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Hydrogen solubility in biphasic liquid reaction mixture of cinnamaldehyde hydrogenation: experimental and mathematical modeling study

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Abstract

The solubility of hydrogen in the biphasic reaction mixture of cinnamaldehyde hydrogenation at 298 to 353 K has been determined in this work experimentally and by using a thermodynamic model. It is evident from many studies that the addition of extra phase, aqueous KOH as the fourth phase, to the three-phase cinnamaldehyde hydrogenation mixture [gas (hydrogen)-liquid (cinnamaldehyde + toluene)-solid (catalyst)] leads to enhancement of cinnamyl alcohol selectivity to a great extent. Determination of hydrogen solubility in this biphasic (organic-aqueous) reaction mixture is crucial to understand the intrinsic reaction kinetics of this reaction. The solubility of hydrogen was experimentally determined using a pressure drop method and reported in terms of Henry’s constant. Firstly, hydrogen solubility was determined in pure components viz. toluene, cinnamaldehyde, and water followed by determination of its solubility in the cinnamaldehyde-toluene mixture, aqueous KOH, and eventually, in the reaction mixture containing the two immiscible liquid phases. The effect of changing concentrations in these mixtures and changing phase holdups in the total reaction mixture on hydrogen solubility was studied. Starting from pure components to the reaction mixture, the hydrogen solubility was predicted using a two-step thermodynamic approach involving regular solution theory and the theory of corresponding states. The solubility predictions from this thermodynamic model will be helpful in the accurate estimation of kinetic parameters.

Graphical abstract

Solubility of the hydrogen was determined experimentally in pure toluene, cinnamaldehyde, water, aqueous KOH and in mixtures of cinnamaldehyde+ toluene, biphasic reaction mixture for cinnamaldehyde hydrogenation (containing cinnamaldehyde + toluene + aq. KOH) in the temperature range of 298-353 K. The same was predicted using a thermodynamic model.

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Abbreviations

\(f_{A}^{L}\) :

Fugacity of hypothetical liquid phase of solute gas (MPa)

\(f_{A}\) :

Fugacity of the solute gas (MPa)

\(H_{v}\) :

Heat of vaporization of solvent (J mol-1)

\(\Delta H_{s}\) :

Heat of solution (J mol-1)

\(k_{h}\) :

Henry’s Constant (kmol m-3 MPa-1)

\(M\) :

Molarity of KOH in aqueous phase (M)

P:

Pressure (MPa)

Pb :

Pressure at boiling point (MPa)

Pc :

Critical pressure of solvent (MPa)

Pr :

Reduced pressure of solvent

T:

Temperature (K)

Tb :

Normal boiling point (K)

Tc :

Critical temperature of solvent (K)

Tr :

Reduced temperature of solvent

Trb :

Reduced temperature at normal boiling point (Tb)

\(v_{A}\) :

Molar volume of hypothetical liquid gas (m3 kmol-1)

\(v_{s}\) :

Molar volume of solvent (m3 kmol-1)

\(x_{A}\) :

Mole fraction of dissolved gas in solvent

\(\emptyset\) :

Volume fraction of solvent

\(\delta_{s}\) :

Hildebrand solubility parameter for solvent (MPa1/2)

\(\delta_{A}\) :

Hildebrand solubility parameter for solute gas (MPa1/2)

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Acknowledgement

Academy of Scientific and Innovative Research (AcSIR), CSIR- Human Resource Development Centre, Campus Postal Staff College Area, Ghaziabad 201002, India. Alkyl Amines Chemicals Limited, Pune, India.

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Authors and Affiliations

  1. Chemical Engineering and Process Development Division, CSIR- National Chemical Laboratory, Dr. Homi Bhabha Road, Pune, 411008, India

    Muzammil Y Khan & Sunil S Joshi

  2. Academy of Scientific and Innovative Research (AcSIR), CSIR- Human Resource Development Centre, Campus Postal Staff College Area, Ghaziabad, 201002, India

    Muzammil Y Khan & Sunil S Joshi

  3. School of Chemistry and Chemical Engineering, Queen’s University, Belfast, Northern Ireland, United Kingdom

    Vivek V Ranade

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  1. Muzammil Y Khan
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Correspondence to Sunil S Joshi.

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Khan, M.Y., Joshi, S.S. & Ranade, V.V. Hydrogen solubility in biphasic liquid reaction mixture of cinnamaldehyde hydrogenation: experimental and mathematical modeling study. J Chem Sci 134, 1 (2022). https://doi.org/10.1007/s12039-021-01987-2

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