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Reaction Kinetics, Mechanisms and Catalysis

, Volume 126, Issue 1, pp 529–546 | Cite as

Kinetic modeling of 1-decene oligomerization to synthetic fuels and base oil over tungstated-zirconia catalyst

  • Tattep Techopittayakul
  • Snunkheam Echaroj
  • Malee SantikunapornEmail author
  • Channarong Asavatesanupap
  • Yi-Hung Chen
  • Min-Hao Yuan
Article
  • 52 Downloads

Abstract

The liquid phase oligomerization reaction of 1-decene to produce dimers and trimers was performed in a semi-batch autoclave reactor over a tungstated-zirconia catalyst at different reaction temperatures. While dimers can be used as a synthetic transportation fuel, trimers and higher compounds can be used as a base oil which can be blended with additives to make synthetic base oil. The conversion of 1-decene increased from 9 to 70% as the reaction temperature was increased from 423 to 483 K. At 483 K, product compositions after 11 h consisted of 50% dimers and 23% trimers. Apparent activation energies for dimerization and trimerization were found to be 21.0 ± 0.5 and 33.0 ± 0.6 kJ/mol, respectively. Kinetic interpretation has been made by studying the kinetic and equilibrium constants. The results of the oligomerization of 1-decene suggest that two active sites are responsible for dimerization. Trimerization proceeds through a combination of dimer with another monomer involving three active sites. According to the mathematical equation, an increase in active sites required for both reactions at higher temperature is necessary to compensate for catalyst deactivation.

Keywords

Oligomerization Kinetic modeling Dimerization Trimerization Tungstated-zirconia 1-Decene 

Nomenclature

DI

Dimer molecule (C20 hydrocarbon)

TRI

Trimer molecule (C30 hydrocarbon)

C10=

1-decene molecule

S

Vacant acid sites

LHHW

Langmuir–Hinshelwood–Hougen–Watson mechanism

E–R

Eley–Rideal

mi

Mass of specie i in product

Wi

Composition of specie i in product (wt%)

KAD

Adsorption equilibrium constant of olefin monomer

KA,i

Adsorption equilibrium constant of specie i (dimer or trimers)

KD,i

Desorption equilibrium constant of specie i (dimers or trimers)

\(r_{i,t}^{model}\)

Reaction rate calculated form kinetic-modeling equation

\(r_{i,t}^{exp}\)

Reaction rate of molecule i from experiment

Ea

Activation energy (kJ/mol)

Wcat

Weight of catalyst

Notes

Acknowledgements

The authors gratefully acknowledge the financial support provided by Thammasat University (Research Fund under the TU Research Scholar, Contract No. 9/2560). Also, Techopittayakul, T. would like to thank Faculty of Engineering, Thammasat University for granting the Research Assistant Scholarship and the Overseas Research Scholarship.

Supplementary material

11144_2018_1485_MOESM1_ESM.docx (309 kb)
Supplementary material 1 (DOCX 309 kb)

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Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2018

Authors and Affiliations

  1. 1.Department of Chemical Engineering, Faculty of EngineeringThammasat UniversityPathum ThaniThailand
  2. 2.Department of Mechanical Engineering, Faculty of EngineeringThammasat UniversityPathum ThaniThailand
  3. 3.Department of Chemical Engineering and BiotechnologyNational Taipei University of TechnologyTaipeiTaiwan
  4. 4.Department of Occupational Safety and HealthChina Medical UniversityTaichungTaiwan

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