Reaction Kinetics of Biodiesel Synthesis from Waste Oil Using a Carbon-based Solid Acid Catalyst

doi:10.1016/S1004-9541(09)60193-2

Chinese Journal of Chemical Engineering

Volume 19, Issue 1, February 2011, Pages 163-168

https://doi.org/10.1016/S1004-9541(09)60193-2 Get rights and content

Abstract

The kinetics of simultaneous transesterification and esterification with a carbon-based solid acid catalyst was studied. Two solid acid catalysts were prepared by the sulfonation of carbonized vegetable oil asphalt and petroleum asphalt. These catalysts were characterized on the basis of elemental analysis, acidity site concentration, the Brunauer-Emmett-Teller (BET) surface area and pore size. The kinetic parameters with the two catalysts were determined, and the reaction system can be described as a pseudo homogeneous catalyzed reaction. All the forward and reverse reactions follow second order kinetics. The calculated concentration values from the kinetic equations are in good agreement with experimental values.

References (20)

Y.C. Sharma et al.
“Advancements in development and characterization of biodiesel: A review”
Fuel
(2008)
J.V. Gerpen
“Biodiesel processing and production”
Fuel. Process. Technol.
(2005)
Q. Shu et al.
“Synthesis of biodiesel from cottonseed oil and methanol using a carbon-based solid acid catalyst”
Fuel. Process. Technol.
(2009)
Q. Shu et al.
“Synthesis of biodiesel from waste oil feedstocks using a carbon-based solid acid catalyst: Reaction and separation”
Bioresour. Technol.
(2010)
M.H. Han et al.
“Preparation of biodiesel from waste oils catalyzed by a Brönsted acidic ionic liquid”
Bioresour. Technol.
(2009)
J.J. Zhang et al.
“Acid-catalyzed esterification of zanthoxylum bungeanum seed oil with high free fatty acids for biodiesel production”
Bioresour. Technol.
(2008)
P. Felizardo et al.
“Production of biodiesel from waste frying oils”
Waste. Manage.
(2006)
Q. Shu et al.
“Preparation of biodiesel using s-MWCNT catalysts and the coupling of reaction and separation”
Food. Bioprod. Process.
(2009)
M.Y. Gan et al.
“The kinetics of the esterification of free fatty acids in waste cooking oil using Fe₂(SO₄)₃/C catalyst”
Chin. J. Chem. Eng.
(2009)
G. Vicente et al.
“Comparative study of vegetable oils for biodiesel production in spain”
Energy. Fuels.
(2006)

There are more references available in the full text version of this article.

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Citation Excerpt :
Some of these are: use of solid catalysts, use of supercritical conditions, FFA separation from ROF and use of reactive distillation (RD) and catalytic distillation (CD) [20–30]. A great effort has been made to develop process technology as well as to develop low cost heterogeneous acid catalysts with better activity and reusability [31–37]. The solid acid catalyzed (SAC) process using a catalytic distillation column (CDC) to convert oils with high FFA levels has been reported as a way to reduce the investment and operation costs [27].
The phase equilibrium of interest in biodiesel production by reactive distillation was modeled. Mixtures were composed of the main components found in esterification and transesterification reactions. The pure component thermophysical properties of acylglycerols were predicted and evaluated by comparison with available experimental data. Databanks of vapour-liquid equilibrium, liquid-liquid equilibrium and vapour-liquid-liquid equilibrium experimental data were created for the mixtures in the biodiesel production process. The experimental data evaluated were then used to develop a rigorous thermodynamic modeling using the NRTL model. Three binary interaction parameter sets were regressed. Two NRTL parameter sets can be used to simulate the catalytic distillation column of interest in the production of biodiesel from residual oil and fats by a solid acid catalyzed process. The third parameter set is useful to simulate the reactive distillation column applicable in the biodiesel production by the homogeneous alkali catalyzed process. The phase behavior of the mixtures studied was correctly described by the proposed modeling for pressures up to 750 kPa. The proposed phase equilibrium modeling was then validated against experimental results reported for biodiesel production by reactive distillation.
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The present study is an effort to optimize the production of biodiesel from dairy scum and Hydnocarpus wightiana oil using Snail shell CaO nanocatalyst for transesterification. Response surface methodology is used to optimize the reaction parameter that affects the transesterification process for the biodiesel yield. The CaO nanocatalyst was characterized by powder X-ray diffraction, Scanning Electron Microscopy, Energy-Dispersive X-ray Spectroscopy, Brunauer-Emmett-Teller, Fourier Transformer Infrared Spectroscopy, Thermo Gravimetric/Differential Thermal Analysis and Atomic Force Microscopy. The maximum biodiesel yield for Scum Oil Methyl Ester and Hydnocarpus wightiana Oil Methyl Ester was (96.929%) and (98.93%) at the optimized condition: Methanol to oil molar ratio 12.7:1 and 12.4:1, catalyst dosage of 0.866 wt.% and 0.892 wt.%, reaction temperature 58.56°C and 61.6°C and reaction time 119.684 min and 145.154 min respectively. A comprehensive kinetic study for the transesterification reaction was performed at different temperatures (50-65°C) for the methanolysis of SO and HWO catalyzed by CaO nanoparticles. A pseudo-first order kinetic reaction was established and the activation energy (Ea) and frequency factor (A) for SO and HWO to be 67.21kJmol-1 & 5.182×108 min-1 & 73.15 kJmol-1 & 4.59×109 min-1 respectively. Recovered CaO nanocatalyst is reused for 5 times with substantial loss in biodiesel yield.

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RESEARCH NOTESReaction Kinetics of Biodiesel Synthesis from Waste Oil Using a Carbon-based Solid Acid Catalyst

Abstract

Fuel

Fuel. Process. Technol.

Fuel. Process. Technol.

Bioresour. Technol.

Bioresour. Technol.

Bioresour. Technol.

Waste. Manage.

Food. Bioprod. Process.

Chin. J. Chem. Eng.

“Comparative study of vegetable oils for biodiesel production in spain”

Energy. Fuels.

RESEARCH NOTES
Reaction Kinetics of Biodiesel Synthesis from Waste Oil Using a Carbon-based Solid Acid Catalyst