Energy Conversion and Management 114 (2016) 188196

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Energy Conversion and Management

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Review

Activity of the carbon-based heterogeneous acid catalyst derived from

bamboo in esterification of oleic acid with ethanol
Yan Zhou a, Shengli Niu a,, Jing Li b
a
School of Energy and Power Engineering, Shandong University, Jinan, Shandong 250061, China
b
School of Chemistry and Chemical Engineering, Shandong University, Jinan, Shandong 250100, China

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

Article history: Heterogeneous acid catalysts are derived from bamboo through the method of partial carbonization with
Received 10 December 2015 sulfonation in succession and the catalytic activity is validated through the esterification of oleic acid
Accepted 8 February 2016 with ethanol for biodiesel production. Meanwhile, catalysts are characterized by thermogravimetric
(TG), nitrogen adsorption, energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Fourier
transform infrared spectroscopy (FT-IR) and acidbase titration. Under the optimal conditions of car-
Keywords: bonization at 350 C with 2 h duration and sulfonation at 105 C with 2 h duration, the bamboo derived
Biodiesel
catalyst possesses amorphous carbon structure with high sulfur content. It shows considerable heat sta-
Esterification
Heterogeneous acid catalyst
bility below 220 C and gains the total acid amount of 1.74 mmol g
1. This catalyst could supply the
Partial carbonization esterification efficiency of 98.4% for acid value reduction with the molar ratio of ethanol to oleic acid
of 7, heterogeneous acid addition of 6%, esterification temperature of 90 C and esterification time of
2 h. In addition, the reused catalyst could be satisfyingly reactivated with the esterification activity of
93.66% under the same esterification condition.
2016 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
2. Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
2.1. Catalyst preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
2.2. Catalyst characterizations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
2.3. Esterification experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
3.1. Catalyst characterization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
3.2. Catalyst activity factors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 192
3.2.1. Effect of carbonization temperature and time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 192
3.2.2. Effect of sulfonation temperature and time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
3.3. Esterification reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
3.4. Reusability of the catalyst. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
4. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195

1. Introduction

Biodiesel or named as fatty acid alkyl esters (FAAEs) is normally

derived from vegetable oils or animal fats through pyrolysis or
transesterification and possesses the similar physicochemical
Corresponding author. Tel.: +86 531 88392414.
properties, such as cetane value and lubricity, with the fossil diesel.
E-mail address: nsl@sdu.edu.cn (S. Niu).

http://dx.doi.org/10.1016/j.enconman.2016.02.027
0196-8904/ 2016 Elsevier Ltd. All rights reserved.
 Y. Zhou et al. / Energy Conversion and Management 114 (2016) 188196
Currently, the main bottleneck for biodiesel production is the high
cost of feedstock, which normally accounts for 70% of the total
investment in commercial biodiesel production [1]. Usage of the
low-cost feedstocks such as waste cooking oils (WCOs) thus
appears. However, high contents of free fatty acids (FFAs) in WCOs
limit the direct basic catalysis approach and esterification as a
pre-treatment to reduce acid value for the WCOs is thus needed.
Compared to basic catalysts, acid catalysts are not affected by
FFAs in the raw materials, especially sulfuric acid, which is used
to catalyze the esterification reaction because its acid strength is
responsible for the release of more H+ species to protonate the car-
boxylic moiety of the fatty acid [2,3]. Nevertheless, traditional
homogeneous acid catalysts are depressed by some drawbacks
such as undesirable side reactions, corrosion of equipment, and a
great deal of waste water for purification, which arguably con-
tribute to environmental pollution. Therefore, heterogeneous acid
catalysts, gaining the advantages of recovered and reused charac-
teristic and environmental benign property, have been investi-
gated as substitutes for homogeneous acid catalysts. Moreover,
the simultaneous esterification and transesterification (SET) cat-
alyzed by the heterogeneous acid [4] has been proved to be the
most economic outlook and development potential technology
for biodiesel production with low-grade feedstocks, where highly
efficient heterogeneous acid catalysts, including zeolites [5,6],
heteropolyacids [7], cation exchange resins (especially the acidic
ion-exchange resins which are widely used in industrial processes
for different esterification reactions) [8,9], have been explored.
Carbon materials are relatively cheap and widely available.
After easily functionalized with ASO3H groups, the derived
carbon-based heterogeneous acids have been reported as the
promising esterification catalysts for biodiesel production. Hara
et al. [10] prepared the carbon-based heterogeneous acid catalysts
from naphthalene through the in situ partial carbonization and sul-
fonation method. However, their activity was drastically weakened
for the aromatic molecules leaching during liquid-phase reactions.
To overcome this drawback, Toda et al. [1113] obtained the
carbon-based heterogeneous acid catalysts through sulfonation of
incompletely carbonized D-glucose to consolidate the physico-
chemical interaction of the carbon structure and the sulfonic acid
group and the achieved catalyst exhibited high acidic active sites
density and strong catalytic stability in esterification. Additionally,
Malins et al. [35] synthesized the 4-sulfophenyl activated carbon
based solid acid catalyst using diazonium salt and obtained a sim-
ilar catalytic performance for biodiesel production with Amberlyst-
15. Subsequenty, biomass resources, such as wood [1], oilseed cake
[25], oil palm trunk and sugarcane bagasse [27], have been taken as
the carbon precursors for the carbon-based heterogeneous acid
catalysts preparation.
Bamboo, which has been widely cultivated in the west and
south of China, is a biomass material and bears the properties of
rapid growth and abundant production. According to statistics
from the state forestry administration of China, Chinas bamboo
forest area is 6.72 million hectares in 2011, accounting for 21% of
the worlds total [14]. Currently, studies on bamboo properties
are focused on the energy of bamboo pellets [15], hydrolysis of
bamboo biomass [16] and adsorption behavior of bamboo carbon
[17]. Indeed, after treated with carbonization, the bamboo charcoal
possesses the potential as catalyst support for its high specific sur-
face area and large pore volume [18]. However, researches on
carbon-based heterogeneous acid catalyst prepared from bamboo
for biodiesel production have been rarely reported.
On the other hand, methanol is commonly used in esterification
and transesterification for the low price, short carbon chain and
strong polarity. However, methanol is primarily generated through
the pressurized catalytic hydrogenation of carbon monoxide and is
toxic. On the contrary, ethanol is obtained from agricultural
189
products and is renewable and environmentally acceptable [19].
Moreover, ethanol has much superior intersolubility with oils than
methanol and mass transfer limitation between reagents is thus
abated to prompt the esterification or transesterification process.
At the same time, ethyl esters present higher cetane number and
calorific value, and better cold properties such as cold filter plug-
ging point, cloud point and pour point than methyl esters
[20,21]. Due to these advantages, ethanol has recently been payed
more attention for biodiesel production. Richard et al. [22] mod-
eled the kinetics of sunflower oil transesterification with ethanol
in microreactors. Jiang et al. [23] studied the sulfonated cation
exchange resin catalyzed esterification of oleic acid with ethanol
and efficiency of 93% was achieved under the condition of catalyst
loading 20 g, reaction temperature 82 C, ethanol to oleic acid
molar ratio 9:1 and magnetic whisk 600 rpm.
In this work, a series of carbon-based heterogeneous acid cata-
lysts are prepared by partial carbonization of bamboo with sul-
fonation in succession under different conditions through varying
the carbonization temperature (Tc), carbonization time (sc), sul-
fonation temperature (Ts), and sulfonation time (ss), and optimized
through the esterification of oleic acid with ethanol for biodiesel.
Meanwhile, characterization methods of thermogravimetric analy-
sis (TG), nitrogen adsorption analysis, energy dispersive X-ray
spectroscopy (EDX), X-ray diffraction (XRD), Fourier transform
infrared spectroscopy (FT-IR) and acidbase titration are con-
ducted to explain the influence of preparation parameters. Further,
catalytic activity of the bamboo derived heterogeneous acid in
esterification of oleic acid with ethanol is investigated from the
aspects of the catalyst added amount (n, based on the oleic acid
mass), molar ratio of ethanol to oleic acid (c), reaction temperature
(Te) and reaction time (sr). Finally, the reused and reactivated prop-
erty of the heterogeneous acid in catalyzing are also investigated.
2. Experiments
2.1. Catalyst preparation
The carbon-based heterogeneous acid catalyst is prepared
through the method of partial carbonization of bamboo with sul-
fonation in succession. For carbonization, the ground bamboo is
beforehand dried at 105 C. Then it is heated under nitrogen atmo-
sphere with a ramp of 5 C min
1 till to the carbonization temper-
ature, which is distributed between 300 C and 500 C. After kept
at the determined carbonization temperature for a certain
duration, basically from 0.5 h to 4 h, the partially carbonized
bamboo is treated with concentrated sulfuric acid (>98%, Laiyang
Fine Chemical Plant, Shandong, China) with vigorous stirring for
15 h. Finally, the partially carbonized and sulfonated bamboo is
washed with hot distilled water (>80 C) until neutrality and then
dried overnight at 105 C till mass constant.
2.2. Catalyst characterizations
Thermal stability of the catalyst is investigated through thermo-
gravimetric (TG) on a Mettler Toledo TGA/SDTA 851e thermogravi-
metric analyzer (with an accuracy of 0.1 lg), Switzerland. During
TG, the initial sample is weighted to 10 0.1 mg and heated from
25 C to 900 C at the linear rate of 10 C min
1, where nitrogen
(with the purity of 99.999%) is used as both the protection gas
(30 mL min
1) and reaction gas (120 mL min
1).
Crystalline phase of the catalyst is analyzed by X-ray diffraction
(XRD) on a Bruker Advanced D8 X-ray diffraction analyzer,
Germany, which uses Cu Ka radiation source with the voltage of
40 kV, electricity of 100 mA, scanning range from 10 to 90,
scanning speed of 4 min
1 and scanning step size of 0.02.
190 Y. Zhou et al. / Energy Conversion and Management 114 (2016) 188196
Functional group of the catalyst is tested by attenuated total
reflectance-Fourier transform infrared spectroscopy (ATR-FTIR)
on a Bruker VERTEX 70 FTIR spectrometer, Germany, with the res-
olution of 4 cm
1 and scanning range from 600 cm
1 to 4500 cm
1.
Microstructure parameters of the esterification catalyst are
measured through nitrogen adsorption and desorption instrument,
Micromeritics ASAP 2020, USA. After the catalyst is desorbed under
vacuum at 150 C, the parameters are isothermally measured at

196 C using nitrogen as the adsorbed substance. Then, surface
area and average particle size with pore area distribution are calcu-
lated by BrunauerEmmettTeller (BET) equation and BarrettJoy-
nerHalenda (BJH) model, respectively.
Energy dispersive X-ray spectroscopy (EDX) for ultimate analy-
sis is carried out using an elemental analyzer through Vario EL
CUBE apparatus, ELEMENTAR, AR, Germany. The accuracy is 0.3%
and the oxygen mass fraction is calculated by difference.
Total acid density of the catalyst is measured by the acidbase
titration method [24]. About 0.05 g catalyst is mixed with 15 mL
NaCl solution (2 mol L
1) under ultrasonic vibration to be equili-
brated. After filtration, the filtrate with phenolphthalein solution
is titrated with NaOH solution (0.01 mol L
1) to be neutral.
2.3. Esterification experiments
Activities of the bamboo derived heterogeneous acids are tested
through the esterification of oleic acid with ethanol in a batch-type
experimental system [25], where a three-necked flask reactor is fit-
ted with a coiled condenser for ethanol reflux, a mechanical stirrer
to prompt mass transfer among the reagents and a water bath to
guarantee the reaction temperature. Oleic acid (Kermel Chemical
Reagent Co., Ltd., Tianjing, China), ethanol (Fuyu Chemical Co.,
Ltd., Tianjing, China) and catalyst are sequentially poured into
the reactor at the preseted temperature and the mixtures are then
vigorously agitated throughout the esterification process. As termi-
nation, the heterogeneous catalyst is mechanically separated from
the liquids products through vacuum filtration and the excess
ethanol and by-produced water are successionally removed
through vacuum distillation. Then, activities of the prepared cata-
lysts are labeled by the efficiency of acid value reduction during
the esterification of oleic acid with ethanol, as shown in Eq. (1).
Ain
Aout
g  100%
Ain
where Ain and Aout are acid values of the original and the esterified
oleic acid, respectively, mg KOH g
1, and tested according to GB/T
5530-2005.
Table 1
Ultimate analysis and microstructure parameters of bamboo based heterogeneous acid.
Samples Mass fraction (%)
C H O N
S1 48.88 6.121 44.691
S2 72.82 4.242 22.426
S3 59.35 3.283 31.077
S4 62.53 3.596 29.449
S5 62.80 3.616 29.174
S1: original bamboo.
S2: partially carbonized bamboo.
S3: bamboo derived catalyst.
S4: bamboo derived catalyst after first usage.
S5: bamboo derived catalyst recovered from the reaction with ethanol.
3. Results and discussion
3.1. Catalyst characterization
Ultimate analysis of the samples reveal the presence of carbon,
hydrogen, oxygen, nitrogen and sulfur in the bamboo based
heterogeneous acid, as showed in Table 1. Obviously, compared
with the original bamboo, contents of both hydrogen and oxygen
are decreased after carbonization, while the carbon content is
enhanced greatly for the dehydration and decomposition during
carbonization. After sulfonation, contents of oxygen and sulfur
are increased promptly for the introduction of ASO3H groups,
where ACOOH groups are subsequently formed. In addition,
hydrogen content is decreased, which is also obtained by Jiang
et al. [29].
Microstructure parameters of the unsulfonated and sulfonated
carbon-based catalysts are given in Table 1. The BET surface area
decreases from 2.71 m2 g
1 to 0.25 m2 g
1, where the pore volume
and average pore diameter are too small to be measured. It is indi-
cated that sulfonation obviously changes the textural of carbon
material for the introduced ASO3H groups on the surface of pore
channels, where structural destruction and collapse is accompa-
nied. In addition, extremely small void volume of the catalyst indi-
cates that the acid sites are primarily located on the surface. And
acid densities are too high to be attributed to ASO3H groups
attached to the small carbon surface areas, suggesting that ASO3H
groups in the amorphous carbon bulk takes part in the acid cat-
alyzed reactions.
Fig. 1a presents FTIR spectra of the partial carbonized bamboo
at different temperatures. Bands at 3342 cm
1 and 2885 cm
1 for
the original bamboo are assigned to OAH stretching and CAH
stretching vibration, respectively [26]. Meanwhile, bands at
1731 cm
1 (for the C@O carboxylic stretching vibration), at
1602 cm
1 and 1506 cm
1 (for C@C aromatic stretching vibration),
and at 1232 cm
1 and 1029 cm
1 (respective for CAOAC vibration
and CAOAH vibration) reflect the cellulose, hemicellulose and lig-
nin structures in the original bamboo [27,28]. After carbonization,
significant structure changes are observed according to the FTIR
spectra, where all the stretching vibration functional groups, like
OAH (3342 cm
1), CAH (2885 cm
1), C@O (1731 cm
1), CAOAC
(1232 cm
1) and CAOAH (1029 cm
1), gradually disappear with
carbonation temperature increasing. It is indicated that the molec-
ular structures of cellulose, hemicellulose and lignin in the original
1 bamboo are suffered from dehydration for the crack of the ether,
hydroxyl and carboxyl bonds. Moreover, C@C stretching vibration
band in the aromatic ring mode (1602 cm
1) is enhanced obviously
at 350 C, which labels the significant partial carbonization of bam-
boo and favors sulfonation [28]. The partial carbonized bamboo,
SBET (m2 g
1) VP (cm3 g
1) DP (nm)
S
0.11 0.188
0.25 0.236 2.71 0.0018 32.78
0.21 6.069 0.25
0.20 4.217
0.21 4.192
 Y. Zhou et al. / Energy Conversion and Management 114 (2016) 188196 191

(a) (b)
o
500 C o
135 C
o
450 C
o
o 120 C
400 C
o o
350 C 105 C
o
300 C
o
bamboo 90 C

75 oC

4500 4000 3500 3000 2500 2000 1500 1000 4500 4000 3500 3000 2500 2000 1500 1000
Wavenumber/cm -1 Wavenumber/cm-1

Fig. 1. FTIR spectra for bamboo after partial carbonization and sulfonation. (a) Partial carbonization; (b) sulfonation.

100 bamboo (a) (b)

the bamboo derived
catalyst
80
bamboo
mass percentage/%

60
partially carbonized bamboo
40

20 the bamboo derived catalyst

0 200 400 600 800 1000 10 20 30 40 50 60 70 80 90

o o
temperature/ C 2 /

Fig. 2. TG curves and XRD patterns of the bamboo based heterogeneous acid. (a) TG curves; (b) XRD patterns.

which is performed at 350 C for the distinct C@C stretching vibra-
tion band as described above, is further sulfonated and FTIR spectra
of the thus achieved catalyst are presented in Fig. 1b. It is seen that
the C@O stretching vibration band at 1695 cm
1 gets strength after
sulfonation which implies the CAOAH or HAC@O groups are par-
tially oxidized into carboxylic groups [29]. Meanwhile, bands at
1155 cm
1 (for ASO3H) and 1033 cm
1 (for S@O), which represent
the sulfonic acid group stretching modes, also confirm incorpora-
tion of the sulfonic acid group into the carbonized materials and
validate the effective substitution of hydrogen by sulfuric acid rad-
ical on the benzene ring for the carbon-based heterogeneous acid
catalyst preparation [2830].
As shown in Fig. 2a, TG curve for the original bamboo is divided
into three stages. The first stage from the initial temperature to
240 C involves evaporation of the free water and physical
adsorbed water, where the TG curve is basically kept flat. Mass loss
of the second stage from 240 C to 400 C is 61.57% and is mainly
attributed to the thermal decomposition of hemicellulose, cellu-
lose and partial lignin [31] for the rupture of the chemical bonds,
like HAO, CAH, CAOAC, etc. Thus, the relative stable polycyclic
mesh aromatic structure forms for the thermal polycondensation
reaction [32]. Mass loss of the third stage, which is from 400 C
to 900 C, becomes slow, for the further decomposition of oxygenic
groups and the more stable carbon network compounds are
formed [32]. TG curve for the bamboo-derived heterogeneous acid
catalyst shown in Fig. 2a is evidently shifted toward the higher
temperature zone if compared with the original bamboo. Mass loss
of 5.57% from the initial temperature to 100 C is attributed to loss
of the adsorbed moisture [33]. In succession, the curve is basically
kept as plateaus in 100220 C and a rapid mass loss is then
observed from 220 C to 510 C. This result confirms that the
carbon-based heterogeneous acid catalyst derived from bamboo
exhibits satisfying thermal stability under esterification condition,
especially below 100 C.
Fig. 2b shows XRD patterns of the original bamboo and its
derived catalyst. Peaks at 2h = 15.7 and 21.6 in the original bam-
boo for the crystalline structure of cellulose disappear in the car-
bonated and sulfated bamboos to imply the destructive effect of
carbonization and sulfonation on the physical and chemical struc-
tures of bamboo. The broad diffraction peak from 10 to 30 and
weak diffraction peak from 35 to 50 for the carbonated bamboo
are assigned to the randomly arranged amorphous carbon struc-
tures containing low content of crystalline graphite [34,35]. After
sulfonation, the broad diffraction peak turns lower and is shifted
toward the right side, meaning the further conversion of carbon
structure to be amorphous under effect of the supported sulfuric
acid and favoring in esterification [29].
Normally, the larger amount of the surface acid means the
stronger activity of catalysts. Total acid amounts of the bamboo-
derived heterogeneous acid catalysts prepared at different condi-
tions are presented in Table 2. At low temperature, decomposition
of the cellulose and hemicellulose in the original bamboo is incom-
pleted and formation of the polycyclic aromatic hydrocarbon is
thus suppressed, which is not conducive to load the sulfonic acid
192 Y. Zhou et al. / Energy Conversion and Management 114 (2016) 188196

Table 2
Total acid amount of catalyst affected by carbonization and sulfonation conditions.

Samples Acid amount (mmol g
1) Samples Acid amount (mmol g
1)
a c
Tc (C) 300 1.04 Ts (C) 75 1.50
350 1.62 90 1.62
400 1.32 105 1.74
450 0.75 120 1.29
500 0.59 135 0.83
sc (h)b 0.5 1.56 ss (h)d 1 1.24
1 1.63 2 1.74
2 1.74 3 1.72
3 1.72 4 1.71
4 1.73 5 1.72
a
Preparation conditions: sc = 2 h, Ts = 90 C, ss = 3 h.
b
Preparation conditions: Tc = 350 C, Ts = 90 C, ss = 3 h.
c
Preparation conditions: Tc = 350 C, sc = 2 h, ss = 3 h.
d
Preparation conditions: Tc = 350 C, sc = 2 h, Ts = 105 C.

group. On the contrary, the mesh structure would be enlarged to
depress activity of the sulfonic acid if the carbonization tempera-
ture is too high. As a result, the total acid amount decreases for
the carbonization temperatures higher than 350 C.
Influence of the carbonization time is different from the one of
carbonization temperature. As listed in Table 2, the total acid
amount exhibits an increasing trend from the carbonization time
of 0.5 h and gets a maximum at sc = 2 h. Further prolonging of car-
bonization time had no significant influence on the total acid
amount, which means that combination of the stable structure of
polycyclic aromatic hydrocarbons with the sulfonic acid group
could be obtained for 2 h, and further increase of heating time
has no effect on it. Meanwhile, this result is similar with the effect
of sulfonation time.
Meanwhile, sulfonation reaction is weak and load capacity of
the carbonized product for sulfonic acid group is suppressed. Thus,
the total acid amount is increased quickly with the sulfonation
temperature rising, and achieved the maximum at 105 C. Then it
decreased rapidly with the temperature increase due to the multi
sulfonated and sulfone side reaction.
3.2. Catalyst activity factors
3.2.1. Effect of carbonization temperature and time
Carbonization temperature is an important factor affecting the
catalyst activity. With carbonization temperature increasing,
hemicellulose, cellulose and lignin of bamboo gradually pyrolysis
so multiple polycyclic aromatic hydrocarbons mesh skeleton struc-
ture of benzene ring are formed through the dehydration conden-
sation reaction. The skeleton structure formed in that way is
favorable in loading the sulfonic acid groups. However, too high
temperature would expand the reticular structure and increase
carbon content in the carbonization products with the reduced
the active sites of the sulfonic acid groups. Hence, a suitable car-
bonization temperature is conducive to the sulfonation reaction.
Fig. 3a exhibits impact of the carbonization temperature for the
bamboo derived heterogeneous acid in catalyzing esterification
and the catalysts carbonized in the temperature of 300400 C per-
form acceptable catalytic capability with the maximum esterifica-
tion efficiency of 97.44% at 350 C. Then, acid reduction rate is
rapidly dropped with carbonization temperature further increased,
which is consistent with variation trend of the surface acid amount
listed in Table 2.
Although carbonization time also influences formation the of
carbon skeleton thereby affecting the load capacity for the sulfonic
acid groups, rare studies about this aspect have been reported. As
presented in Fig. 3b, esterification efficiency continuously
increases up to 2 h, and remains almost constant with prolonging
carbonization time, which is in agreement with the results pre-
sented in Table 2. It is indicated that when the carbonization time
is short, carbonization degree is low and the polycyclic aromatic
hydrocarbons structure is not fully formed, which is not benefit
for sulfonation. With carbonization time increasing, the formation
of polycyclic aromatic hydrocarbons structure gradually com-

100 98.5
(a) (b)

90 98.0
o
Tc=350 C
o
%

o
%

80 Ts=90 C Ts=90 C
97.5
=9 =9
=10% =10%
o o
70 Te=90 C 97.0 Te=90 C
=2h =2h

60 96.5
300 350 400 450 500 0 1 2 3 4
o
Tc / C c /h

Fig. 3. Effect of carbonization conditions on catalytic activity of the bamboo derived heterogeneous acid in esterification. (a) Carbonization temperature; (b) carbonization
time.
 Y. Zhou et al. / Energy Conversion and Management 114 (2016) 188196
98 (a)
96
Tc=350 C
o 96
94
%
=9
=10%
92 o 94
Te=90 C
=2h
90
88
75 90 105
o
Ts / C
Fig. 4. Effect of sulfonation conditions on catalytic activity of the bamboo derived heterogeneous acid in esterification. (a) Sulfonation temperature; (b) sulfonation time.
pletes. Thus further increase beyond the appropriate time shows
no significance on the catalytic esterification efficiency because
the variation of molecular structure is not distinct.
3.2.2. Effect of sulfonation temperature and time
Sulfonation temperature influences leading of the sulfonic acid
group into the carbon based structure and the subsequent activity
and stability of the thus derived heterogeneous acid in catalyzing
esterification. The restricted sulfonation reaction leads low con-
nected number of sulfonic acid group and the thus generated sul-
fonated products is not stable, which performs weak catalytic
activity and is easily to be decomposed. On the other side, exces-
sive sulfonation temperature might bring negative side effects of
multi sulfonated and sulfone, which also decreases the introduc-
tion of sulfonic acid groups and reduces the catalyst activity, sub-
sequently. As a result shown in Fig. 4a, the catalyzed esterification
of oleic acid with ethanol could be strengthened through heighten-
ing the sulfonation temperature from 75 C to 105 C, where the
maximum efficiency of 98.05% could be achieved. And a further
increment in sulfonation temperature would suppress the catalytic
capability with an reduced esterification efficiency.
Sulfonation reaction, a process of introducing ASO3H groups
into carbon materials with chemical bond to concentrate sulfonic
acid, needs a certain reaction time. As explored in Fig. 4b, esterifi-
cation efficiency from 92.01% to 98.40% is obtained with the incre-
ment of sulfonation time for catalyst preparation from 1 h to 2 h.
Further prolonging sulfonation time to 3 h, 4 h and 5 h, respec-
tively, esterification efficiency catalyzed by thus derived heteroge-
neous acid varies indistinctly. It is indicated the sulfonation
process for introducing the ASO3H groups into the partial carbon-
ated bamboo is relatively fast and could be completed within 2 h
which is superior to the 6 h sulfonation duration for the oil palm
trunk and sugarcane bagasse derived heterogeneous acid prepara-
tion [30].
The catalyst prepared at optimal sulfonation conditions pos-
sesses high sulfur content (approximate 6%), that the high ASO3H
density which is estimated from the sulfur content is investigated
(1.82 mmol g
1). These results show the effective utilization of
concentrated sulfuric acid and validates the efficiency and econ-
omy of sulfonation process which is superior to many other
carbon-based catalysts [28,30].
3.3. Esterification reaction
A detailed study about the influence of the catalyst added
amount in catalyzing esterification is made as depicted in Fig. 5a.
It can be observed that the non-catalyzed esterification is very
193
(b)
98
Tc=350 oC
Ts=105 oC
%
=9
=10%
Te=90 oC
=2h
92
120 135 1 2 3 4 5
s /h
slow, while catalyst could strongly prompt the esterification of
oleic acid with ethanol. Thus, efficiency of 98.34% for acid reduc-
tion through esterification could be achieved with the added cata-
lyst amount of 6 wt.%. However, further heightening the catalyst
added amount to 10 wt.% makes no distinct increment in esterifi-
cation efficiency. Heterogeneous acid catalyst is validated in pro-
moting esterification through providing strong acid sites, so
increasing catalyst added amount will drive esterification toward
the products. However, excess catalysts would lead to a mixing
problem among reactants, products and catalyst, which has an
impact on the mass transfer between the catalyst and reactants.
Therefore, 6 wt.% is chosen as the optimum catalyst added amount
which is comparable to 1 wt.% sulfuric acid used as control and
superior to 20 wt.% sulfonation of oilseed cake used [26].
Esterification is reversible and the required molar ratio of etha-
nol to oleic acid should be bigger than the theoretical value of 1 to
prompt the forward reaction. As shown in Fig. 5b, with the molar
ratio of ethanol to oleic acid increased from 3 to 5, esterification
efficiency is obtained from 86.46% to 97.71%. As the molar ratio
exceeds 7, where efficiency of 98.39% is supplied, no significant
improvement in acid reducing rate is observed and may be
ascribed to the phase equilibrium. Due to the hydrophilia of cata-
lyst and the miscibility of ethanol and oleic acid, increasing ethanol
is benefit for the distribution of catalyst and the flow profile of liq-
uid phase. However, too large excess ethanol would dilute the
reaction system thereby reducing the frequence of cillision or even
shield palmitic acid molecules from the catalyst active sites [28].
Similar observation were reported by Jiang et al. [23] and Yin
et al. [36] which obtained the optimal molar ratio of ethanol to
oleic acid at 9 and 8.8, respectively.
Raising reaction temperature could drive the equilibrium
toward the products due to the endothermic property of esterifica-
tion, and promote the diffusion of bamboo derived catalyst into the
liquid mixtures rapidly. As shown in Fig. 5c, when reaction temper-
ature is increased from 75 C to 90 C, esterification efficiency rises
quickly and attains the peak value of 98.4% at 90 C. Yet, the acid
reduced rate decreases a little at 95 C. Increasing temperature
could strengthen molecule motion and mass transfer to induce
the high acid reducing rate [23]. Meanwhile, water generated dur-
ing esterification could also be evaporated at high temperature to
be favor for the positive going esterification. However, excessive
high temperature would aggravate the ethanol evaporation,
though the esterification experimental system is fitted with a
coiled condenser for ethanol reflux. Therefore, the optimum reac-
tion temperature in this work is considered to be 90 C.
Esterification of oleic acid with ethanol catalyzed by the
bamboo derived heterogeneous acid occurs in a liquidliquidsolid
194 Y. Zhou et al. / Energy Conversion and Management 114 (2016) 188196

100
(a) 99 (b)

96
80
=9 =6%
Te =90 oC 93 Te =90oC
/%

60
=2h =2h
90
40

87
20

0 2 4 6 8 10 2 4 6 8 10 12

100 100
(c) (d)
96 96

=7 =7
=6%
/%

/%
92 92 =6%
=2h Te=90 oC

88 88

84 84
75 80 85 90 95 1 2 3 4 5
o
Te/ C h

Fig. 5. Influence of esterification parameters on catalytic capability of the bamboo derived heterogeneous acids (a) catalyst added amount (n); (b) molar ratio of ethanol to
oleic acid (c); (c) esterification temperature (Te); (d) esterification time (se).

system, where a certain time duration is required to guarantee
both the sufficient mass transfer among the liquid mixtures and
the solid catalyst and the thorough chemical reaction of esterifica-
tion on the catalyst surface. Thus, influence of esterification dura-
tion on acid reduced rate is investigated. As presented in Fig. 5d,
under the catalytic effect of the bamboo derived heterogeneous
acid, esterification of oleic acid with ethanol could be consolidated
through prolonging the reaction time within 2 h, where esterifica-
tion efficiency of 98.4% could be achieved. However, esterification
is reversible and promotion in esterification through further pro-
longing reaction time is weakened for the equilibrium limitation.
This result is more advantage than the catalysts prepared from oil-
seed cake [26], oil palm trunk and sugarcane bagasse [30].
The high catalytic activity cannot be explained simply by the
high density of strongly acidic ASO3H groups and good access of
reactants to the ASO3H groups in the carbon material [37]. It is
reported that in addition to the high density of acidic ASO3H
groups, the hydrophilic ACOOH and AOH groups in the carbon cat-
alyst also played an important role in promoting the activity of the
catalyst [38]. One possible explanation for the high catalytic activ-
ity of the heterogeneous acid carbon catalyst may be the strong
affinity between the hydrophilic parts of the reactants and the
almost neutral AOH groups bonded to the polycyclic aromatic car-
bon rings [37].
3.4. Reusability of the catalyst
Biodiesel of ethyl oleate is produced through esterification of
oleic acid with ethanol, where water is also by produced. In succes-
sion, the generated water would exacerbate the reversible reaction
and deactivate the heterogeneous acid catalysts [39]. Therefore,
catalyst with strong stability in the presence of water produced
during esterification is desirable. To investigate the catalyst
reusability, esterification is conducted with 5 cycles under the
same optimum conditions. After each run, the catalyst is separated
from the liquid products through vacumm filtration and then
washed by ethanol. After dried in oven at 105 C overnight, catalyst
is reused for the next run. As shown in Fig. 6a, esterification effi-
ciency is drastically decreased from 98.4% for the first usage to
83.42% for the second usage. Finally, efficiency is decreased to
27.84% for the fifth usage to illustrate poor reusability of the bam-
boo derived heterogeneous acid. Meanwhile, total acid amounts of
the reused catalysts are also measured, which presents remarkably
higher decrease than esterification efficiency, as shown in Fig. 6a.
Thus, the sulfur content of recycled catalysts is determined by ulti-
mate analysis to assess the stability of the ASO3H acid sites, which
can be seen in Table 1. The results show a decrease in sulfur con-
tent from 6.069% to 4.217% after the first cycle of reuse, which is
not in line with the result of total acid amount. The decrease in sul-
fur content observed here showes that the route of deactivation is
through leaching of the ASO3H bearing small polycyclic com-
pounds and/or formation of sulfonate esters, similar behavior
was observed by Fraile et al. [40].
Further study on the deactivation of catalyst is explored by FTIR
spectra before each run in Fig. 6b. Bands at 1155 cm
1 (for ASO3H)
and 1033 cm
1 (for S@O) gradually become weakened implying the
loss of sulfonic acid groups during each reaction. Beside, band at
1695 cm
1 (for ACOOH) gradually gets strength that should favor
the dispersion of catalysts. The change of the functional groups
illustrate the variation of esterification efficiency to some extent.
 Y. Zhou et al. / Energy Conversion and Management 114 (2016) 188196
(a)
90 acid reducing rate
acid amount
75
60 =7
=6%
45 Te=90 oC
=2h
30
1 2 3 4 5 4500
reused times
Fig. 6. Reusability of catalyst in esterification (a) acid reducing rate and total acid amount; (b) FTIR spectra.
As previous reports showed, the leaching of ASO3H groups from
catalyst occurred due to the good solubility of catalyst in polar
reaction mixture [41]. Hence, fresh sulfonated carbon catalyst with
ethanol vigorously stirring at 90 C for 2 h has been undertaken.
After separation by vacuum filtration and drying, this catalyst is
used for the esterification of oleic acid with fresh ethanol. The
esterification efficiency is 4% lower than this for the fresh catalyst.
In addition, the sulfur content of this catalyst is measured by EDX
in Table 1, the weight loss is similar with the first reused catalyst,
indicating the leaching of ASO3H groups from carbon-based cata-
lyst is mainly due to the ethanol. To examine whether formation
of sulfuric acid takes place in reaction, ethanol and water filtrated
after the first run is submitted to a test of sulfates with barium
chloride. The result is negative, indicating that free sulfonic acid
groups is not present in the solution in the form of sulfuric acid
although the esterification with this mixture has good efficiency.
Nevertheless, the fifth reused catalyst can be easily regenerated
by sulfonation again, where the total acid amount of
1.31 mmol g
1 and the esterification efficiency of 93.66% can be
reached.
4. Conclusions
The carbon-based heterogeneous acid catalyst derived from
bamboo is prepared through partial carbonization followed by sul-
fonation with concentrated sulfuric acid. After carbonization at
350 C with 2 h duration, the bamboo derived product possesses
amorphous carbon structure and subsequently achieves the total
acid amount up to 1.74 mmol g
1 after introducing sulfonic acid
groups by sulfonation at 105 C with 2 h duration. Moreover, the
catalyst exhibits a good thermal stability below 220 C. Under
the optimize conditions of n = 6 wt.%, c = 7, Te = 90 C and s = 2 h,
the carbon-based heterogeneous acid catalyst catalyzed esterifica-
tion of oleic acid with ethanol could achieve an efficiency of 98.4%.
The reusability of catalyst is tested by consecutive batch experi-
ments and the esterification efficiency decreases from 98.4% to
27.84% after five runs for the loss of the acid sites. Even so, the cat-
alytic activity could be reactivated by sulfonation at 105 C with
2 h duration, where esterification efficiency of 93.66% is achieved.
Acknowledgements
This work is supported by the National Natural Science Founda-
tion of China (51206098), the Young Scholars Program of Shandong
195
1.8
(b)
1.5
regeneration
Acid amount/mmol g-1
1.2 4th usage
3rd usage
0.9
2nd usage
1st usage
0.6
no usage
0.3
4000 3500 3000 2500 2000 1500 1000
Wavenumber/cm-1
University (YSPSDU, 2015WLJH33) and the Fundamental Research
Funds of Shandong University (2015JC024).
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