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Microwave-assisted synthesis of malic acid involving hydrochloric acid as catalyst

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Abstract

The competing acid catalyzed reactions of fumaric acid (F) isomerization to form maleic acid (Mx) (reaction R1), and the hydration of F to malic acid (M) (reaction R2) were investigated under microwave heating. The kinetic experiments were performed in a sealed microwave-irradiated batch reactor operated at pressures between 615 and 1715 kPa, in the temperature range from 433 to 478 K, and for reaction times up to 21,600 s. Hydrochloric acid at three different concentrations (C H  = 0.65, 1.30 and 1.94 M) was used as the catalyst. The concentrations of F, Mx and M were periodically determined by HPLC analyses. The Arrhenius parameters for the forward rate constants of the reactions R1 and R2 were tuned on the experimental data of species concentrations (k 10 = 5.63 ± 0.04 M−1 s−1, E a1/R = 4837 ± 121 K, k 20 = (6.9 ± 0.3) × 107 M−2 s−1, E a2/R = 13,532 ± 212 K). The tuning procedure involved the Simplex method of optimization, and a kinetic model represented by a system of four ordinary differential equations from material balances on species F, Mx, M and HCl. The model was able to reproduce the variation in species concentrations with time for all experimental conditions investigated, just with a partial set of the currently obtained data used to adjust the model parameters (C H  = 0.65 M and 1.94 M). The current results at C H of 1.30 M and analogous data from the literature under quite different reaction conditions (e.g.; C H  = 0.97 M, non-isothermal reactor externally heated with glycerol) confirm the reliability of the modeling approach. The catalyst concentration had the expected significant effect on the reaction rates, but the influence of microwave irradiation on the kinetics of the conversion of F and on the selectivity of M was small.

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Abbreviations

C F :

Concentration of fumaric acid (mol l−1)

C F0 :

Initial concentration of fumaric acid (mol l−1)

C H :

Concentration of hydrochloric acid (mol l−1)

C M :

Concentration of malic acid (mol l−1)

C Mx :

Concentration of maleic acid (mol l−1)

C W :

Concentration of water (mol l−1)

C WR :

Concentration of water in experiments reported in the literature (mol l−1)

E a1 :

Tuned activation energy of the isomerization reaction (J kmol−1)

E a2 :

Tuned activation energy of the hydration reaction (J kmol−1)

f :

Objective function defined by Eq. 5

k 1 :

Forward-rate constant of the isomerization reaction R1 (M−1 s−1)

k 10 :

Tuned preexponential factor of the isomerization reaction R1 (M−1 s−1)

K 1 :

Equilibrium constant for the isomerization reaction R1 at a temperature T

k 2 :

Forward-rate constant of the hydration reaction R2 (M−2 s−1)

k 20 :

Tuned preexponential factor of the hydration reaction R2 (M−2 s−1)

k 2R :

Model parameter of Eq. 10

K 2 :

Equilibrium constant for the hydration reaction R2 at a temperature T (M−1)

K 2R :

Model parameter of Eq. 10

P :

Reaction pressure (kPa)

R :

Gas constant (J kmol−1 K−1)

t :

Reaction time (s)

t max :

Longest reaction time for a given experimental run (s)

T :

Reaction temperature (K)

x F :

Conversion of fumaric acid

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Authors and Affiliations

  1. Department of Chemical Engineering, Federal University of Paraná, Curitiba, PR, Brazil

    Ronald Wbeimar Pacheco Ortiz & Everton Fernando Zanoelo

  2. Instituto de Tecnologia e Pesquisa, Universidade Tiradentes, Aracajú, SE, Brazil

    Brendha Gonçalves de Jesús, Elton Franceschi & Cláudio Dariva

  3. Department of Chemical Engineering, Universidade Estadual de Maringá, Maringá, PR, Brazil

    Lúcio Cardozo-Filho

  4. Centro Universitário da Fundação de Ensino Octávio Bastos (UNIFEOB), São João da Boa Vista, SP, Brazil

    Lúcio Cardozo-Filho

Authors
  1. Ronald Wbeimar Pacheco Ortiz
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  2. Brendha Gonçalves de Jesús
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  3. Elton Franceschi
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  4. Cláudio Dariva
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  5. Lúcio Cardozo-Filho
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  6. Everton Fernando Zanoelo
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Corresponding author

Correspondence to Everton Fernando Zanoelo.

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Ortiz, R.W.P., de Jesús, B.G., Franceschi, E. et al. Microwave-assisted synthesis of malic acid involving hydrochloric acid as catalyst. Reac Kinet Mech Cat 122, 793–802 (2017). https://doi.org/10.1007/s11144-017-1287-7

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  • DOI: https://doi.org/10.1007/s11144-017-1287-7

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