Escolar Documentos
Profissional Documentos
Cultura Documentos
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 5 May 2015
Received in revised form
16 July 2015
Accepted 26 July 2015
Available online 31 July 2015
A porous carbon solid acid was synthesized from biomass rice husk by incompletely carbonization, sodium hydroxide leaching and concentrated H2SO4 sulfonation. The solid acid was characterized by XRD,
FT-IR, N2 adsorption-desorption and solid-state NMR spectroscopy. The characterization results reveal
that the carbon solid acid shows ultra high surface area of 1233 m2/g and stronger acid strength than that
of HZSM-5(Si/Al 38) zeolite. The catalytic performance was tested by the esterication of oleic acid
with methanol. The results indicate that this solid acid catalyst is an excellent catalyst compared with
other conventional solid acid.
2015 Elsevier Inc. All rights reserved.
Keywords:
Solid acid
Rice husk
Acidity
Esterication
1. Introduction
Currently industrial esterication processes are carried out by
the catalysis of homogeneous Brnsted acids such as sulfuric acid.
However, these homogeneous acid catalysts are difcult 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 esterication reactions [6,7]. Although
strong acidic ion-exchange resins such as Naon 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 esterication of
fatty acids, and higher stability than sulfonated mesoporous silica
55
Fig. 1. XRD patterns of (a) rice husk; (b) rice husk carbon and (c) the carbon solid acid.
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
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 conrmed 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 hysteresis 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 maintained 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 properties 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 Brnsted acidity will result in stronger hydrogen
bonding between the carbonyl carbon and the acidic proton, and
consequently, the more downeld 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 characterization has conrmed the existence of eCOOH and eSO3H functional groups, the resonances at 229 and 242 can be assigned to
Fig. 4. The N2 adsorptionedesorption isotherm (a), and pore size distribution (b) of
the rice husk carbon and carbon solid acid.
Fig. 3. 13C CP/MAS NMR spectrum of (a) rice husk carbon and (b)the carbon solid acid.
The asterisk denotes spinning sidebands.
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.
Catalysts
SBET
(m2/g)
Vtot
(cm3/g)
D
(nm)
Yield
(%)
Solid acid
SO2
4 /ZrO2
HZSM-5
Naon NR50
1233
151
370
0.018
0.744
0.232
0.122
e
38.96
5.23
0.59
e
5.25
4.41
1.13
0.92
91
65
30
18
SBET, specic surface area from BET method; Vtot, total pore volume; D, average pore
diameter.
Reaction condition: 20 mmol oleic acid; 100 mmol methanol; 0.015 g catalyst;
80 C; 9 h.
Fig. 6. SEM of (a) rice husk; (b) rice husk carbon and (c)the carbon solid acid.
58
References
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 performance was tested by the esterication 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
nd wide applications in reactions catalyzed by liquid acids.
Acknowledgments
We acknowledge the nancial supports from the National Natural Science Foundation of China (21473126), the Fund of Hubei