Preparation of KF/CaO nanocatalyst and its application in biodiesel

production from Chinese tallow seed oil

Libai Wen, Yun Wang
*
, Donglian Lu, Shengyang Hu, Heyou Han
College of Science, Huazhong Agricultural University, Wuhan 430070, China
a r t i c l e i n f o
Article history:
Received 1 October 2009
Received in revised form 24 January 2010
Accepted 26 January 2010
Available online 6 February 2010
Keywords:
Biodiesel
Nanocatalyst
Chinese tallow seed oil
Transesterication
a b s t r a c t
KF/CaO nanocatalyst was prepared by using impregnation method and used to convert Chinese tallow
seed oil to biodiesel. The effects of different preparation conditions on biodiesel yield were investigated
and the structure of the catalyst was characterized. Transmission electron microscopy (TEM) photograph
showed that the catalyst had porous structure with the particle size of 30100 nm. BrunauerEmmet
Teller (BET) analysis indicated that the catalyst specic surface area was 109 m
2
g
1
and average pore size
was 97 nm. X-ray diffractometer (XRD) analysis demonstrated that the new crystal KCaF
3
was formed in
catalyst, which enhanced catalytic ability. Under the optimal conditions, the biodiesel yield was 96.8% in
the presence of as-prepared KF/CaO catalyst, showing potential applications of catalyst in biodiesel
industry.
2010 Elsevier Ltd. All rights reserved.
1. Introduction
With the increase of environment protection consciousness and
decrease of petroleum reserves, biodiesel, dened as the monoal-
kyl esters of fatty acids, has been the focus of a considerable
amount of recent research as an alternative renewable fuel. More
and more biodiesel is being used in many countries such as Ger-
many, France, Italy, USA, Japan and so on [1,2]. The general method
for the preparation of biodiesel is transesterication reaction of oil
and alcohol with homogeneous catalyst [3,4]. However, the homo-
geneous catalyst has many shortcomings, such as the difculty in
product isolation, requirement of large quantity of water and envi-
ronmental pollution by the liquid wastes [57]. A new trend in the
preparation of biodiesel is to use green method based on
heterogeneous catalyst [8,9]. Despite the solid phase catalytic
methods are intensively studied, the industrial applications are
limited. This fact suggests that further research is necessary to
solve current problems [10,11]. Heterogeneous catalytic methods
are usually mass transfer resistant, time consuming and inefcient
[12]. Nanocatalysts have high specic surface and high catalysis
activities, may solve the above problems. They have become the
focus of recent research [13,14].
Another problem in biodiesel production is the source of raw
material. It is well known that grain and oil are in short supply
in many countries. Thus, it is necessary to develop non-edible oil
as the raw material of biodiesel. As an ideal source for biodiesel
production, Chinese tallow seed oil is woody plant oil containing
4070% fatty acid and has more than 100,000 metric tons of pro-
duction in China [15,16]. Chinese tallow seed oil causes intoxica-
tion and saponication problems if transesterication is
catalyzed with homogeneous catalyst such as KOH, NaOH and
CH
3
ONa, because its acid value (28 mg KOH g
1
oil) is higher than
rapeseed oil and soybean oil [1720]. Therefore, an acid-tolerant
solid base catalyst has some advantageous alternative for biodiesel
production from Chinese tallow seed oil [21].
Here, we report the preparation of KF/CaO solid base nanocata-
lyst from KF and CaO with impregnation method. The preparation
conditions of the catalyst were studied with orthogonal design. The
structure and properties were characterized by transmission elec-
tronmicroscopy (TEM), X-ray diffractometer (XRD), BrunauerEm-
metTeller (BET) et al. We further optimized the conditions of
transesterication for the preparation of biodiesel from Chinese
tallow seed oil. The reusable, anti-acidic ability and mechanism
of catalysis were also investigated.
2. Experiment
Chinese tallow seed oil had an acid value of 2.4 mg KOH g
1
oil.
It contained 0.08% (wt) water and its molecular mass was
896 g mol
1
. Absolute methanol, CaO, KF, methyl oleate and oleic
acid were analytical reagents.
The catalyst was prepared by impregnation method [22]. Typi-
cally, 10.0 g of CaO was powderized and immersed in 1520 mL KF
solution with certain amount (1.5 g, 2.5 g, 3.5 g) for 1 h, then baked
at 105 C for 46 h followed by 24 h calcination in mufe furnace
at certain temperature (450 C, 600 C, 750 C). The as-prepared
catalyst was preserved in dryer for further use.
0016-2361/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2010.01.028
* Corresponding author. Tel.: +86 27 87284018; fax: +86 27 87282133.
E-mail address: yunwang123@126.com (Y. Wang).
Fuel 89 (2010) 22672271
Contents lists available at ScienceDirect
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Surface structure of the catalyst was analyzed with JEM-100SX
TEM. Catalyst phase was analyzed with D/Max-IIIA XRD with Cu
Ka target (scanning parameter: speed 10 min
1
, step 0.02, 2h an-
gle 1070, voltage 35 kV, current 30 mA). Pore size was analyzed
with Autosorb-1 pore size analyzer using N
2
adsorptiondesorp-
tion method with measure range of 0.13500 m
2
g
1
specic area
and 2200 nm pore diameter. The repeatability error was within
2%.
1
The transesterication reactions (Eq. 1) were carried out in a
250 mL three-necked ask. The reaction procedure was as follows:
rst, Chinese tallow seed oil was added to the ask. Methanol and
catalyst were mixed and then added to the ask. Reux reaction
was done at indicated temperature. After that, catalyst and glycerol
were isolated. Methanol was isolated from the biodiesel with ro-
tary evaporator. The reusable stability and anti-acidic ability were
evaluated with biodiesel yield. Biodiesel yield was obtained
according to the method reported by Liu et al. [11]. The mass
concentration of biodiesel was measured with HITACHI163 gas
chromatography instrument [23]. Column temperature and tem-
perature program were set as follows: the initial temperature
was set at 190 C, and then was rised up to 280 C with heating rate
of 10 C min
1
, sampler temperature was 300 C, detector temper-
ature was set at 280 C, ow velocity of H
2
was kept at
40 mL min
1
, ow velocity of N
2
was kept at 25 mL min
1
, ow
velocity of air was kept at 400 mL min
1
.
3. Results and discussion
3.1. Conditional optimization of KF/CaO preparation
An orthogonal optimization for the catalyst preparation was
performed. The design of orthogonal experiment was shown in Ta-
ble 1. The catalytic property was evaluated by biodiesel yield. The
transesterication was performed at 65 C for 2 h with 9:1 M ratio
of methanol to oil and 3% w/w catalyst of oil.
As shown in Table 2, the KF content had the greatest effect, fol-
lowed by calcination temperature. The optimal conditions were
0.25 mass ratio of KF to CaO, calcination temperature 600 C and
calcination time 4 h.
Orthogonal test revealed that as the increase in KF content, the
biodiesel production rate increased. The catalyst had best catalytic
activity when KF content was 25% w/w. However, when the load-
ing amount of KF was greater than 25%, the catalytic activity de-
creased. Since KF was supported on CaO, it is evenly distributed
on CaO surface if the KF content was lower than a threshold with
mono-molecular layer. When the KF content became higher than
the threshold, it covered the activity sites, resulting in decrease
of catalytic ability. During the preparation of the solid catalyst,
high temperature calcination favors the interaction between car-
rier and active component to form new crystal, activity sites. How-
ever, overheating can result in the surface sintering and the
reduction of specic surface area, which in turn leads to the reduc-
tion in catalytic activity [24]. The current experiment showed that
calcination at 600 C produced highly active catalyst.
3.2. Characterization of KF/CaO catalyst
The TEM photograph showed that the catalyst was granular and
porous with evenly distributed granules and abundant large pores.
As shown in Fig. 1, the granules were made up of several smaller
granules with 30100 nm in diameter which formed a porous
net-like structure. These results showed that the catalyst was
porous which increased the contact between the catalyst and the
substrates. These improved catalytic ability and increased transe-
sterication efciency. It was demonstrated that the catalyst is a
type of supported solid base nanocatalyst.
Fig. 2 depicted the XRD proles of KF/CaO calcined under vari-
ous temperatures. The results indicated that KCaF
3
was produced
during the impregnation stage. Since impregnation releases heat,
Table 1
Design table of orthogonal experiment.
Number A B C
Factor KF/CaO mass
ratio
Calcination temperature
(C)
Calcination time
(h)
Level 1 0.15 450 2
Level 2 0.25 600 3
Level 3 0.35 750 4
Table 2
Orthogonal optimization of catalyst preparation.
Number A B C Biodiesel
yield (%)
Factor KF/CaO
mass ratio
Calcination
temperature (C)
Calcination
time (h)
Experiment 1 1 1 1 80.2
Experiment 2 1 2 2 84.9
Experiment 3 1 3 3 87.3
Experiment 4 2 1 3 92.8
Experiment 5 2 2 1 93.7
Experiment 6 2 3 2 93.6
Experiment 7 3 1 2 89.6
Experiment 8 3 2 3 91.5
Experiment 9 3 3 1 90.2
K
1
84.1 87.5 88.0
K
2
93.4 90.8 89.4
K
3
90.4 90.0 90.5
R 9.3 3.3 2.5
K
1
, K
2
and K
3
are the average value of biodiesel yield at level 1, level 2 and level 3,
respectively. R is pole difference of average value of biodiesel yield.
Fig. 1. TEM photograph of as-prepared KF/CaO catalyst.
2268 L. Wen et al. / Fuel 89 (2010) 22672271
the temperature may reach 120 C. New crystal structure of KCaF
3
can formunder lowtemperature with the peak intensity increasing
from room temperature to 400 C and decreasing from 400 C to
600 C. As the temperature increases, Ca(OH)
2
diffraction peak
diminished while CaO diffraction peak formed. The peak of CaO
started to form at 400 C while the peak of Ca(OH)
2
was completely
disappeared at 600 C. The 2h angles () of the three phases were:
18.02, 34.08, 47.14, 50.82, 54.36, 62.60, 64.26 of Ca(OH)
2
, 28.74,
41.22, 51.26, 59.52, 59.69, 67.59 of KCaF
3
, 32.12, 37.28, 53.80,
64.12, 67.34 of CaO. Considering all the factors mentioned above,
and that Ca(OH)
2
can cause easily saponication in biodiesel prep-
aration [25], we concluded that catalyst should be calcined at
600 C, which is identical with the orthogonal test results about
the catalyst activity. The addition of KF lead to the formation of
KCaF
3
, which enhanced catalytic activity, improved saponication
resistance. Therefore, the catalytical activity of KF/CaO for transe-
sterication was markedly better than that of CaO.
The data from nitrogen adsorptiondesorption isotherms of the
catalyst demonstrated that the catalyst was porous with surface
area of 109 m
2
g
1
. The average pore size was 97 nm, which is con-
sistent with TEM data. The high specic area and large pore are the
major reason for the high catalytic activity of KF/CaO.
3.3. Transesterication of Chinese tallow seed oil catalyzed by KF/CaO
The effect of molar ratio of alcohol to oil on biodiesel yield was
examined under 3% w/w catalyst of oil at 65 C. Fig. 3 showed the
relationship between the molar ratio of alcohol to oil and biodiesel
yield. The biodiesel yield was small in a lower molar ratio of alco-
hol to oil. The equilibrium constant of transesterication is not af-
fected by the alcoholoil molar ratio. However, the biodiesel yield
is affected by it. With the increment in alcoholoil molar ratio, the
reaction conversion rate increased rapidly and reached a higher va-
lue at 12:1 of alcoholoil molar ratio. When the alcoholoil molar
ratio was more than 12:1, the increase of the reaction conversion
rate was not signicant. This experiment demonstrates that the
optimal molar ratio between alcohol and oil is 12:1.
The effect of temperature on biodiesel yield was examined with
3% w/w catalyst and 12:1 alcoholoil molar ratio. Fig. 4 showed
that the conversion rate signicantly increased from 50 C to
65 C. From Fig. 4, it could be seen that the biodiesel yield was in-
creased with the rise of temperature, since the reaction could not
reach equilibrium. However, it was decreased when the tempera-
ture was higher than 65 C. This is mainly because the evaporation
of methanol reduces the contact time between methanol and oil,
resulting in a lower biodiesel yield.
The effect of catalyst usage on the biodiesel yield was studied at
65 C with 12:1 alcoholoil molar ratio. Fig. 5 displayed that when
the usage of solid base catalyst was between 1% and 5% w/w of oil,
the biodiesel yield increased steeply, reaching the peak at 4%. This
suggests that solid base rst neutralized free fatty acids when basic
catalyst was used. When the concentration of free fatty acid rises
up, the consumption of basic catalyst is increased. If the solid base
was not sufcient, catalyst was consumed for neutralization with
no catalytic activity [26]. So the increased usage of basic catalyst
is favorable for the transesterication reaction. The current exper-
iment shows that the optimal usage of the catalyst is 4%.
From the above results, the optimal condition for biodiesel pro-
duction from Chinese tallow seed oil under KF/CaO catalyst is the
Fig. 2. XRD proles of KF/CaO prepared under various temperature.
Fig. 3. Effect of alcoholoil molar ratio on biodiesel yield. (ae) Alcoholoil molar
ratio 6:1, 9:1, 12:1, 15:1, 18:1.
Fig. 4. Effect of reaction temperature on biodiesel yield. (ae) Reaction temperature
50 C, 55 C, 60 C, 65 C, 70 C.
Fig. 5. Effect of catalyst usage on biodiesel yield. (ae) Catalyst usage 1%, 2%, 3%, 4%,
5%.
L. Wen et al. / Fuel 89 (2010) 22672271 2269
molar ratio 12:1 of alcohol to oil, the catalyst 4% w/w of the oil,
reaction temperature 65 C and reaction time 2.5 h.
3.4. Solubility and catalytic mode of the catalyst in the reaction system
Under the optimal conditions, biodiesel was prepared with
either CaO or KF/CaO as catalyst. After removal of the catalyst
CaO or KF/CaO, free Ca
2+
concentration in the biodiesel was ana-
lyzed with atomic absorption spectrometry. The result showed
that the concentrations of dissolved Ca
2+
from KF/CaO and CaO cat-
alysts were 31.6 and 150 mg L
1
, respectively. It indicates that KF/
CaO catalyst is more stable than CaO in the reaction system as a re-
sult of the existence of KCaF
3
crystal phase. The main reason is that
the crystal phase shift occurs with part of KCaF
3
converted into KF
and CaO under high temperature. These results consist with the
previous XRD characterization.
We veried whether the biodiesel production from Chinese tal-
low seed oil was catalyzed homogeneously or heterogeneously.
Under the optimal conditions, the catalyst was rst mixed with
methanol, and stirred for 1 h, and then the catalyst was removed
by ltration. The methanol was then mixed with Chinese tallow
seed oil and reuxed for 1 h. Esterication rate was then measured
with GC, which showed no transesterication reaction under this
paradigm. This result suggests that calcium and other matters dis-
solved in the methanol during the stirring had no catalytic activity.
Therefore, the transesterication from Chinese tallow seed oil and
methanol was catalyzed heterogeneously.
3.5. Stability and anti-acidic ability of catalyst
After the completion of reaction, the reaction mixture was cen-
trifuged and separated to provide catalysts in order to reuse the
catalyst and to investigate the catalyst lifetime and stability. Before
reaction, the same amount of fresh Chinese tallow seed oil and
methanol were added. The results indicate that KF/CaO catalyzed
biodiesel yield was in excess of 91% after 16 cycles (Fig. 6). From
economic point of view, the cost of the catalyst accounts for a large
part of the cost of biodiesel production. Therefore, the stability and
sustained activity of the catalyst are of great importance for indus-
trial applications. Therefore, KF/CaO can contribute much to
decreasing the cost of biodiesel production due to its long catalyst
lifetime and good stability.
The effects of acid values on biodiesel yields were also studied.
Chinese tallow seed oil with different acid value were achieved by
mixing with oleic acid. Biodiesel was produced under the opti-
mized conditions. As shown in Fig. 7, the KF/CaO catalyst had good
anti-acidic ability and could bring about over 80% of biodiesel yield
when the acid values of oil were less than 7 mg KOH g
1
oil. The
KF/CaO catalyst is more acidic tolerant than Ca/Mg catalyst which
requires oil of less than 4 mg KOH g
1
oil to maintain 80% of bio-
diesel yield [26,27]. The above described data indicate that KF/
CaO improved catalytic activity, stability and anti-acidic ability.
3.6. The mechanism of catalysis
The catalyst described here is made up of CaO supported KF. The
superior activity and stability are due to its structure and active
component. On one hand, the impregnation and calcination pro-
cesses have allowed the formation of porous structure with an
average pore size of 97 nm. The large porous catalytic surface in-
creased the contact between alcohol and oil, leading to increase
catalytic effectiveness. On the other hand, the addition of KF has
led to the formation of KCaF
3
active crystal, which is more efcient.
Since uorine has greater electronegativity than oxygen, the Ca
2+
in KCaF
3
is a stronger Lewis acid that has stronger attraction for
CH
3
O

. Simultaneously, F

is a stronger Lewis base with stronger

attraction to H
+
. So, KCaF
3
converts CH
3
OH to CH
3
O

more easily
than does CaO. The surface of the catalyst KF/CaO gathers more
CH
3
O

, which makes it easier to attack carbonyl carbon and leads

further to increase of rate and efciency of transesterication.
Therefore, the KF/CaO with active KCaF
3
has higher catalytic activ-
ity than single CaO. Thus, catalyst KF/CaO is more tolerant to fatty
acid poisoning than that of CaO.
4. Conclusions
The solid base nanocatalyst KF/CaO can be used for biodiesel
production with yield of more than 96%. The catalyst is well used
to convert the oil with higher acid value into biodiesel. It is porous
with particle sizes of 30100 nm. XRD analysis showed the catalyst
has new crystal KCaF
3
, which increase catalytic activity and stabil-
ity. The high specic surface area and large pore size are favorable
for contact between catalyst and substrates, which effectively im-
proved efciency of transesterication. Production of biodiesel
from Chinese tallow seed oil has positive impact on the utilization
of agricultural and forestry products.
Acknowledgments
We acknowledge the support of the National High Technology
Research and Development Program of China (863 Program, No.
2007AA100703) and Hubei Province Natural Science Foundation
(No. 2008CDB040).
Fig. 6. Effect of repeated use of KF/CaO on biodiesel yield. Reaction conditions: the
molar ratio 12:1 of alcohol to oil, the catalyst 4% w/w of the oil, temperature 65 C
and reaction time 2.5 h.
Fig. 7. Biodiesel yield from oil of various acid values. Reaction conditions: the molar
ratio 12:1 of alcohol to oil, the catalyst 4% w/w of the oil, temperature 65 C and
reaction time 2.5 h.
2270 L. Wen et al. / Fuel 89 (2010) 22672271
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