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Catalysis Letters

, Volume 149, Issue 12, pp 3508–3524 | Cite as

Kinetic Modelling of Heterogeneous Methanolysis Catalysed by Iron Induced on Microporous Carbon Supported Catalyst

  • Sumit H. DhawaneEmail author
  • E. G. Al-Sakkari
  • Gopinath HalderEmail author
Article
  • 71 Downloads

Abstract

The investigation describes detailed kinetic modelling of biodiesel synthesis catalysed by waste derived carbonaceous catalyst in a batch reactor. The modelling is conducted via three approaches i.e. power law equation, Eley–Rideal (E–R) and Langmuir–Hinshelwood (L–H) mechanism. Reversible and irreversible pathways with respect to triglycerides (TG) and fatty acid methyl esters (FAME) for first and second order reactions were considered for developing model equations. The kinetics of heterogeneous catalysis is studied using E–R and L–H mechanism to assess the exact rate controlling step by considering all the possible resistances offered by solid catalyst. The rate expressions for adsorption and desorption of individual reactant and product and surface chemical reaction were also developed. The influence of diffusional resistance offered by solid catalyst on conversion is also determined. The best fitted model is identified from calculated regression coefficients. The results revealed that glycerol desorption from catalyst surface given by E–R and L–H mechanisms is controlling the biodiesel synthesis process. The best suited model equation is considered for evaluating the kinetic parameters of the transesterification process. Thus, the study gives exact rate controlling step for heterogeneous catalysis to be used for reactor design and cost-effective production of biodiesel.

Graphic Abstract

Keywords

Biodiesel Heterogeneous catalysis Carbon catalyst Kinetic modelling Mass transfer studies 

Abbreviations

%x

Percentage conversion

TG

Triglyceride (rubber seed oil)

MA

Methanol

DG

Diglyceride

MG

Monoglyceride

Deff

Effective diffusivity

CA

Concentration of component A (mol L−1)

DAB

Diffusivity of component A in component B

r

Rate (mol L−1 h−1)

t

Time (min)

K

Rate constant at constant methanol concentration

\({{\text{K}^{\prime}}},\,{{\text{K}^{\prime\prime}}}\,{\text{and}}\,{{\text{K}^{\prime\prime}}}_{{\text{i}}}\)

Constants

(k1)

Rate constant for conversion of TG → DG

(k2)

Rate constant for conversion of DG → TG

(k3)

Rate constant for conversion of DG → MG

(k4)

Rate constant for conversion of MG → DG

(k5)

Rate constant for conversion of MG → G

(k6)

Rate constant for conversion of G → MG

(kt)

Rate constant for conversion of TG → G (for overall reaction)

(kt−)

Rate constant for conversion of G → TG (for  overall reaction)

K1, K2, K3, K4

Constants

(kad)

Rate constant for methanol adsorption in forward reaction

(kad−)

Rate constant for methanol adsorption in backward reaction (ER)

(ks)

Rate constant for forward surface reaction (ER)

(ks−)

Rate constant for backward surface reaction (ER)

(kd)

Rate constant for desorption of glycerol in forward reaction (ER)

(kd−)

Rate constant for desorption of glycerol in backward reaction (ER)

S

Active sites

\(\left({{{\text{K}^{\prime}}}_{{{\text{ad}}}} } \right)\)

Equilibrium constant methanol adsorption(ER)

\(\left({{{\text{K}^{\prime}}}_{{{\text{d}}}} } \right)\)

Equilibrium constant for glycerol desorption (ER)

Ct

Concentration of total active sites

Cv

Concentration of vacant active sites

K1, K2, K3, K4

Constants

E

Activation energy

R

Universal gas constant

Ao

Pre-exponential factor

Notes

Acknowledgements

The authors would like to thank Rashmi Dhurandhar and Sumona Show for their technical support in characterisation of catalyst.

Compliance with Ethical Standards

Conflict of interest

Authors declare there is no conflict of interest.

Supplementary material

10562_2019_2905_MOESM1_ESM.docx (18 kb)
Supplementary material 1 (DOCX 17 kb)

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Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of Chemical EngineeringNational Institute of TechnologyDurgapurIndia
  2. 2.Department of Chemical EngineeringCairo UniversityGizaEgypt

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