Global Kinetics of Direct Dimethyl Ether Synthesis Process from Syngas in Slurry Reactor over a Novel Cu-Zn-Al-Zr Slurry Catalyst
The direct synthesis process of dimethyl ether (DME)
from syngas in slurry reactors is considered to be promising because
of its advantages in caloric transfer. In this paper, the influences of
operating conditions (temperature, pressure and weight hourly space
velocity) on the conversion of CO, selectivity of DME and methanol
were studied in a stirred autoclave over Cu-Zn-Al-Zr slurry catalyst,
which is far more suitable to liquid phase dimethyl ether synthesis
process than bifunctional catalyst commercially. A Langmuir-
Hinshelwood mechanism type global kinetics model for liquid phase
DME direct synthesis based on methanol synthesis models and a
methanol dehydration model has been investigated by fitting our
experimental data. The model parameters were estimated with
MATLAB program based on general Genetic Algorithms and
Levenberg-Marquardt method, which is suitably fitting experimental
data and its reliability was verified by statistical test and residual
error analysis.
[1] H.-T. Zhang, D.-Y. Fang, "Dimethyl ether directly synthesizing from
syngas," Chemical Industry and Engineering Progress, vol. 21, no. 2, pp.
97-10, Feb. 2002.
[2] J. Ere├▒a, R. Garo├▒a, J. M. Arandes, A.T. Aguayo, J. Bilbao, "Effect of
operating conditions on the synthesis of dimethyl ether over
CuO-ZnO-Al2O3/NaHZSM-5 bifunctional catalyst," Catal. Today, vol.
107-108, pp. 467-473, Oct. 2005.
[3] A.T. Aguayo, J. Ere├▒a, D. Mier, J. M.Arandes, M. Olazar, J. Bilbao,
"Kinetic modeling of dimethyl ether synthesis in a single step on a
CuO-ZnO-Al2O3/╬│-Al2O3 catalyst," Ind. Eng. Chem. Res., vol. 46, no. 17,
pp. 5522-5530, July. 2007.
[4] Z.-L. Wang, J.-F. Wang, J. Diao, Y. Jin, "The synergy effect of process
coupling for dimethyl ether synthesis in slurry reactor," Chemical
Reaction Engineering and Technology, vol. 17, no. 3, pp. 233- 237,
Sept. 2001.
[5] A. T. Aguayo, J. Ere├▒a, I. Sierra, M. Olazar, J. Bilbao, "Deactivation and
regeneration of hybrid catalysts in the single-step synthesis of dimethyl
ether from syngas and CO2," Catalysis Today, vol. 106, no. 1-4, pp.
265-270, Oct. 2005.
[6] D. Song, W. Cho, G. Lee, D. K. Park, E. S. Yoon, "Numerical analysis of
a pilot-scale fixed-bed reactor for dimethyl ether (DME) synthesis," Ind.
Eng. Chem. Res., vol. 47, no. 13, pp. 4553-4559 May. 2008.
[7] W.-Z. Lu, L.-H. Teng, W.-D. Xiao, "Simulation and experiment study of
dimethyl ether synthesis from syngas in a fluidized-bed reactor," Chem.
Eng. Sci., vol. 59, no.22-23, pp.5455-5464, Nov-Dec. 2004.
[8] K. L. Ng, D. Chadwick, B. A. Toseland, "Kinetics and modeling of
dimethyl ether synthesis from synthesis gas," Chem. Eng. Sci., vol. 54,
no. 15-16, pp. 3587- 3592, July.1999.
[9] X. D. Peng, B.A. Toseland, P. J. A. Tijim, "Kinetic Understanding of the
Chemical Synergy under LPDME Conditions Once-through
Applications," Chem. Eng. Sci., vol. 54, no.13-14, pp. 2787-2792, July.
1999.
[10] G. R. Moradi, J. Ahmadpour, F. Yaripour, "Intrinsic kinetics study of
LPDME process from syngas over bi-functional catalyst," Chem. Eng.
J., vol. 144, no.1, pp. 88-95, Oct. 2008.
[11] G. H. Graaf, E. J. Stamhuis, A. A. C. M. beenackers, "Kinetics of low
pressure methanol synthesis," Chem. Eng. Sci., vol. 43, no.12, pp. 3185-
3195, July .1988.
[12] G. Bercic, J. Levec, "Intrinsic and global reaction rate of methanol
dehydration over ╬│-Al2O3 pellets," Ind. Eng. Chem. Res., vol. 31, no.4,
pp. 1035- 1040, Apr.1992.
[13] Z.-G. Nie, H.-W. Liu, D.-H. Liu, W.-Y. Ying, D.-Y.Fang, "The global
kinetics of synthesis of dimethyl ether from syngas containing N2 over
bifunctional catalyst," Chemical Reaction Engineering and Technology,
vol. 20, no. 1, pp. 1-7, Mar. 2004.
[14] D.-H. Liu, X. Hua, D.-Y. Fang, "Mathematical Simulation and Design of
three-phase bubble column reactor for direct synthesis of dimethyl ether
from syngas," Journal of Natural Gas Chemistry, vol. 16, no.2, pp.
193-199, Apr. 2007.
[15] Z.-H. Gao, W. Huang, J.-Y. Wang, L.-H. Yin, K.-C. Xie, "Complete
liquid-phase preparation and characterization of Cu-Zn-Al-Zr slurry
catalysts for synthesis of dimethyl ether," Acta Chimica Sinica, vol. 66,
no. 3, pp. 295-300, Feb. 2008.
[16] W.-D. Song, B.-C. Zhu, Z.-C. Luo, L.-B. Yu, G.-X. Feng, X. Xu,
"Computation for heat of reaction and equilibrium constant of methanol
synthesis under pressure by using SHBWR equation of state," Journal of
East China University of Science and Technology, vol. 17, no. 1, pp.
11-24, Jan. 1981.
[17] Q. Zhang, J. Yang, W.-Y. Ying, D.-Y.Fang, "Calculation of equilibrium
conversion and selectivity for dimethyl ether synthesis from syngas,"
Chemical Engineering, vol. 33, no. 2, pp. 64-68, Apr. 2005.
[1] H.-T. Zhang, D.-Y. Fang, "Dimethyl ether directly synthesizing from
syngas," Chemical Industry and Engineering Progress, vol. 21, no. 2, pp.
97-10, Feb. 2002.
[2] J. Ere├▒a, R. Garo├▒a, J. M. Arandes, A.T. Aguayo, J. Bilbao, "Effect of
operating conditions on the synthesis of dimethyl ether over
CuO-ZnO-Al2O3/NaHZSM-5 bifunctional catalyst," Catal. Today, vol.
107-108, pp. 467-473, Oct. 2005.
[3] A.T. Aguayo, J. Ere├▒a, D. Mier, J. M.Arandes, M. Olazar, J. Bilbao,
"Kinetic modeling of dimethyl ether synthesis in a single step on a
CuO-ZnO-Al2O3/╬│-Al2O3 catalyst," Ind. Eng. Chem. Res., vol. 46, no. 17,
pp. 5522-5530, July. 2007.
[4] Z.-L. Wang, J.-F. Wang, J. Diao, Y. Jin, "The synergy effect of process
coupling for dimethyl ether synthesis in slurry reactor," Chemical
Reaction Engineering and Technology, vol. 17, no. 3, pp. 233- 237,
Sept. 2001.
[5] A. T. Aguayo, J. Ere├▒a, I. Sierra, M. Olazar, J. Bilbao, "Deactivation and
regeneration of hybrid catalysts in the single-step synthesis of dimethyl
ether from syngas and CO2," Catalysis Today, vol. 106, no. 1-4, pp.
265-270, Oct. 2005.
[6] D. Song, W. Cho, G. Lee, D. K. Park, E. S. Yoon, "Numerical analysis of
a pilot-scale fixed-bed reactor for dimethyl ether (DME) synthesis," Ind.
Eng. Chem. Res., vol. 47, no. 13, pp. 4553-4559 May. 2008.
[7] W.-Z. Lu, L.-H. Teng, W.-D. Xiao, "Simulation and experiment study of
dimethyl ether synthesis from syngas in a fluidized-bed reactor," Chem.
Eng. Sci., vol. 59, no.22-23, pp.5455-5464, Nov-Dec. 2004.
[8] K. L. Ng, D. Chadwick, B. A. Toseland, "Kinetics and modeling of
dimethyl ether synthesis from synthesis gas," Chem. Eng. Sci., vol. 54,
no. 15-16, pp. 3587- 3592, July.1999.
[9] X. D. Peng, B.A. Toseland, P. J. A. Tijim, "Kinetic Understanding of the
Chemical Synergy under LPDME Conditions Once-through
Applications," Chem. Eng. Sci., vol. 54, no.13-14, pp. 2787-2792, July.
1999.
[10] G. R. Moradi, J. Ahmadpour, F. Yaripour, "Intrinsic kinetics study of
LPDME process from syngas over bi-functional catalyst," Chem. Eng.
J., vol. 144, no.1, pp. 88-95, Oct. 2008.
[11] G. H. Graaf, E. J. Stamhuis, A. A. C. M. beenackers, "Kinetics of low
pressure methanol synthesis," Chem. Eng. Sci., vol. 43, no.12, pp. 3185-
3195, July .1988.
[12] G. Bercic, J. Levec, "Intrinsic and global reaction rate of methanol
dehydration over ╬│-Al2O3 pellets," Ind. Eng. Chem. Res., vol. 31, no.4,
pp. 1035- 1040, Apr.1992.
[13] Z.-G. Nie, H.-W. Liu, D.-H. Liu, W.-Y. Ying, D.-Y.Fang, "The global
kinetics of synthesis of dimethyl ether from syngas containing N2 over
bifunctional catalyst," Chemical Reaction Engineering and Technology,
vol. 20, no. 1, pp. 1-7, Mar. 2004.
[14] D.-H. Liu, X. Hua, D.-Y. Fang, "Mathematical Simulation and Design of
three-phase bubble column reactor for direct synthesis of dimethyl ether
from syngas," Journal of Natural Gas Chemistry, vol. 16, no.2, pp.
193-199, Apr. 2007.
[15] Z.-H. Gao, W. Huang, J.-Y. Wang, L.-H. Yin, K.-C. Xie, "Complete
liquid-phase preparation and characterization of Cu-Zn-Al-Zr slurry
catalysts for synthesis of dimethyl ether," Acta Chimica Sinica, vol. 66,
no. 3, pp. 295-300, Feb. 2008.
[16] W.-D. Song, B.-C. Zhu, Z.-C. Luo, L.-B. Yu, G.-X. Feng, X. Xu,
"Computation for heat of reaction and equilibrium constant of methanol
synthesis under pressure by using SHBWR equation of state," Journal of
East China University of Science and Technology, vol. 17, no. 1, pp.
11-24, Jan. 1981.
[17] Q. Zhang, J. Yang, W.-Y. Ying, D.-Y.Fang, "Calculation of equilibrium
conversion and selectivity for dimethyl ether synthesis from syngas,"
Chemical Engineering, vol. 33, no. 2, pp. 64-68, Apr. 2005.
@article{"International Journal of Chemical, Materials and Biomolecular Sciences:64445", author = "Zhen Chen and Haitao Zhang and Weiyong Ying and Dingye Fang", title = "Global Kinetics of Direct Dimethyl Ether Synthesis Process from Syngas in Slurry Reactor over a Novel Cu-Zn-Al-Zr Slurry Catalyst", abstract = "The direct synthesis process of dimethyl ether (DME)
from syngas in slurry reactors is considered to be promising because
of its advantages in caloric transfer. In this paper, the influences of
operating conditions (temperature, pressure and weight hourly space
velocity) on the conversion of CO, selectivity of DME and methanol
were studied in a stirred autoclave over Cu-Zn-Al-Zr slurry catalyst,
which is far more suitable to liquid phase dimethyl ether synthesis
process than bifunctional catalyst commercially. A Langmuir-
Hinshelwood mechanism type global kinetics model for liquid phase
DME direct synthesis based on methanol synthesis models and a
methanol dehydration model has been investigated by fitting our
experimental data. The model parameters were estimated with
MATLAB program based on general Genetic Algorithms and
Levenberg-Marquardt method, which is suitably fitting experimental
data and its reliability was verified by statistical test and residual
error analysis.", keywords = "alcohol/ether fuel, Cu-Zn-Al-Zr slurry catalyst,global kinetics, slurry reactor", volume = "4", number = "8", pages = "525-7", }
