Preparation of Amberlyst-coated pervaporation membranes and their application in the esterification of acetic acid and butanol

doi:10.1016/j.apcata.2006.10.006

Applied Catalysis A: General

Volume 317, Issue 1, 27 January 2007, Pages 113-119

https://doi.org/10.1016/j.apcata.2006.10.006 Get rights and content

Abstract

Catalytic Amberlyst 15 layers have been deposited on composite ceramic/poly(vinyl)alcohol membranes by the dip-coat technique using Aculyn^® as a rheology modifier. Tuning of the catalytic layer thickness is possible by varying the number of dip-coat steps. The obtained “dried-mud like” Amberlyst 15 layers are stable during pervaporation and reaction experiments. The catalytic activity of the Amberlyst-coated pervaporation membrane equals the activity of the unsupported catalyst. In the pervaporation-assisted esterification reaction between acetic acid and 1-butanol the catalytic membrane is able to couple catalytic activity and water removal. Due to the high activity of the Amberlyst catalyst the conversion of the esterification reaction is limited by the removal rate of water through the membrane. This is in contrast to zeolite-coated pervaporation membranes, for which the conversion of the esterification reaction between acetic acid and 1-butanol is limited by the catalytic activity.

Graphical abstract

In the manuscript we describe the preparation of composite catalytic membranes by deposition of catalytic Amberlyst 15 layers on top of ceramic supported PVA membranes via the dip-coating technique. We show that this approach allows independent optimisation of both the catalytic and separation functions of the membranes, facilitating efficient integration of reaction and separation.

Introduction

Pervaporation can be used to increase the conversion of reversible condensation reactions, generating water as a by-product. Several authors have shown that the equilibrium displacement is enhanced by means of catalytically active membranes [1], [2], [3], [4], [5]. The integration of the selective and catalytic function into one single layer, however, demands contradicting material properties [6]. For example, to achieve a high separation selectivity the diffusion of the reactants and the wanted product inside the material should be low, whereas efficient use of the catalytic properties requires the diffusion of both reactants and products to be high. The conflicting demands on materials properties can be avoided by accommodating the selective and catalytic features in two different distinct layers, which are in close physical contact [4], [7], [8]. This approach allows independent optimisation of the selective and the catalytic properties.

Previously, we have prepared H-USY zeolite-coated silica membranes by means of the dip-coat technique [7] and evaluated their performance in the esterification reaction between acetic acid and 1-butanol. Due to low catalyst activity the performance of these composite membranes is limited by the reaction kinetics and a more active catalyst would improve performance. Ion-exchange resins, such as Amberlyst 15, have proven to be effective heterogeneous catalysts in liquid phase esterification reactions [9], [10], [11], [12], [13], [14] and have previously been used as catalytic coating in the hydration of alkenes [15] and dimerisation of isobutene [16]. The weight-based activity of Amberlyst 15 in the esterification of acetic acid and 1-butanol is roughly ten times higher compared to the activity of the H-USY zeolite.

The present study focuses on the preparation of Amberlyst 15-coated water-selective membranes. Amberlyst coatings have been applied on top of composite ceramic/polymer membranes by means of the dip-coat technique. This versatile technique allows controlling of the catalyst layer thickness [17], which is important because an optimal catalytic layer thickness exists [6]. The performance of the catalytic membranes in the esterification reaction between acetic acid and 1-butanol has been examined.

Section snippets

Activity of catalysts

The activity of unsupported Amberlyst 15 was measured in the esterification of acetic acid and 1-butanol in a batch reflux system [14]. Amberlyst 15 was obtained from Rohm and Haas (Germany) and was dried for 24 h at 90 °C prior to use. A three-necked flask equipped with a condenser and stirrer was charged with a certain amount of acid (0.66 mol) and pre-activated catalyst. Then, the system was heated up to the reaction temperature after which the pre-heated alcohol (0.66 mol) was added. The

Amberlyst 15 activity

The activity of Amberlyst 15 in the esterification reaction between acetic acid and 1-butanol is evaluated at 75 °C. In addition, the effect of milling and Aculyn^® addition on the Amberlyst activity is investigated. The results listed in Table 3.

From Table 3 it can be seen that the activity of the powderous Amberlyst 15 is higher as compared to the Amberlyst 15 beads. Possibly there is a slight contribution of internal mass transfer limitations in the bead-shaped Amberlyst particles [10]. The

Conclusions

Composite catalytically active membranes can be used to enhance conversion of esterification reactions as the reaction and separation function are efficiently coupled. An additional advantage is that both the selective layer and the catalytic layer can be optimised independently. In this work composite catalytic membranes have been prepared by the dip-coating technique, which allows tuning of catalytic layer thickness by varying the number of dip-coat steps. Catalytic Amberlyst 15 layers have

Acknowledgements

This work was performed in a cooperative project of the Centre for Separation Technology and was financially supported by TNO and NOVEM.

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¹: Current address: SINTEF Materials Technology, P.O. Box 124, Blindern, N-0314 Oslo, Norway.

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Preparation of Amberlyst-coated pervaporation membranes and their application in the esterification of acetic acid and butanol

Abstract

Graphical abstract

Introduction

Section snippets

Activity of catalysts

Amberlyst 15 activity

Conclusions

Acknowledgements

Trans. IChemE A: Chem. Eng. Res. Des.

Appl. Catal. A

Catal. Today

Chem. Eng. Sci.

Appl. Catal. A

React. Funct. Polym.

Appl. Catal. A: Gen.

Catal. Today

Appl. Catal. A

J. Membr. Sci.

J. Membr. Sci.