Beruflich Dokumente
Kultur Dokumente
Fuel
journal homepage: www.elsevier.com/locate/fuel
School of Environmental Science and Engineering, Tianjin University, Tianjin 300072, China
State Key Laboratory of Internal Combustion Engines, Tianjin University, Tianjin 300072, China
c
Key Laboratory of Efcient Utilization of Low and Medium Grade Energy (Tianjin University), Ministry of Education, Tianjin 300072, China
b
h i g h l i g h t s
g r a p h i c a l a b s t r a c t
a r t i c l e
i n f o
Article history:
Received 23 November 2014
Received in revised form 4 February 2015
Accepted 24 February 2015
Available online 7 March 2015
Keywords:
Biomimetic silicication
Biodiesel
CaOSiO2 catalyst
Eggshell
Transesterication
a b s t r a c t
In the present study, CaOSiO2 catalysts were successfully synthesized through a biomimetic silicication
approach by using eggshell and Na2SiO3 as raw materials. More specically, the powdered egg shells,
where lysozyme (the inducer) was located, were dispersed into Na2SiO3 aqueous solution to implement
the biomimetic silicication under ambient conditions. The as-obtained egg shell-SiO2 composites were
then calcined at 800 C under oxygen atmosphere, thus acquiring the CaOSiO2 catalysts. These catalysts
were detailedly characterized by SEM, EDS, 29Si NMR, FTIR, XRD, BET analysis, and Hammett indicator.
When utilized for catalytic transesterication of palm oil, the CaOSiO2 catalysts exhibited decreased
catalytic activity and increased reusability as the amount of Si compounds increased. Particularly, when
the Na2SiO3 concentration was below 0.4 M, a slight decrease in the catalytic activity could be observed
(0Si5Ca, 1Si5Ca and 2Si5Ca showed good performance with biodiesel yields of 90.2%, 87.7% and 80.1%, respectively), whereas the reusability of the catalyst was signicantly improved (little deactivation was found
after 12 cycles on the 2Si5Ca catalyst during the transesterication reaction). Hopefully, this biomimetic
silicication approach can be applied for the synthesis of a wide range of efcient and stable solid base
catalysts for transesterication/esterication reactions.
2015 Elsevier Ltd. All rights reserved.
1. Introduction
Corresponding author. Tel./fax: +86 22 27890566.
E-mail address: shijiafu@tju.edu.cn (J. Shi).
http://dx.doi.org/10.1016/j.fuel.2015.02.109
0016-2361/ 2015 Elsevier Ltd. All rights reserved.
49
50
Fig. 1. SEM images of the (a) 0Si5Ca and (b) 2Si5Ca catalysts.
Table 1
EDS analysis of the surface of the 0Si5Ca and 2Si5Ca catalysts.
Image
Text point
Fig. 1a
Fig. 1b
A
A
B
C
Others
Ca
Si
36.58
32.42
26.88
28.26
0
5.48
11.21
9.58
57.64
58.28
59.23
58.77
2.24
1.45
1.24
1.60
3.54
2.37
1.24
1.79
871
1470
(a)
Transmittance (%)
(b)
991
(c)
(d)
(e)
1050
20%
2000
1800
1600
1400
1200
1000
800
600
Wavenumber (cm-1)
Fig. 2.
29
Fig. 3. FTIR spectra of the (a) 0Si5Ca, (b) 1Si5Ca, (c) 2Si5Ca, (d) 3Si5Ca and (e)
5Si5Ca catalysts.
51
Intensity (a.u.)
5Si5Ca
3Si5Ca
2Si5Ca
1Si5Ca
0Si5Ca
20
30
40
50
60
70
80
2 ()
Fig. 4. XRD patterns of the 0Si5Ca, 1Si5Ca, 2Si5Ca, 3Si5Ca and 5Si5Ca catalysts.
Table 2
Basic strengths and surface area of series of the catalysts.
871 cm1 that was the out-of-plane band vibration mode of the
CO2
3 groups could be found. Accordingly, another absorption band
that was ascribed to the asymmetric stretch of CO2
3 groups was
also found at 1417 cm1 [36]. The appearance of this absorption
band with similar intensity for all the ve catalysts may be
attributed to the basic carbonates generated by the adsorption of
gaseous CO2 from atmosphere onto the catalysts [37].
Furthermore, the SiOCa bond (the adsorption band at around
991 cm1 [18]) on the catalysts surface appeared as the Na2SiO3
concentration reached 0.2 M, while the SiOSi bonds (the absorption band around 1050 cm1 [26]) appeared with the Na2SiO3 concentration reached 1.0 M. This was suggested that, in the lower
Na2SiO3 concentration, all the SiO2 generated from the biomimetic
silicication process was reacted with CaO to form the new phase
CaSiO3 or Ca2SiO4 compound. when the Na2SiO3 concentration was
too high, excessive SiO2 was found on the catalyst surface.
Fig. 4 showed the XRD patterns of the 0Si5Ca, 1Si5Ca, 2Si5Ca,
3Si5Ca and 5Si5Ca catalysts. The peaks those appeared at
2h = 37.2, 64.2, 76.1 and 2h = 20.2, 33.4, 39.7, 55.3, 59.8
were the characteristic peaks of CaO and Ca(OH)2, respectively.
When the Na2SiO3 concentration increased from 0 to 0.4 M, a mixture of CaO and Ca(OH)2 in the catalysts could be found. Besides,
with the increase of Na2SiO3 concentration, the peak intensity of
CaO and Ca(OH)2 decreased gradually. This might be primarily
due to the increased coverage ratio of Si compounds (SiO2 and
CaSiO3) on the CaO surface. Subsequently, as the Na2SiO3 concentration increased to 0.6 M, the peak of Si compounds could be
found and the peak intensity of CaO and Ca(OH)2 decreased sharply, suggesting that the occurrence of chemical reaction between
SiO2 and CaO/Ca(OH)2 phases in the catalyst. As the Na2SiO3 concentration increased to 1.0 M, the peak of SiO2 (2h = 26.8 and
42.2), CaSiO3 (2h = 39.2) and Ca2SiO4 (2h = 35.1) could be then
observed, while CaO and Ca (OH)2 phases completely disappeared.
Interestingly, no CaCO3 peak could be found on the catalyst surface
for all the catalysts. This result seemed to be contrast with the FTIR
and EDS analysis (only 1.242.24 wt.% content in catalyst surface)
results as described above. The probable explanation could be
described as follows: the content of CaCO3 in the catalysts was
too low to be detected by the XRD instrument. Similar results were
also found in some previous literatures [18,38,39].
100
80
-- CaO
-- Ca(OH)2
-- CaSiO3
-- Ca2SiO4
-- SiO2
0Si5Ca
1Si5Ca
2Si5Ca
3Si5Ca
5Si5Ca
60
40
20
Catalyst
Basic strength
(H_)
Total basicity
(mmol g1)
Surface area
(m2 g1)
Biodiesel
yield (%)
0Si5Ca
1Si5Ca
2Si5Ca
3Si5Ca
5Si5Ca
9.3
8.0
5.5
0.4
0.1
15.47
8.67
5.78
4.29
4.01
90.2
87.7
80.1
40.7
13.5
10
52
100
90
80
0Si5Ca
1Si5Ca
2Si5Ca
3Si5Ca
5Si5Ca
60
50
40
30
20
10
0
50
55
60
65
70
100
100
90
90
80
80
70
0Si5Ca
1Si5Ca
2Si5Ca
3Si5Ca
5Si5Ca
60
50
40
70
70
0Si5Ca
1Si5Ca
2Si5Ca
3Si5Ca
5Si5Ca
60
50
40
30
30
20
20
10
10
0
0
6
12
15
18
21
10
11
53
90
0Si5Ca
1Si5Ca
2Si5Ca
80
70
60
50
40
0
10
12
Number of cycle
Fig. 9. Reusability study of the 0Si5Ca, 1Si5Ca and 2Si5Ca catalysts. Conditions for
0Si5Ca: reaction time, 3 h; methanol-to-oil molar ratio, 9; catalyst loading, 5 wt.%;
temperature, 65 C. Conditions for 1Si5Ca: reaction time, 4 h; methanol-to-oil
molar ratio, 12; catalyst loading, 7 wt.%; temperature, 65 C. Conditions for 2Si5Ca:
reaction time, 8 h; methanol-to-oil molar ratio, 15; catalyst loading, 9 wt.%;
temperature, 65 C.
3500
(a)
3000
1Si5Ca
0Si5Ca
2Si5Ca
2500
--Ca(OH)2
2000
--Ca-glyceroxide
1500
500
0
1
200
10
(b)
11
12
1Si5Ca
0Si5Ca
2Si5Ca
150
Intensity (a.u.)
Ca content (ppm)
1000
(a)
100
(b)
50
0
1
10
11
12
Number of cycle
Fig. 10. Leaching content of Ca
2+
10
15
20
25
30
35
40
2 ()
Fig. 11. XRD patterns of recovered (a) 0Si5Ca and (b) 2Si5Ca catalysts.
54
CaO to the bulk reaction medium, thus preventing not only the
leaching of Ca2+ ions in some extent but also the unnecessary
reaction between CaO and glycerol (or H2O) [26,42,43]; and (2)
the leached Ca2+ ions from the catalysts could be adsorbed by
SiO2 on the catalyst surface to form CaOSi bond (as shown
in Fig. 3), which could also enhance the catalyst stability. As
was well known, once applying CaO as a catalyst, both the
homogeneous system and the heterogeneous system contributed
to activity in the reaction [17], and if the leaching problem was
well solved, the activity of catalyst may decrease, but the stability could be improved. For practical applications in the transesterication reaction, it was important to acquire a more stable
catalyst rather than a more active one [26].
90
80
70
Palm Oil
1 wt.% water
3 wt.% water
1 wt.% FFA
3 wt.% FFA
60
50
40
30
20
10
10
was improved. Although the catalytic activity of the 2Si5Ca catalyst was lower than that of the 0Si5Ca catalyst, little deactivation
could be found up to 12 consecutive cycles. Additionally, the catalytic activity of the 2Si5Ca catalyst was higher than that of the
0Si5Ca catalyst after conducting the reaction for more than four
cycles. This indicated that the CaOSiO2 catalyst prepared through
the biomimetic silicication approach had a much better
reusability.
Moreover, the biodiesel phase after the removal of the catalysts
was measured by ICP analysis to detect the leached Ca2+ ions. As
shown in Fig. 10, the Ca2+ ions were indeed leached into the biodiesel and glycerol phase after each reaction cycle. Typically, the highest amount of leached Ca2+ ions in either biodiesel phase or
glycerol phase could be detected for the rst reaction cycle. The
concentrations of the dissolved Ca2+ ions in biodiesel phase for
the 0Si5Ca, 1Si5Ca and 2Si5Ca catalysts were 168, 108 and
40 ppm, respectively. In glycerol phase, the concentration of dissolved Ca2+ ions for the three catalysts was 3240, 2514 and
2001 ppm, respectively. However, the concentration of Ca2+ ions
for the three catalysts decreased signicantly with subsequent
reaction cycles, becoming lower than 5 ppm (in biodiesel phase)
and 100 ppm (in glycerol phase) after the 12th cycle. And the order
of Ca2+ content leaching in the reaction media for the catalysts was
as follows: 0Si5Ca > 1Si5Ca > 2Si5Ca.
Additionally, in order to investigate the chemical composition
revolution of catalysts before and after use, the XRD patterns of
recovered catalysts (0Si5Ca and 2Si5Ca) after the 12th cycle were
studied. As illustrated in Fig. 11, no peaks of CaO were found in
the XRD patterns of the recovered 0Si5Ca and 2Si5Ca catalysts,
which was mainly owing to the formation of new phases such as
Ca(OH)2 (2h = 18 and 34) and calcium diglyceroxide (2h = 8,
10, 21, 24 and 26) on the catalyst surface. It was notable that
the intensities of calcium diglyceroxide and Ca(OH)2 peaks for
the 2Si5Ca catalyst were much lower than that of the 0Si5Ca catalyst. The result might be owing to the Si compounds on the 2Si5Ca
preventing the formation of the new phases calcium diglyceroxide
and Ca(OH)2 during reaction.
In light of the experiments mentioned above, the good stability of the 2Si5Ca catalyst may be owing to the following
two reasons: (1) the better distribution of Si compounds on
the CaO surface protected the direct exposure of Ca2+ ions or
4. Conclusions
In summary, the CaOSiO2 catalysts were prepared through a
biomimetic silicication approach and exploited as novel solid
base catalysts for biodiesel production. Along with the increase
of the amount of Si compounds in the CaOSiO2 catalysts, the catalytic activity was gradually decreased, while the reusability was
signicantly improved. Particularly, in comparison to the 0Si5Ca
catalyst, the 2Si5Ca catalyst only showed a slightly lower catalytic
activity (biodiesel yield: 80.1% vs. 90.2%), however, little deactivation
could be found after 12 cycles reuse during the transesterication
reaction. Hopefully, the CaOSiO2 catalyst prepared through this
biomimetic silicication approach will be a promising solid base
catalyst for biodiesel or other fuels/chemicals production.
Acknowledgements
This paper is nancially supported by National Natural Science
Funds of China (21406163), National High-tech Research and
Development Program (863 Program) through project
(2012AA051801).
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