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

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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.

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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

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Acknowledgements

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

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Authors and Affiliations

  1. Department of Chemical Engineering, National Institute of Technology, Durgapur, West Bengal, 713209, India

    Sumit H. Dhawane & Gopinath Halder

  2. Department of Chemical Engineering, Cairo University, Giza, 12613, Egypt

    E. G. Al-Sakkari

Authors
  1. Sumit H. Dhawane
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  2. E. G. Al-Sakkari
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  3. Gopinath Halder
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Dhawane, S.H., Al-Sakkari, E.G. & Halder, G. Kinetic Modelling of Heterogeneous Methanolysis Catalysed by Iron Induced on Microporous Carbon Supported Catalyst. Catal Lett 149, 3508–3524 (2019). https://doi.org/10.1007/s10562-019-02905-5

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