Microporous and Mesoporous Materials 219 (2016) 54e58

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Microporous and Mesoporous Materials

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

Synthesis porous carbon-based solid acid from rice husk for

esterification of fatty acids
Danlin Zeng*, Qi Zhang, Shiyuan Chen, Shenglan Liu, Guanghui Wang
The State Key Laboratory of Refractories and Metallurgy, Hubei Key Laboratory of Coal Conversion and New Carbon Material, College of Chemical
Engineering and Technology, Wuhan University of Science and Technology, Wuhan 430081, China

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

Article history: A porous carbon solid acid was synthesized from biomass rice husk by incompletely carbonization, so-
Received 5 May 2015 dium hydroxide leaching and concentrated H2SO4 sulfonation. The solid acid was characterized by XRD,
Received in revised form FT-IR, N2 adsorption-desorption and solid-state NMR spectroscopy. The characterization results reveal
16 July 2015
that the carbon solid acid shows ultra high surface area of 1233 m2/g and stronger acid strength than that
Accepted 26 July 2015
Available online 31 July 2015
of HZSM-5(Si/Al ¼ 38) zeolite. The catalytic performance was tested by the esterification of oleic acid
with methanol. The results indicate that this solid acid catalyst is an excellent catalyst compared with
other conventional solid acid.
Keywords:
Solid acid
© 2015 Elsevier Inc. All rights reserved.
Rice husk
Acidity
Esterification

1. Introduction [5,9,10]. However, such materials were nonporous and exhibited

Currently industrial esterification processes are carried out by
the catalysis of homogeneous Brønsted acids such as sulfuric acid.
However, these homogeneous acid catalysts are difficult to be
separated, and also cause serious environmental and corrosion
problems. Recently, the application of solid catalysts instead of
homogeneous liquid catalysts has been paid much attention in
view of their convenience of separation and lack of corrosion or
toxicity problems [1e5].
Due to the low densities of effective acid sites, inorganic-oxide
solid acids such as zeolite or composite oxide cannot satisfy
adequate requirement in esterification reactions [6,7]. Although
strong acidic ion-exchange resins such as Nafion contain abundant
sulfonic acid groups (eSO3H), that function as strong acid sites,
their catalytic activities are generally much lower for their very low
surface area [8]. These limitations have restricted the practical
utility of acidic cation-exchangeable resins. Recently, a new type of
sulfonated carbons derived from incomplete carbonization of
simple natural product such as sugar, starch or cellulose, has been
reported to show better catalytic performance for esterification of
fatty acids, and higher stability than sulfonated mesoporous silica
low surface area, which may limit the accessibility to the active
sites. The carbon solid acid with unique porous properties is syn-
thesized here as an ideal candidate for the development of the high
active catalyst.
Every year three million tons of rice husk (RH) are produced in
China. So far, such a resource is mainly considered as a waste, and
consequently burnt without any profit, except in a few cases of
domestic uses for cooking and heating [11]. The main objective of
the present work was to prepare carbon based solid acid from rice
husk by incomplete carbonization, leaching and sulfonation. The
solid acid catalyst was also characterized by X-ray diffraction (XRD),
Fourier-transform infrared spectra (FT-IR), scan electron micro-
scope (SEM) and solid state nuclear magnetic resonance (NMR)
spectroscopy. The research results will be helpful to obtain the
fundamental information of the roles of surface functional groups
in the solid acid, which is crucial in the design of a novel carbon-
based solid acid for industrial application.
2. Experimental
2.1. Sample preparation

Rice husk from a grain depot in Wuhan was used as raw mate-
* Corresponding author. Tel./fax: þ86 27 6886 2181. rial. Rice husk was calcined at 450  C for 15 h under a N2 flow, and
E-mail address: zdanly@163.com (D. Zeng). then followed by grinding and leaching with 1 M NaOH at 100  C K

http://dx.doi.org/10.1016/j.micromeso.2015.07.028
1387-1811/© 2015 Elsevier Inc. All rights reserved.
 D. Zeng et al. / Microporous and Mesoporous Materials 219 (2016) 54e58 55

for 5 h at the ratio of solid to liquid of 1 g: 10 ml to remove silica in

the rice husk. After carefully washing with deionized water, the
dried rice husk carbon was sulfonated with concentrated H2SO4
(98wt%), at 150  C under a N2 flow for 8 h at the ratio of solid to
liquid of 1 g: 10 ml. At last, the mixture was diluted with deionized
water, filtered, washed thoroughly, and dried at 120  C for 12 h to
obtain the carbon solid acid catalyst.
The elemental analysis of the rice husk is listed in Table 1.
Recycling experiments were performed to determine the cata-
lytic stability of the solid acid catalysts. At the end of each esteri-
fication cycle, the catalyst was centrifuged, washed with ethanol
and dried at 105  C for 2 h before reusing.

2.2. Sample characterization

The concentration of acid sites on the catalysts was determined

by titration method in aqueous solution. One gram of the sample
was placed in 50 ml of 0.05 M NaOH solution. The vials were sealed
and shaken for 24 h and then 5 ml of the filtrate was pipetted and
the excess of base was titrated with HCl. The numbers of acidic sites
were calculated from the amount of NaOH that reacted with the
catalyst.
Surface area and porosity properties of samples were evaluated
by N2 adsorption/desorption isotherms carried out on a Micro-
meritics ASAP 2020 sorption analyzer. Prior to the adsorp-
tionedesorption measurements, all the samples were degassed at
150  C in N2 flow for 12 h.
X-ray diffraction (XRD) was performed with a Philips X'PERT-
Pro-MPD diffractometer, operating with Cu Ka radiation (40 kV,
30 mA) and Ni filter.
All the NMR experiments were carried out at 9.4 T on a Varian
Infinityplus-400 spectrometer with resonance frequencies of
400.12, 100.4 MHz for 1H, 13C, respectively. The 90 pulse widths for
H, 13C were measured to be 3.7, 4.4 ms, respectively. The chemical
1
Fig. 1. XRD patterns of (a) rice husk; (b) rice husk carbon and (c) the carbon solid acid.
2q ¼ 25 is corresponded to the diffraction of C (002) [13].
Compared with that of rice husk, the peak of the impurities
(2q ¼ 18 , silica) was disappeared in the spectrum of rice husk
carbon and the solid acid. According to Dahn's conclusion [14], it
indicates that the solid acid and rice husk carbon consist of a single
layer of polyhexagonal carbon atoms after leaching, implying that
the BET surface area of the solid acid may be dramatically high.
FT-IR spectroscopy was employed to explore the changes in
functional groups induced by preparation process. It shows that the
difference of the spectroscopy is mainly the bands of oxygen
functionalities in the samples (Fig. 2). Two bands at 1039 and
1182 cm1 in the solid acid can be assigned to the SO2 asymmetric

shifts were referenced to tetramethylsilane (TMS) for 1H, to hex- and symmetric stretching modes, respectively [5]. It indicates that
amethylbenzene (HMB) for 13C, respectively. The magic angle sulfonic acid group was found on the surface of the sulfonated solid
spinning rate was 5 kHz. acid. The band at 1700 cm1 can be attributed to the C]O
For the adsorption of probe molecules 2-13C-acetone, the sam- stretching mode of the eCOOH groups, while the broad band
ples were kept at 400  C under the vacuum less than 1  103 Pa for centered at 3429 cm1 was assigned to the eOH stretching mode
at least 8 h. The adsorption of 2-13C-acetone was performed at [5]. The band at 1647 cm1 can be attributed to the C]C stretching
room temperature with a loading of ca. 0.1 mmol per gram catalyst. mode of the samples. Therefore, eCOOH, eSO3H and eOH were
The various solid acids were employed as catalysts for the found as the functional groups on the solid acid.
esterification of oleic acid with methanol. The SO2
4 /ZrO2 catalyst in
this case was prepared using the classic two-step method [12]. The
HZSM-5 zeolite (Si/Al ¼ 38) and Nafion NR 50 were pursed from
Shanghai Guoyao Corporation. Prior to the reaction, all the catalysts
were dried at 120  C for 5 h. The experiments were carried out by
mixing oleic acid with methanol in a flask equipped with a reflux
condenser, an oil bath and a magnetic stirrer. Once the mixture had
reached the reaction temperature, the catalyst was added. The
mixtures were withdrawn and centrifuged to separate the solution
from the catalyst. Analysis of the reaction mixtures was carried out
in an HP 6890 series gas chromatograph equipped with a flame
ionization detector (FID).

3. Results and discussion

Fig. 1 illustrates the XRD patterns of rice husk, rice husk carbon
and the carbon solid acid. The diffraction peak arising at around

Table 1
Element analysis of rice husk (wt%).

Sample C H O N S

Rice husk 88.15 5.20 3.55 1.84 1.26

Fig. 2. FT-IR spectra of (a) rice husk, (b) rice husk carbon and (c) the carbon solid acid.
56 D. Zeng et al. / Microporous and Mesoporous Materials 219 (2016) 54e58

Fig. 3 shows the 13C CP/MAS NMR spectra of rice husk carbon
and the solid acid. The peaks at 128 and 153 ppm are due to
polycyclic aromatic carbon atoms and aromatic carbon bonded to
phenolic OH, respectively [15]. Compared with the spectra of rice
husk carbon, the signals at 139 ppm (due to aromatic carbon
bonded to the SO3H group, CeSO3H) can be clearly observed in the
samples after sulfonation [16]. In addition, the existence of SO3H
groups was confirmed in by FT-IR characterization. Thus, it can be
concluded that the SO3H groups are successfully formed on the
solid acid.
N2 adsorption-desorption measurements were also performed
to obtain more insights into the rice husk materials. The N2
adsorption-desorption isotherm of rice husk carbon and the carbon
solid acid (Fig. 4) shows that both samples exhibit type II patterns,
which are typical macropores materials. Furthermore, the hyster-
esis loop of both samples showed H3 categories, indicating many
slit-like pores exist in the samples [17]. These results also prove that
the textural properties of the solid acid were substantially main-
tained during the sulfonation process. The characterization results
of the pore size distribution evaluated from adsorption data are also
shown in Fig. 4b, implying that the average pore sizes of the two
samples are in nanometers.
The type and strength of acid sites are the fundamental prop-
erties of solid acid. As a sensitive and reliable technique [18], 13C
MAS NMR spectra of 2-13C-acetone adsorbed on the catalysts are
used to characterize the acidity of the solid acid derived from rice
husk. The stronger Brønsted acidity will result in stronger hydrogen
bonding between the carbonyl carbon and the acidic proton, and
consequently, the more downfield of the 13C isotropic chemical
shift. As shown in Fig. 5, the resonance at 113 ppm is due to the
background of the NMR probe. The strong signal (at 219 ppm) is
ascribed to acetone adsorbed on the weakly acidic OH groups
present on the catalyst [19] (Fig. 5a). For the carbon solid acid
(Fig. 5b), three clear resonances at 219 ppm (due to acetone
adsorbed on the weak acidic eOH groups), 229 and 242 ppm are
observed in the 13C MAS NMR spectra. Since the FT-IR character-
ization has confirmed the existence of eCOOH and eSO3H func- Fig. 4. The N2 adsorptionedesorption isotherm (a), and pore size distribution (b) of
tional groups, the resonances at 229 and 242 can be assigned to the rice husk carbon and carbon solid acid.

2-13C-acetone adsorbed on the Brønsted acid sites eCOOH and

Fig. 3. 13C CP/MAS NMR spectrum of (a) rice husk carbon and (b)the carbon solid acid.
The asterisk denotes spinning sidebands.
eSO3H groups, respectively [5]. The resonance at 229 ppm (due to-
COOH groups) indicates that acid strength of eCOOH acid site on
the catalyst is stronger than that of the bridging OH group in HZSM-
5 zeolite, while the 242 ppm signal corresponding to Brønsted sites
of SO3H groups exhibits its acid strength is weaker than that of
100% H2SO4 (shown a 31C chemical shift of 245 ppm) [20].
The morphology of rice husk, rice husk carbon and carbon solid
acid catalyst is shown in Fig. 6. The rice husk exhibited a typical
network structure of the biological tissue (Fig. 6a). While after
calcinations and leaching process lots of pores with sizes of mi-
crometers can be clearly found in rice husk carbon. Fig. 6c shows
that after the sulfonation treatment the porous structure still exists
in the carbon solid acid, implying that the prepared carbon catalyst
has a high surface area and abundant porous structure, which is in
favor of catalysis reaction.
In order to evaluate the activity of the solid acid in the reaction, a
comparative study was made between the carbon solid acid,
sulfated zirconia, HZSM-5(Si/Al ¼ 38) and Nafion NR 50 (Fig. 7). The
reaction used was the esterification of oleic acid (20 mmol) with
methanol (100 mmol) at 80  C for 9 h. The same amount (0.015 g) of
all the catalysts was used in the reactions. A remarkable enhance-
ment in the reactivity and the yield was observed with carbon
catalyst as compared with the other solid acid catalysts examined.
 D. Zeng et al. / Microporous and Mesoporous Materials 219 (2016) 54e58 57

Fig. 7. Comparison of catalytic activity for conversion of oleic acid over the carbon
solid acid and other typical solid acid.
Fig. 5. 13C CP/MAS NMR spectra of 2-13C-acetone adsorbed on (a) rice husk carbon and
(b) the carbon solid acid. The asterisk denotes spinning sidebands.
Table 2
Textural properties and the catalytic performance of the various catalysts.

It is known that strong acid strength of solid acid leads to high Catalysts SBET Vtot D Total acid density Yield
(m2/g) (cm3/g) (nm) (mmol/g) (%)
esterification reaction activity. In this case, compared the 2-13C-
acetone NMR characterization results of the carbon solid acid (the Solid acid 1233 0.744 38.96 5.25 91
13
C chemical shift is 242 ppm) with sulfated zirconia ([21], the 13C SO2
4 /ZrO2 151 0.232 5.23 4.41 65
HZSM-5 370 0.122 0.59 1.13 30
chemical shift is 234 ppm from the reference), H-ZSM-5 ([22], the
13 Nafion NR50 0.018 e e 0.92 18
C chemical shift is 223 ppm) and Nafion NR50 [23], it can be
SBET, specific surface area from BET method; Vtot, total pore volume; D, average pore
concluded that the carbon solid acid shows the stronger acid
diameter.
strength than other three solid acids, consequently, it will exhibit Reaction condition: 20 mmol oleic acid; 100 mmol methanol; 0.015 g catalyst;
higher activity in the esterification reaction, which is also consis- 80  C; 9 h.
tent with the catalytic performance results in Table 2. The rice husk-
derived carbon solid acid catalyst afforded a high yield of above
90%. Therefore, it can be inferred that high reactivity in esterifica- shows good reusability for the esterification of oleic acid with
tion reaction is due to the strong acid strength and high surface area methanol, which can be attributed to its ultra high surface area and
of the carbon solid acid. the tight attachment of strong acid groups to the framework.
To test the reusability of the catalyst, the carbon solid acid was Consequently, this kind of solid acid from rice husk is a promising
reused for ten cycles for the esterification of oleic acid. After the green catalyst for esterification.
esterification was completed, the used catalyst was separated from
the reaction mixture by filtration, and then it was washed with 4. Conclusions
ethanol to remove the residual reactants off the catalyst surface.
Finally, the catalyst was dried at 105  C for 2 h before reusing. The In summary, a novel carbon solid acid was prepared from
results are presented in Fig. 8. Compared with those of the typical biomass rice husk by incompletely carbonization, sodium hydrox-
solid acid sulfated zirconia, the yields of the carbon solid acid ide leaching and concentrated H2SO4 sulfonation. The solid acid
gradually decreased after the first two cycles and then remained was characterized by XRD, FT-IR, N2 adsorption-desorption and
almost constant for the later cycles. The carbon solid acid catalyst solid-state NMR. The characterization results show that the carbon

Fig. 6. SEM of (a) rice husk; (b) rice husk carbon and (c)the carbon solid acid.
58 D. Zeng et al. / Microporous and Mesoporous Materials 219 (2016) 54e58
Fig. 8. Stability test of the carbon solid acid and the typical solid acid SO2
4 /ZrO2.
solid acid exhibits ultra high surface area of 1233 m2/g and stronger
acid strength than that of HZSM-5 zeolite. The catalytic perfor-
mance was tested by the esterification of oleic acid with methanol.
The results indicate that this solid acid catalyst is an excellent
catalyst compared with other conventional solid acid. In addition, it
is possible that this green and active porous carbon catalyst may
find wide applications in reactions catalyzed by liquid acids.
Acknowledgments
We acknowledge the financial supports from the National Nat-
ural Science Foundation of China (21473126), the Fund of Hubei
Provincial Department of Education (B2014094) and the Open
Research Fund of Hubei Province Key Laboratory of Coal Conversion
and New Carbon Material (WKDM2013010).
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