera-
ture of all ILs used in this study is above 300 C according to the
(7)
weight loss curve of the ionic liquids, which indicates that the
ionic liquids possess good thermal stability and wide liquid
range.
3.2. Catalytic performance of different ILs
Our previous study demonstrated that N-methyl-imidazole
based ILs exhibit high catalytic activity in transesterication
reaciton (Wang et al., 2014). Therefore, two N-methyl-
imidazole based ILs [Ps-mim][p-TSA] (C) and [Ps-mim][HSO4 ]
(D) were also chosen as catalysts for the synthesis of biodiesel
via the transesterication of tung oil with methanol for a
comparison study to the new ILs (A) and (B). The reaction con-
ditions: 20 g tung oil, 0.60 g ILs catalysts (3% based on the mass
of tung oil), molar ratio of methanol to oil = 15:1, 110 C, 90 min,
400 rpm.
It can be observed from Table 3 that the biodiesel yield
produced from the reactions using the different ILs followed
the trend of A > C > B > D. Two new quaternary ammonium-
based ILs exhibit higher activity than the imidazolium-based
ILs. It is well known that different Brnsted acidities of
the anions have different catalytic activity. [p-TSA] has
a higher Brnsted acidity than [HSO4 ] , and hence the
transesterication of tung oil with methanol has a higher
yield in [p-TSA] . In addition, the cation type also has
a remarkable inuence on the transesterication reaction.
The N,N-dimethylcyclohexylamine cation-based ILs exhibit a
higher efciency, whether its anions is tosylate or bisulfate.
Among the four investigated ILs, the [Ps-N-Ch(Me)2 ]+ cation-
based ILs have some clear advantages. Firstly, it produces
higher biodiesel reaction yield. Secondly, the precursor N,N-
dimethylcyclohexylamine (80 RMB/100 mL) is cheaper than
N-methyl-imidazole (168 RMB/100 mL). Moreover, the [Ps-N-
Ch(Me)2 ]+ cation-based ILs can be easily prepared and the high
yield of ILs product were obtained. Hence, for the follow-up
experiments, the effect of reactant molar ratio, reaction tem-
perature, catalyst dosage, reaction time, and stirring speed
588 chemical engineering research and design 1 1 7 ( 2 0 1 7 ) 584592
100
90
80
70
Yield (%)
60
50
40
30
20
0 100 200 300 400 500
Stirring speed (rpm)
Fig. 4 Effect of stirring speed on the biodiesel yield.
Reaction conditions: catalyst dosage, 4.0 wt.%; molar ratio
of methanol to oil, 18:1; temperature, 110 C; reaction time,
2 h. The error bars indicate the standard deviation of the
mean.
on the transesterication reaciton were further investigated
using [Ps-N-Ch(Me)2 ][p-TSA] as catalyst.
3.3. Optimization study of the experimental conditions
3.3.1. Effect of stirring speed
The stirring intensity plays a signicant role in the transes-
terication reaction, because it can increase the intact area
between oils and ILs methanol solution and enhance the
reaction rate. Without stirring, the transesterication reac-
tion only occurs at the interface of the two phases, which
leads to the slow reaction rate. Therefore, the effect of stir-
ring speed on the biodiesel yield at different rates of stirring
intensity ranging from 0 to 600 rpm was investigated, exper-
iments were carried out at the catalyst dosage of 4.0 wt.%,
molar ratio of 18:1, reaction time of 120 min and tempera-
ture of 110 C. As can be seen from Fig. 4, it was observed that
the transesterication reaction was practically incomplete at
0, 50 and 100 rpm, which only exhibited a yield of 34.4%,
50.7% and 81.6%, respectively. The biodiesel yield appears to
increase signicantly with the increase in stirring speed, up
to 97.0% at 400 rpm. However, when the stirring speed was
further increased, the biodiesel yield changes insignicantly,
yet it causes an increase in energy consumption. The result is
consistent with the literatures (Rashid and Anwar, 2008; Ma
et al., 1999), which reported the effect of stirring speed on
the transesterication reaction of vegetable oil and concluded
that higher stirring speed promotes the homogenization of the
reactants and thus leads to higher yields. Thus, 400 rpm is con-
sidered as the optimum stirring speed, which can sufciently
avoid mass transfer resistances.
3.3.2. Effect of molar ratio of methanol to oil
The molar ratio of methanol to tung oil is one of the most sig-
nicant factors that can affect the biodiesel yield. In order to
study the effect of molar ratio on the biodiesel yield, experi-
ments were carried out at molar ratios of methanol to tung oil
from 9:1 to 21:1, respectively. The results were shown in Fig. 5.
As presented in Fig. 5, we can nd an asymptotic trend for
the biodiesel yield. Theoretically, transesterication requires
three moles of methanol and one mole of tung oil to yield three
moles fatty methyl esters and one mole of glycerine. However,
transesterication is an equilibrium reaction in which excess
methanol is required to drive the reaction close to completion.
70
65
60
Yield (%)
55
50
45
40
600 9 12 15 18 21
Molar ratio of methanol to oil
Fig. 5 Effect of molar ratio of methanol to oil on the
biodiesel yield. Reaction conditions: catalyst dosage,
3.0 wt.%; reaction temperature, 100 C; stirring speed,
400 rpm; reaction time, 2 h. The error bars indicate the
standard deviation of the mean.
100
80
Yield (%)
60
40
20
85 90 95 100 105 110 115 120 125 130 135
Reaction temperature (o C)
Fig. 6 Effect of reaction temperature on the biodiesel yield.
Reaction conditions: catalyst dosage, 3.0 wt.%; molar ratio
of methanol to oil, 18:1; stirring speed, 400 rpm; reaction
time, 2 h. The error bars indicate the standard deviation of
the mean.
The maximum biodiesel yield was obtained at a molar ratio
of 18:1. When the molar ratio is increased from 9:1 to 18:1,
the biodiesel yield rises from 54.5% to 67.1%. There is very lit-
tle effect on the biodiesel yield beyond 18:1. The ILs becomes
diluted as the excess methanol was increased and it was
observed that when the molar ratio of methanol to oil exceed
18:1, the increase in reaction yield reduces signicantly. The
increasing presence of excess methanol in the mixture also
poses more difcult separation process and hence raising the
cost for methanol recovery (Zhang et al., 2009). Therefore, the
optimum molar ratio of methanol to oil is 18:1.
3.3.3. Effect of reaction temperature
Reaction temperature is also an important factors affecting
the reaction rate and biodiesel yield. Experimental trials were
conducted at temperatures in the range of 90130 C, and the
results were illustrated in Fig. 6. As can be seen in gure,
only 23.2% of tung oil was converted into biodiesel when the
reaction temperature was 90 C. The increment of tempera-
ture is apparently favorable to accelerate the biodiesel yield,
which reaches a high yield of 91.3% at 110 C. This is prob-
ably because of the progressive intensication in molecular
collision and the decrease in viscosity of tung oil as the tem-
perature increased, such a situation is favorable to reduce
the mass transfer resistance and improve the reaction rate.
 chemical engineering research and design 1 1 7 ( 2 0 1 7 ) 584592 589

100 100

90 80

80
60

Yield (%)
Yield (%)

70
40
60

20
50

40 0
1 2 3 4 5 0 30 60 90 120 150 180
Catalyst dosage (wt.%) Reaction time (min)

Fig. 7 Effect of catalyst dosage on the biodiesel yield.
Reaction conditions: molar ratio of methanol to oil, 18:1;
reaction temperature, 110 C; stirring speed, 400 rpm;
reaction time, 2 h. The error bars indicate the standard
deviation of the mean.
Fig. 8 Effect of reaction time on the biodiesel yield.
Reaction conditions: catalyst dosage, 4.0 wt.%; molar ratio
of methanol to oil, 18:1; reaction temperature, 110 C;
stirring speed, 400 rpm. The error bars indicate the
standard deviation of the mean.

However, the biodiesel yield changes slightly with a further

increase in reaction temperature, which may be due to the
fast evaporation of methanol. Under the reaction pressure of
0.101 and 1.0 MPa, the boiling temperature of methanol is 64.6
and 136.7 C, respectively. When the reaction temperature is
close to 136.7 C, a greater amount of vaporization of methanol
takes place, thereby reducing the molar ratio of methanol to oil
(Chang et al., 2015; Zhang et al., 2016). Furthermore, the solu-
tion after reaction at 130 C exhibited a very dark brown color.
Hence, 110 C is chosen for the optimum reaction temperature
in the present study.
3.3.4. Effect of catalyst dosage
During the course of the experiments, the catalyst dosage,
dened as the mass percentage of the catalyst to the mass of
tung oil, was varied in the range of 1.05.0 wt.% at the temper-
ature of 110 C and the initial molar ratio of methanol to oil of
18:1. As shown in Fig. 7, it has been observed that the biodiesel
yield increases initially as the catalyst dosage was increased
from 1.0 to 4.0 wt.% due to the increase in the number of
acidic sites available for reaction, reaching a maximum value
of 97.0% (Ghiaci et al., 2011). However, further increase in cata-
lyst dosage results in reduction of the biodiesel yield to 95.4%.
This is because transesterication of tung oil with methanol is
the typical reversible reactions and the catalyst could catalyze
both the forward and reverse reactions (Wu et al., 2015). Addi-
tion of excess ILs may promote the reverse reaction, thereby
reducing the biodiesel yield. Thus, the optimum concentration
for catalyst ILs is 4.0 wt.%.
3.3.5. Effect of reaction time
The effect of reaction time on the biodiesel yield was con-
ducted with 4.0 wt.% catalyst dosage, 18:1 molar ratio, and
at the temperature of 110 C. Experimental result was shown
in Fig. 8. As can be observed, the biodiesel yield increases
from 39.4% to 97.0% when the reaction time was increased
from 30 min to 120 min, after which the yield remained rela-
tively constant. Accordingly, it can be concluded that 120 min
is considered as the optimum reaction time for the transes-
terication of tung oil.
The above single factor experiments show that [Ps-N-
Ch(Me)2 ][p-TSA] performs excellent catalytic activity in the
transesterication of tung oil with methanol. Based on these
results, an orthogonal experiment was employed to further
Table 4 Factors and levels affecting the biodiesel yield.
Name Factors Level
1 2 3
Methanol to tung oil (mol/mol) A 15 18 21
Catalyst dosage (wt.%) B 3 4 5
Reaction time (min) C 90 120 150
Reaction temperature ( C) D 100 110 120
optimize the reaction conditions using [Ps-N-Ch(Me)2 ][p-TSA]
as catalyst.
3.3.6. Orthogonal experiment
According to the analysis of above single-factor experiments,
four inuencing factors of molar ratio of methanol to oil (fac-
tor A), catalyst dosage (factor B), reaction time (factor C) and
reaction temperature (factor D) were chosen to do further
optimization, and three levels were set for each factor (Cao
et al., 2016). Therefore, a L9 [34] orthogonal experiment, which
is an orthogonal array of four factors and three levels (Wu and
Leung, 2011), was conducted to assign the considered factors
and levels as shown in Table 4.
The biodiesel yield was set as the target for the investiga-
tion, to qualitatively analyze effects of the selected factors. Ki , j
is the summation of the optimizing index which corresponds
with the j list factor and i level; ki , j being the average of Ki , j and
Rj being the difference between maximum and minimum val-
ues of levels for the corresponding j list factor. The larger the
value of Rj , the bigger the effect of the corresponding j list fac-
tor on optimization index. The optimization results were listed
in Table 5. The optimum value for the different factors can
be easily determined using the range analysis. It was found
that the order of signicance of these factors on the biodiesel
yield follows: molar ratio of methanol to oil > reaction tem-
perature > reaction time > catalyst dosage. It was observed that
molar ratio of methanol to oil is one of the most signicant fac-
tors affecting the biodiesel yield and the optimum condition
is A3 B3 C2 D3 . Hence, the optimum reaction conditions are as
follows: molar ratio of methanol to oil, 21:1; reaction temper-
ature, 120 C; reaction time, 2 h; catalyst dosage, 5.0 wt.%; and
stirring speed, 400 rpm. Finally, the experiment was repeated
thrice under the optimum conditions, and a yield of biodiesel
590 chemical engineering research and design 1 1 7 ( 2 0 1 7 ) 584592

Table 5 Yield of biodiesel in the orthogonal experiment design.

Levels Factors Results

A B C D Yielda (%)

Trial 1 1 1 1 1 43.49 0.34

No. 2 1 2 2 2 90.52 0.40
3 1 3 3 3 95.63 0.35
4 2 1 2 3 96.82 0.28
5 2 2 3 1 88.16 0.32
6 2 3 1 2 93.27 0.50
7 3 1 3 2 96.62 0.14
8 3 2 1 3 94.45 0.24
9 3 3 2 1 97.60 0.22
K1j 229.64 236.92 231.22 229.25
K2j 278.25 273.13 284.94 280.41
K3j 288.68 286.51 280.41 286.90
k1j 76.55 78.97 77.07 76.42
k2j 92.75 91.04 94.98 93.47
k3j 96.23 95.50 93.47 95.63
Range Rj 19.68 16.53 17.91 19.22
Important order A>D>C>B
Optimum level 3 3 2 3
Optimum combination A3 B3 C2 D3 98.98 0.18

a
Data are means standard deviation.

100 was observed beyond the 5th cycle. The recovered ILs after
With Gly cerin Without Gly cerin
seven reuses has no obvious change in structure, referring to
90 the FTIR spectrum in comparison with fresh catalyst listed in
Fig. 10. Therefore, it can be concluded that the decrease of
80
catalytic activity could be attributed to the weight loss of ILs
during its recovery, not to the change in molecular structure,
Yield (%)

70
which exhibits its excellent reusability.
60

50 3.5. Physical properties of biodiesel from tung oil

40 After reaction, the synthesized biodiesel was washed with

hot distilled water (50 C) repeatedly to remove the impurities,
30
1 2 3 4 5 6 7 and then collected in vacuum distillation for 5 h (160260 C,
Catalyst reusability 2 kPa). The physical properties of the rened biodiesel was
determined and presented in Table 6. As shown in table, high-
Fig. 9 Reusability of [Ps-N-Ch(Me)2 ][p-TSA] catalyst under
quality biodiesel with less impurities was obtained, which
optimum reaction conditions. The error bars indicate the
meets the biodiesel standard ASTM D6751-07.
standard deviation of the mean.

98.98% was obtained, which is higher than any former orthog-

onal experimental result.

3.4. Reusability of catalyst

C 1720 683 567
The recovery and reuse of catalyst is clearly preferable from 2940 2880
1450 1210

both an environmental and a economic points of view. In

3360
order to study the possibility of recycling of the ILs [Ps-N- 1700
1040
Transmittance

B
Ch(Me)2 ][p-TSA], a recycling experiment was carried out under 1230 1030
575
1460
optimum conditions determined above (Table 5). The catalyst 2870
3430 2940
1450
was recovered as described in Section 2.4.2. The reusability 1720
A 565
results obtained are summarised in Fig. 9 where the biodiesel 1230
yield was used to reect the changes in the catalyst activity. 2940
2870

3440 681
As shown in the gure, when the glycerine was not sepa- 1030
rated from the catalyst, the catalytic activity decreases rapidly
through the seven application cycles. This is due to the pres-
ence and accumulation of the glycerine by-product within the 4000 3600 3200 2800 2400 2000 1600 1200 800 400
ILs during each cycle. However, when the glycerine was sepa- Wavenumbers(cm )
-1

rated from the ILs, the catalyst reusability was found to better
where only slight drop in the activity was observed between Fig. 10 FT-IR spectra of ILs. (A) [Ps-N-Ch(Me)2 ][p-TSA]; (B)
each cycle. Nevertheless, larger drop in the catalyst activity [Ps-N-Ch(Me)2 ][HSO4 ]; (C) recovered [Ps-N-Ch(Me)2 ][p-TSA].
 chemical engineering research and design 1 1 7 ( 2 0 1 7 ) 584592
Table 6 Comparison of physical properties of rened
biodiesel.a
Entry Value ASTM D6751-07
Density (288 K) (kg/m3 ) 892 2 870900
Kinematic viscosity (313 K) (mm2 /s) 5.2 0.2 1.96.0
Acid value (mg KOH/g) 0.73 0.1 0.80
Water content (mg/kg) 160 3 500
Flash point ( C) 192.3 0.4 130
Copper strip corrosion 1 3
Cetane 51.4 0.3 47
Sulfur (ppm) No detected 15
a
Data are means standard deviation.
4. Conclusions
In this work, two new Brnsted acidic ionic liquids were
synthesized and used as the catalysts in the preparation of
biodiesel via the transesterication of tung oil and methanol
for the rst time. The experiment results demonstrated that
[Ps-N-Ch(Me)2 ][p-TSA] exhibits higher catalytic activity than
the other three ILs including two imidazole-based ionic liq-
uids. The optimum reaction conditions were obtained through
orthogonal experiments based on the single factor experi-
ments. According to the range analysis, the order of signicant
factors on the biodiesel yield was determined to be as
follows: molar ratio of methanol to oil > reaction tempera-
ture > reaction time > catalyst dosage. The optimum biodiesel
yield was found to occur at a molar ratio of methanol to oil of
21:1, a reaction temperature of 120 C, a reaction time of 2 h
and a catalyst dosage of 5.0 wt.%. The biodiesel yield under
optimum conditions is 98.98%, which is higher than any for-
mer orthogonal experimental result. Moreover, the reusability
experiment exhibits that the catalyst can be reused ve times
with negligible loss of the activity. The rened biodiesel meets
the biodiesel standard ASTM D6751-07, which can be used as
fuel in diesel engines.
Acknowledgements
We acknowledge the nancial support for this work from the
National Natural Science Foundation of China (Nos. 21576053
and 91534106), the International S&T Cooperation Program of
China (No. 2013DFR90540), the Science Foundation for Distin-
guished Young Scholars of Fujian (No. 2014J06004), the Natural
Science Foundation of Fujian Province (No. 2016J01689), the
Key Project of Fujian Provincial Department of Science and
Technology (No. 2014Y0066).
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