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Green etherification of bioglycerol with 1-phenyl ethanol over supported heteropolyacid

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Abstract

Escalating demand for biodiesel production has generated surplus glycerol. Therefore, the consumption of glycerol for valuable conversions has become a global challenge. In an effort to convert glycerol, we have etherified it to make a biologically active component, 3-(1-phenylethoxy) propane-1,2-diol. Etherification of glycerol with 1-phenyl ethanol was carried out by using heterogeneous acid catalysts. The process is green and clean. Different types of heteropolyacids (HPAs) supported on hexagonal mesoporous silica (HMS) and K-10 clay were prepared by incipient-wetness technique and screened to get high selectivity towards monoether of glycerol. 20% w/w dodeca-tungstophosphoric acid (DTP)/HMS was found to be the best. The effects of various reaction parameters such as speed of agitation, catalyst loading, mole ratio of reactants and temperature were evaluated systematically to prove that the reaction obeys Langmuir–Hinshelwood–Hougen–Watson (LHHW) type of mechanism. It was also observed that the reaction was free from any external mass transfer as well as intra-particle diffusion limitations and was intrinsically kinetically controlled. An overall second order kinetic equation was used to fit the experimental data, under the assumption that all the species are weakly adsorbed on the catalytic sites. Apparent activation energy was estimated as 27.0 kcal/mol. Solvent-free condition for this reaction has also added the green chemistry perception to the reaction.

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Abbreviations

a p :

Solid–liquid interfacial area (cm2/cm3 of liquid phase)

A:

Reactant species A—1-phenyl ethanol

AS:

Chemisorbed A

B:

Reactant species B—Glycerol

BS:

Chemisorbed B

P:

Monoether of glyceryl ether (product)

PS:

Chemisorbed Product

W:

Water

C A, C B :

Concentration of A and B (mol/cm3)

C A0, C B0 :

Initial concentration of A and B (mol/cm3)

C AS, C BS :

Concentration of A and B at solid (catalyst) surface (mol/g cat)

C PS, C WS :

Concentration of P and W at solid (catalyst) surface (mol/g cat)

C S :

Concentration of vacant sites (mol/g cat)

C t :

Total concentration of the sites (mol/g cat)

C WP :

Weisz–Prater constant

D P :

Diameter of catalyst particle (m)

D AB :

Diffusion coefficient of A in B (m2/s)

D BA :

Diffusion coefficient of B in A (m2/s)

D e :

Effective diffusivity (cm2/s)

Rp:

Radius of catalyst particle (m)

−r A :

Rate of disappearance of A (cm3/gmol s)

k SLA, k SLB :

Solid–liquid mass transfer coefficients (m/s)

K A :

Equilibrium constant for adsorption of A on catalyst surface (l mol−1 min−1)

K B :

Equilibrium constant for adsorption of B on catalyst surface (l mol−1 min−1)

k SR :

Surface reaction rate constant for forward reaction (l mol−1 min−1)

k SR′ :

Surface reaction rate constant for reverse reaction (l mol−1 min−1)

K P :

Equilibrium constant for adsorption of P on catalyst surface (min−1)

K W :

Equilibrium constant for adsorption of W on catalyst surface (min−1)

r obs :

Observed rate of reaction (mol/g cat/s)

S:

Vacant site

Sh :

Sherwood number

t :

Time (min)

w :

Catalyst loading (g/cm3 of liquid phase)

X A :

Fractional conversion of A

ϵ:

Porosity

ρ p :

Density of catalyst particle (g/cm3)

τ :

Tortuosity (-)

μ :

Viscosity of reaction mixture (kg/m.s)

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Acknowledgments

G. D. Yadav received support for personal chairs from Darbari Seth and R. T. Mody Distinguished Professor endowments and J.C. Bose National Fellowship from Department of Science and Technology, Govt. of India. Financial support from the CSIR-NMITLI is gratefully acknowledged. Payal Chandan received SRF from this grant. Nirupama Gopalaswami received a summer fellowship for undergraduate students from the National Academies.

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  1. Department of Chemical Engineering, Institute of Chemical Technology (ICT), Matunga, Mumbai, 400 019, India

    Ganapati D. Yadav, Payal A. Chandan & Nirupama Gopalaswami

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  1. Ganapati D. Yadav
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  2. Payal A. Chandan
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  3. Nirupama Gopalaswami
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Correspondence to Ganapati D. Yadav.

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Yadav, G.D., Chandan, P.A. & Gopalaswami, N. Green etherification of bioglycerol with 1-phenyl ethanol over supported heteropolyacid. Clean Techn Environ Policy 14, 85–95 (2012). https://doi.org/10.1007/s10098-011-0380-2

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