RSC Advances
Paper
8 A. Hiremath, M. Kannabiran and V. Rangaswamy, New
Biotechnol., 2011, 28, 19–23.
Conclusions
Lipase-catalyzed glycerol carbonate synthesis from glycerol
and a dialkyl carbonate was studied. CalB was selected as the
most effective catalyst, and the influence of reaction condi-
tions was investigated. A reaction system was identified that
offers dramatically higher productivity than previously
reported.
Our system offers high glycerol conversion and glycerol
carbonate selectivity without the use of environmentally toxic
solvents53 or additional treatment of the reactants, and
9 H. Habe, Y. Shimada, T. Yakushi, H. Hattori, Y. Ano,
T. Fukuoka, D. Kitamoto, M. Itagaki, K. Watanabe,
H. Yanagishita, K. Matsushita and K. Sakaki, Appl.
Environ. Microbiol., 2009, 75, 7760–7766.
10 A. Rywinska, W. Rymowicz, B. Zarowska and
M. Wojtatowicz, Food Technology and Biotechnology, 2009,
47, 1–6.
11 W. Rymowicz, A. Rywinska and M. Marcinkiewicz,
Biotechnol. Lett., 2009, 31, 377–380.
12 M. H. A. Ibrahim and A. Steinbuchel, Appl. Environ.
Microbiol., 2009, 75, 6222–6231.
requires
a minimal amount of excess reactant (DMC).
Through control of the reaction parameters, particularly the
relative substrate concentrations, the reaction can be tuned to
deliver high conversion as well as high selectivity towards
glycerol carbonate. Additionally, substitution of an alternate
dialkyl carbonate offers the possibility of an expanded product
profile. As new glycerol chemistries are being explored as a
basis for renewable biorefineries, these side products deserve
further study.
As biofuel production expands, new strategies for enhan-
cing the economics of the process must be implemented.
Glycerol carbonate production from waste glycerol offers not
only an economic advantage, but will allow biodiesel facilities
to recycle their waste stream into a sustainable chemical
source. Furthermore, as CalB is a suitable catalyst for both
biodiesel and glycerol carbonate production, practical imple-
mentation of these processes can be streamlined. In addition,
we observed increased conversion rates and interesting side
products when using diethyl and dibutyl carbonate in place of
dimethyl carbonate. These additional products show the
substrate versatility of CalB and indicate the potential of
glycerol as a feedstock for biorefineries.
13 Z. T. Dobroth, S. Hu, E. R. Coats and A. G. McDonald,
Bioresour. Technol., 2011, 102, 3352–3359.
14 G. Sabourin-Provost and P. C. Hallenbeck, Bioresour.
Technol., 2009, 100, 3513–3517.
15 W. Choi, M. Hartono, W. Chan and S. Yeo, Appl. Microbiol.
Biotechnol., 2011, 89, 1255–1264.
16 K. A. Taconi, K. P. Venkataramanan and D. T. Johnson,
Environ. Prog. Sustainable Energy, 2009, 28, 100–110.
17 M. S. Fountoulakis and T. Manios, Bioresour. Technol.,
2009, 100, 3043–3047.
18 Y. G. Zheng, X. L. Chen and Y. C. Shen, Chem. Rev., 2008,
108, 5253–5277.
19 D. P. Abraham, US Patent 20110117445A1, 2011.
20 G. Rokicki, P. Rakoczy, P. Parzuchowski and M. Sobiecki,
Green Chem., 2005, 7, 529–539.
´
21 C. L. Bolıvar-Diaz, V. Calvino-Casilda, F. Rubio-Marcos, J.
´
˜
F. Fernandez and M. A. Banares, Appl. Catal., B, 2013, 129,
575–579.
22 G. Ou, B. He and Y. Yuan, Enzyme Microb. Technol., 2011,
49, 167–170.
23 R. A. Grey, US Patent 5091543, 1992.
24 J. B. Bell, V. A. Currier, J. D. Malkemus, US Patent 2915529,
1959.
25 C. Vieville, J. W. Yoo, S. Pelet and Z. Mouloungui, Catal.
Lett., 1998, 56, 245–247.
26 J. George, Y. Patel, S. M. Pillai and P. Munshi, J. Mol. Catal.
A: Chem., 2009, 304, 1–7.
27 A. Corma, Chem. Rev., 2007, 107, 2411–2502.
28 M. J. Climent, A. Corma, P. De Frutos, S. Iborra, M. Noy,
Acknowledgements
This research was supported by the US Department of
Agriculture (NIFA) under award number 2009-10003-05141
and by the NSF under award number 0832498.
´
A. Velty and P. Concepcion, J. Catal., 2010, 269, 140–149.
29 J. R. Ochoa-Gomez, O. Gomez-Jimenez-Aberasturi,
B. Maestro-Madurga, A. Pesquera-Rodriguez, C. Ramirez-
Lopez, L. Lorenzo-Ibarreta, J. Torrecilla-Soria and M.
C. Villaran-Velasco, Appl. Catal., A, 2009, 366, 315–324.
References
1 M. Watanabe, T. Lida, Y. Aizawa, T. M. Aida and
H. Inomata, Bioresour. Technol., 2007, 98, 1285–1290.
2 W. Yan and G. J. Suppes, Ind. Eng. Chem. Res., 2009, 48,
3279–3283.
3 M. A. Dasari, P. P. Kiatsimkul, W. R. Sutterlin and G.
J. Suppes, Appl. Catal., A, 2005, 281, 225–231.
4 J. Barrault, J. M. Clacens and Y. Pouilloux, Top. Catal.,
2004, 27, 137–142.
5 M. Kohlmayr, G. Zuckerstatter and A. Kandelbauer, J. Appl.
Polym. Sci., 124, 4416–4423.
6 S. J. Yoon, Y.-C. Choi, Y.-I. Son, S.-H. Lee and J.-G. Lee,
Bioresour. Technol., 2010, 101, 1227–1232.
7 Y. N. Zhao, G. Chen and S. J. Yao, Biochem. Eng. J., 2006, 32,
93–99.
´
´
´
30 J. R. Ochoa-Gomez, O. Gomez-Jimenez-Aberasturi,
´
´
C. Ramırez-Lopez and B. Maestro-Madurga, Green Chem.,
2012, 14, 3368–3376.
31 M. C. Dezoete, F. Vanrantwijk and R. A. Sheldon, Catal.
Today, 1994, 22, 563–590.
32 R. G. Bistline, A. Bilyk and S. H. Feairheller, J. Am. Oil
Chem. Soc., 1991, 68, 95–98.
33 G. Guanti, L. Banfi and R. Riva, Tetrahedron: Asymmetry,
1994, 5, 9–12.
34 F. van Rantwijk, M. W. V. Oosterom and R. A. Sheldon, J.
Mol. Catal. B: Enzym., 1999, 6, 511–532.
35 V. L. Lassalle and M. L. Ferreira, J. Chem. Technol.
Biotechnol., 2008, 83, 1493–1502.
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RSC Adv., 2013, 3, 18596–18604 | 18603