46
V. Eta et al. / Applied Catalysis A: General 404 (2011) 39–46
Fig. 12. The fit of the kinetic model compared with the experimental data at 150 ◦C, initial pressure of CO2 at 45 bar. The concentrations of different species as a function of
time for the experimental (points) and estimated values (continuous lines).
6. Conclusions
References
[1] M. Aresta, A. Dibenedetto, Dalton Trans. (2007) 2975–2992.
[2] M. Aresta, Quimica Nova 22 (1999) 269–272.
[3] R. Srivastava, T.H. Bennur, D. Srinivas, J. Mol. Catal. A: Chem. 226 (2005)
199–205.
[4] R. Srivastava, D. Srinivas, P. Ratnasamy, J. Catal. 233 (2005) 1–15.
[5] E. Fujita, B.S. Brunschwig, T. Ogata, S. Yanagida, Coord. Chem. Rev. 132 (1994)
195–200.
[6] M.A. Casadei, A. Inesi, L. Rossi, Tetrahedron Lett. 38 (1997) 3565–3568.
[7] Y. Ono, Catal. Today 35 (1997) 15–25.
[8] P. Tundo, Pure Appl. Chem. 73 (2001) 1117–1124.
[9] D. Aurbacha, Y. Talyosefa, B. Markovskya, E. Markevicha, E. Zin-
igrada, L. Asrafa, J.S. Gnanaraja, H.-J. Kimb, Electrochim. Acta 50 (2004)
247–254.
[10] V. Eta, P. Mäki-Arvela, D. Murzin, Y. Salmi, T.J.-P. Mikkola, in: D.L. Marmaduke
(Ed.), Progress in Heterogeneous Catalysis, Nova Science Publishers, Haup-
pauge, NY, 2008, pp. 135–155.
[11] Z.-F. Zhang, Z.-W. Liu, J. Lu, Z.-T. Liu, Ind. Eng. Chem. Res. 50 (2011)
1981–1988.
[12] M. Honda, A. Suzuki, B. Noorjahan, K. Fujimoto, K. Suzuki, K. Tomishige, Chem.
Commun. (2009) 4596–4598.
The kinetics of the synthesis of DMC from methanol and CO2
using butylene oxide as a chemical trap for water over ZrO2–MgO
was studied with the temperature range 120–180 ◦C. Mass trans-
fer resistances were eluded by using catalysts with particle sizes
<100 m and 700 rpm of stirring speed. The methanol-to-butylene
oxide ratio of 30 showed a reasonable conversion of methanol
and DMC selectivity at 150 ◦C. DMC and butylene glycol were
formed via the reaction of adsorbed mono-methoxycarbonate
intermediate and methoxybutanol. DMC was also formed via
the mono-methoxycarbonate reaction with methanol, producing
water as by-product in the absence of butylene oxide. Regression
analysis performed for the advanced mechanism provided reason-
able description of the concentration dependencies of the species
over time for reactions performed at different temperatures. The
apparent activation energy was determined as 62 kJ/mol.
[13] V. Eta, P. Mäki-Arvela, A.-R. Leino, K. Kordás, T. Salmi, D. Murzin, J.-P. Mikkola,
Ind. Eng. Chem. Res. 49 (2010) 9609–9617.
[14] S. Brunauer, P.H. Emmett, E. Teller, J. Am. Chem. Soc. 60 (1938) 309–319.
[15] Y. Kishimoto, I. Ogawa, Ind. Eng. Chem. Res. 43 (2004) 8155–8162.
[16] H. Hattori, Chem. Rev. 95 (1995) 537–558.
[17] K.T. Jung, A.T. Bell, Top. Catal. 20 (2002) 97–105.
[18] Y. Zhang, A.T. Bell, J. Catal. 255 (2008) 153–216.
[19] K.T. Jung, A.T. Bell, J. Catal. 204 (2001) 339–347.
[20] S. Xie, A.T. Bell, Catal. Lett. 70 (2000) 137–143.
Acknowledgements
This work is part of the activities of Åbo Akademi Process Chem-
istry Centre within the Finnish Centre of Excellence (2006–2011),
and the KETJU Research Programme (2006–2010) by the Academy
of Finland. The authors are grateful to the Academy of Finland for
the financial support under the Grants 120853, 124357 and 128626.
This work is also associated with the activities of Umeå Univer-
sity Chemical-Biological Centre whereupon financial support from
Bio4Energy Programme, Kempe Foundations and Knut and Alice
Wallenberg Foundation are acknowledged.
[21] H. Haario, MODEST User’s Manual
2001.
, Profmath Oy, Helsinki, Finland,
[22] A. Hindmarsh, in: R. Steppleman (Ed.), C. OPEPARK – A Systematized Collec-
tion of ODE Solvers in Scientific Computing, IMACS/North Holland Publishing
Company, Amsterdam, The Netherlands, 1983, pp. 55–64.