Inorganic Membrane Reactors E-Book

Xiaoyao Tan

• Herausgeber: John Wiley & Sons
• Kategorie: Fachliteratur
• Sprache: Englisch

Seitenzahl: 431

Veröffentlichungsjahr: 2015

Beschreibung

Membrane reactors combine membrane functions such as separation, reactant distribution, and catalyst support with chemical reactions in a single unit. The benefits of this approach include enhanced conversion, increased yield, and selectivity, as well as a more compact and cost-effect design of reactor system. Hence, membrane reactors are an effective route toward chemical process intensification.

This book covers all types of porous membrane reactors, including ceramic, silica, carbon, zeolite, and dense metallic reactors such as Pd or Pd-alloy, oxygen ion-conducting, and proton-conducting ceramics. For each type of membrane reactor, the membrane transport principles, membrane fabrication, configuration and operation of membrane reactors, and their current and potential applications are described comprehensively. A summary of the critical issues and hurdles for each membrane reaction process is also provided, with the aim of encouraging successful commercial applications.

The audience for Inorganic Membrane Reactors includes advanced students, industrial and academic researchers, and engineers with an interest in membrane reactors.

Leseprobe

Inorganic Membrane Reactors

Fundamentals and Applications

Xiaoyao Tan

Department of Chemical EngineeringTianjin Polytechnic UniversityChina

Kang Li

Department of Chemical Engineering

and Chemical Technology

Imperial College London

UK

This edition first published 2015© 2015 John Wiley & Sons, Ltd

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Library of Congress Cataloging-in-Publication Data

Tan, Xiaoyao.Inorganic membrane reactors : fundamentals and applications / Xiaoyao Tan, Kang Li.  pages cm Includes bibliographical references and index.

 ISBN 978-1-118-67284-6 (cloth)1. Membrane reactors. I. Li, Kang, 1960– II. Title.  TP248.25.M45T36 2015 660′.2832–dc23    2014021348

A catalogue record for this book is available from the British Library.

Preface

Membrane reactors combine membrane functions such as product separation, reactant distribution, and catalyst support with chemical reactions in a single unit, leading to enhanced conversion and/or improved selectivity/yield. This combination also provides advantages compared with conventional reaction/separation systems – such as lower energy requirements, the possibility of heat integration, and safer operation. Such advantages lead potentially to compact and cost-effective design of reactor systems with substantial savings in processing costs. As one of the most effective solutions in chemical process intensification, membrane reactor technology has attracted substantial worldwide research and process development efforts in the last 30 years, and the subject is still currently undergoing rapid development and innovation.

Nowadays, membrane reactors have found commercial applications in biochemical processes (thus called membrane bioreactors) – for example, the production of fine chemicals via use of enzymes, large-scale biogas production from wastes, and environmental clean-up (wastewater treatment). These processes operate at low temperatures, seldom exceeding 60 °C, and thus polymeric membranes can be used. However, most chemical reactions of interest operate at temperatures well in excess of the limitation of polymeric membranes (100–150 °C). The development of inorganic membrane materials (zeolites, ceramics, and metals) with inherent high-temperature structural and chemical stability has broadened the application potential of membrane reactors toward the (petro)chemical industry. Many of these materials can be applied at elevated temperatures (up to 1000 °C), allowing their application in catalytic processes. Nevertheless, inorganic membrane reactors have not found any large-scale commercial applications so far, which implies that there are still a lot hurdles to their practical application. The challenges involve not only fundamentals but also engineering aspects. On the contrary, many novel inorganic membranes and membrane reaction processes have been developed in recent years. Review articles and book chapters have also emerged on all types of inorganic membrane reactors in the past few years. The present book aims to describe the fundamentals of various types of inorganic membrane reactors, demonstrate the extensive applications in a variety of chemical reaction processes, and elucidate the limitations, challenges, and potential areas for future innovation. It is nevertheless not the intention to provide a complete overview of all the relevant literature, but rather to highlight the current state and advances in inorganic membrane reactors. It is hoped that this book will serve as a useful source of information for both novices learning about membrane reactors and scientists and engineers working in this field.

The book starts with a general description of inorganic membranes and membrane reactors, followed by a detailed description of each type – porous, zeolite, metallic, and ionic transport ceramic membrane reactors – in separate chapters. We are conscious of the importance of producing membranes with the desired properties of good separation and selectivity, and enough robustness to withstand the severe operating conditions often encountered in industrial practice. For each type of membrane reactor, all the important topics such as the membrane transport principle, membrane fabrication, configuration and operation, current and potential applications are described comprehensively. A summary of critical issues and hurdles for each membrane reaction process is also provided to help readers focus on the key problems in making the technology succeed commercially. As the modeling methodology contributes significantly to the knowledge-based development of membrane reactors and engineering, a separate chapter involving a general modeling process for membrane reactors and their applications to typical reaction systems is included at the end of the book.

This book may serve as introductory material for novices learning about membrane reactors, and also as a reference for professionals. Novices can grasp the elementary concepts, and professionals can familiarize themselves with the most recent developments in the area. The audience for this book will be industrial and institutional researchers, scientists and engineers with an interest in membrane reactors, and also senior undergraduate and postgraduate students pursuing advanced membrane separation/reaction courses.

We are deeply indebted to many colleagues and students for the completion of this book. A number of people contributed to this book, including Jian Song, Zhigang Wang, Zhaobao Pan, Nan Liu, Haiping Pan, Yang Liu, Zhentao Wu, Franciso Garcia Garcia, Nur Othman, and Ana Gouveia Gil, and they are acknowledged for their assistance with various aspects.

Our special thanks go to several members of staff at John Wiley: Emma Strickland, Sarah Keegan, and Audrey Koh for their patience and advice, and Rebecca Stubbs for initiating the book. Also Jayavel Radhakrishnan of SPi Global.

Finally, we would like to acknowledge financial support provided by the Royal Academy of Engineering in the UK for writing the book and our ongoing research funding in ceramic membranes and catalysis provided by EPSRC in the UK and NSFC in China.

1Fundamentals of Membrane Reactors

1.1 Introduction

A membrane reactor (MR) is a device integrating a membrane with a reactor in which the membrane serves as a product separator, a reactant distributor, or a catalyst support. The combination of chemical reactions with the membrane functions in a single step exhibits many advantages, such as preferentially removing an intermediate (or final) product, controlling the addition of a reactant, controlling the way for gases to contact catalysts, and combining different reactions in the same system. As a result, the conversion and yield can be improved (even beyond the equilibrium values), the reaction conditions can be alleviated, and the capital and operational costs can be reduced significantly. Different reactions usually require different types of membranes. Membrane reactors are also operated in different modes. The purpose of this chapter is to introduce readers to the main concepts of membranes and membrane reactors. The principles, structure, and operation of inorganic membrane reactors are presented below.

1.2 Membrane and Membrane Separation

A membrane is defined as a region of discontinuity interposed between two phases [1]. It restricts the transport of certain chemical species in a specific manner. In most cases, the membrane is a permeable or semi-permeable medium and is characterized by permeation and perm-selectivity. In other words, the membrane may have the ability to transport one component more readily than others due to the differences in physical and/or chemical properties between the membrane and the permeating components.

1.2.1 Membrane Structure

Membranes can be classified according to different viewpoints – for example, membrane materials, morphology and structure of the membranes, preparation methods, separation principles, or application areas. In general, the most illustrative means of classifying membranes is by their morphology or structure, because the membrane structure determines the separation mechanism and the membrane application. Accordingly, two types of membranes may be distinguished: symmetric and asymmetric membranes. Symmetric membranes have a uniform structure in all directions, which may be either porous or non-porous (dense). A special form of symmetric membrane is the liquid immobilized membrane (LIM) that consists of a porous support filled with a semi-permeable liquid or a molten salt solution. Asymmetric membranes are characterized by a non-uniform structure comprising a selective top layer supported by a porous substrate of the same material. If the selective layer is made of a different material from the porous substrate, we have a composite membrane. Figure 1.1 shows schematically the principal types of membranes.

Figure 1.1 Schematic diagrams of the principal types of membranes: (a) porous symmetric membrane; (b) non-porous/dense symmetric membrane; (c) liquid immobilized membrane; (d) asymmetric membrane with porous separation layer; (e) asymmetric membrane with dense separation layer.

Sometimes, the porous support itself may also possess different pores and exhibit an asymmetric structure. Figure 1.2 depicts the cross-section of an asymmetric membrane where the structural asymmetry is clearly observed [2]. The asymmetric membranes usually have a thin selective top layer to obtain high permeation flux and a thick porous support to provide high mechanical strength. The resistance of the membrane to mass transfer is largely determined by the thin top layer.

Figure 1.2 Cross-sectional SEM image of an asymmetric membrane.

Reproduced from [2]. With permission from Elsevier.

Based on the membrane structure and separation principle, membranes can also be classified into porous and dense (non-porous) membranes, as depicted schematically in Figure 1.3. The porous membranes have a porous separation layer and induce separation by discriminating between particle (molecular) sizes (Figure 1.3(a)). The separation characteristics (i.e., flux and selectivity) are determined by the dimensions of the pores in the separation layer. The membrane material is of crucial importance for chemical, thermal, and mechanical stability but not for flux and rejection. The non-porous/dense membranes have a dense separation layer, and separation is achieved through differences in solubility or reactivity and the mobility of various species in the membrane. Therefore, the intrinsic properties of the membrane material determine the extent of selectivity and permeability. The LIMs can be considered as a special dense membrane since separation takes place via the filled liquid semi-permeable phase, although a porous structure is contained within the membrane.

Figure 1.3 Schematic drawing of the permeation in porous and dense membranes.

1.2.2 Membrane Separation

The membrane separation process is characterized by the use of a membrane to accomplish a particular separation. Figure 1.4 shows the concept of a membrane separation process. By controlling the relative transport rates of various species, the membrane separates the feed into two streams: the retentate and the permeate. Either the retentate or the permeate can be the product of the separation process.

Figure 1.4 Schematic drawing of the membrane separation process.

The performance of a membrane in separation can be described in terms of permeation rate or permeation flux (mol m–2 s–1) and perm-selectivity. The permeation flux is usually normalized per unit of pressure (mol m–2 s–1 Pa–1), called the permeance, or is further normalized per unit of thickness (mol m m–2 s–1 Pa–1), called the permeability, if the thickness of the separation layer is known. In many cases only a part of the separation layer is active, and the use of permeability gives rise to larger values than the real intrinsic ones. Therefore, in case of doubt, the flux values should always be given together with the (partial) pressure of the relevant components at the high-pressure (feed) and low-pressure (permeate) sides of the membrane as well as the apparent membrane thickness.

The permeation flux is defined as the molar (or volumetric or mass) flow rate of the fluid permeating through the membrane per unit membrane area. It is determined by the driving force acting on an individual component and the mechanism by which the component is transported. In general cases, the permeation flux (J) through a membrane is proportional to the driving force; that is, the flux–force relationship can be described by a linear phenomenological equation:

(1.1)

where L is called the phenomenological coefficient and dX/dx is the driving force, expressed as the gradient of X (temperature, concentration, pressure, etc.) along the coordinate (x) perpendicular to the transport barrier. The mass transport through a membrane may be caused by convection or by diffusion of an individual molecule – induced by a concentration, pressure, or temperature gradient – or by an electric field. The driving force for membrane permeation may be the chemical potential gradient (Δμ) or the electrical potential gradient (Δϕ) or both (the electrochemical potential is the sum of the chemical potential and the electrical potential). In case the concentration gradient serves as the driving force, the transport equation can be described by Fick's law:

(1.2)

where DAm (m2 s–1) is the diffusion coefficient of component A within the membrane. It is a measure of the mobility of the individual molecules in the membrane and its value depends on the properties of the species, the chemical compatibility of the species, the membrane material, and the membrane structure as well. In practical diffusion-controlled separation processes, useful fluxes across the membrane are achieved by making the membranes very thin and creating large concentration gradients across the membrane.

For the pressure-driven convective flow, which is most commonly used to describe flow in a capillary or porous medium, the transport equation may be described by Darcy's law:

(1.3)

where dp/dx is the pressure gradient existing in the porous medium, cA is the concentration of component A in the medium, and K is a coefficient reflecting the nature of the medium. In general, convective-pressure-driven membrane fluxes are high compared with those obtained by simple diffusion. More details of the transport mechanisms in membranes can be found elsewhere [3].

The perm-selectivity of a membrane toward a mixture is generally expressed by one of two parameters: the separation factor and retention. The separation factor is defined by

(1.4)

where yA and yB, xA and xB are the mole fractions of components A and B in the permeate and the retentate streams, respectively.

The retention is defined as the fraction of solute in the feed retained by the membrane, which is expressed by

(1.5)

where cf and cp are the solute concentrations in the feed and the permeate, respectively. For a selective membrane, the separation factors have values of 1 or greater whereas values of the retention are l or less.

Membrane separations are driven by pressure, concentration, or electric field across the membrane and can be differentiated according to type of driving force, molecular size, or type of operation. Common membrane processes include microfiltration, ultrafiltration, nanofiltration/reverse osmosis, gas separation, pervaporation, and dialysis/electrodialysis [3, 4]. Some processes have been applied extensively for separation and purification of gas and liquid mixtures in industry.

1.2.3 Membrane Performance

The membrane performance can be evaluated using permeability, selectivity, and stability. Ideally, a membrane with both high selectivity and permeability is required, but the attempt to maximize one factor will usually compromise the other. Comparatively, selectivity is a more important characteristic of a membrane because low permeability can be compensated to a certain extent by an increase in membrane surface area, whereas low selectivity leads to multi-stage processes which in most cases are not economical compared with established conventional processes.

The permeability and selectivity of a membrane are determined by the material and the structure of the membrane, which essentially determine the separation mechanism and application. Asymmetric membranes are mostly applied in practical applications because they have a thin selective layer to obtain high permeation fluxes and a thick porous support to provide high mechanical strength. For a certain mass separation, the type of membrane and the driving force required depend on the specific properties of the chemical species in the mixture.

In addition to permeability and selectivity, the following membrane stabilities are also required in various industrial applications:

chemical resistance

mechanical stability

thermal stability

stable operation.

Although the stability of a membrane depends on the membrane structure to some extent, it is mainly determined by the nature of the membrane material. For example, the upper temperature limit of polymeric membranes never exceeds 500°C, but inorganic materials can withstand very high temperatures and are inherently more stable at high temperatures and with various chemicals such as aggressive organic compounds and liquids with extreme pH values.

1.3 Inorganic Membranes

1.3.1 Types of Inorganic Membranes

Inorganic membranes are made of inorganic materials such as metals, ceramics, zeolites, glasses, carbon, and so on. Actually, inorganic membranes usually consist of several layers from one or more different inorganic materials. Details of inorganic membranes with respect to their syntheses, characterizations, transport theories, and scaling-up problems have been well reviewed and summarized by several authors [5, 6].

Inorganic membranes may be of either symmetric or asymmetric structure. Symmetric membranes often have considerable thickness to obtain sufficient mechanical strength. This is unfavorable for obtaining large fluxes, which usually require thin separation layers. In order to obtain high fluxes, most applicable inorganic membranes possess a multi-layered asymmetric structure as shown in Figure 1.5(a). A porous substrate with large pores (1–15 µm for low flow resistance) but sufficient mechanical strength is used to support a thin selective layer for separation. Commonly used materials for the macroporous support include Al2O3, ZrO2, TiO2, Si3N4, carbon, glass, stainless steel, and so on. Figure 1.5(b) shows the pore structure of a silica membrane supported on a cylindrical α-Al2O3 porous tube (outer diameter (OD) 10 mm; thickness 2 mm; average pore size 1 µm) [7].

Figure 1.5 (a) Schematic representation of the asymmetric inorganic membrane and (b) cross-sectional SEM image of the silica/Al2O3 composite membrane.

Reproduced from [7]. With permission from Elsevier.

In general, it is difficult to produce a thin separation layer directly on top of a support with large pores because the precursor system from which the separation layer is made will penetrate significantly into the pores of the support (e.g., the small particles from which small-pore membranes are made will penetrate much larger pores), leading to an increase in flow resistance. Furthermore, the thin layers covering large pores are mechanically unstable and would crack or peel off easily. A practical solution is to produce a graded structure by adding one or more intermediate layers with gradually decreasing layer thickness and pore size between the bulk support and the separation layer. An intermediate layer is also applied to match the thermal expansion difference of the membrane with the substrate, and as a buffer zone in case of chemical incompatibility during the membrane preparation process.

The separation layer may be dense (non-porous), such as Pd or Pd-alloy membranes for hydrogen separation and mixed (electronic, ionic) conducting oxide membranes for oxygen separation, or porous, such as metal oxides, silicalite, or zeolite membranes. Inorganic membranes are generally named for this separation layer, since it determines the properties and application of the membrane. The flux and selectivity of inorganic membranes are mainly determined by the quality of the separation layer, which is required to be defect-free and as thin as possible.

In addition to the planar geometry, inorganic membranes can also be produced in flat disk, tubular (dead-end or not), monolithic multi-channel, or hollow fiber configurations as shown in Figure 1.6. Disk membranes are often used in the laboratory because they can easily be fabricated by the conventional pressing method. In the case of tubes, they can be assembled in a module containing a number of tubes connected to a single manifold system.

Figure 1.6 Tubular (a), monolithic (b), and hollow fiber (c) inorganic membranes.

The multi-channel monolithic form is developed to increase the mechanical robustness and the surface area-to-volume ratio, which gives more separation area per unit volume of membrane element. In the monolithic membranes, the monolith bulk is a porous support and the separation layer is produced on the inner surface of the channels. Therefore, feed is introduced in the channels and the permeate is obtained from the membrane wall, as shown in Figure 1.7. The surface area-to-volume ratio of the multi-channel monolithic membrane ranges from 130–400 m2 m–3 compared with 30–250 m2 m–3 for tubes. Honeycomb multi-channel monolithic membranes can even reach up to 800 m2 m–3 of surface area-to-volume ratio.

Figure 1.7 Schematic picture of a multi-channel monolithic membrane.

Reproduced from [8]. With permission from Elsevier.

It is possible to increase the surface area-to-volume ratio of tubular membranes by decreasing their diameter. If the diameter of the membrane tube is reduced to a certain level, it is then called a hollow fiber membrane. Such hollow fiber membranes usually have an internal diameter ranging from 40–300 µm and wall thicknesses of 10–100 µm, and can provide surface area-to-volume ratios of more than 3000 m2 m–3 [4].

A variety of inorganic membranes are summarized in Table 1.1. The metal membranes mainly include palladium-based membranes for hydrogen permeation and silver-based membranes for oxygen permeation. Currently, the commercially available inorganic membranes are porous membranes made from alumina, silica and titania, glass, and stainless steel. These membranes are characterized by high permeability, but low selectivity. ZrO2- or CeO2-based membranes are solid oxide electrolytes and their permeability depends on their ionic conductivity.

Table 1.1 Types of inorganic membranes

Material

Structure

Configuration

Metal or alloys (Pd, Ag, Ni)

Symmetric/composite

Dense

Tube; plate; hollow fiber

Stainless steel

Symmetric

Porous

Tube; hollow fiber

Metal oxides (Al

2

O

3

, ZrO

2

, TiO

2

, etc.)

Symmetric/asymmetric

Porous/mesoporous

Tube; hollow fiber; monolith

Glass

Symmetric

Mesoporous

Hollow fiber; tube

Silica (SiO

2

)

Composite

Microporous

Plate; tube; hollow fiber; monolith

Zeolites (NaA, ZSM-5, etc.)

Composite

Microporous

Plate; tube; hollow fiber

Carbon

Symmetric/asymmetric

Microporous

Tube; hollow fiber

Mixed ionic–electronic ceramic conductors

Symmetric/asymmetric/composite

Dense

Tube; disk; plate; hollow fiber

ZrO

2

- or CeO

2

-based ionic conductors

Symmetric/asymmetric

Dense

Tube; disk; plate; hollow fiber

LIM (molten salt)

Symmetric

Dense

Tube; disk

1.3.2 Fabrication of Inorganic Membranes

As inorganic membranes have a multi-layered asymmetric structure consisting of porous support, intermediate layers and a selective separation layer, the fabrication of inorganic membranes is a multi-step process, as illustrated in Figure 1.8.

Figure 1.8 Fabrication process of inorganic membranes.

The fabrication starts with the preparation of porous substrates, with which the shape and configuration of the final membrane products can be determined. The porous substrate is critical for the quality of the membrane itself, because it not only provides sufficient mechanical strength but also takes effect on the permeability and selectivity of the membrane. Therefore, the commercial availability of high-quality substrates is a critical issue in the further development of membrane separation units.

Porous substrates are mostly made from ceramics like α-Al2O3, but also from other materials such as metal or glass. They are formed by shaping inorganic powders and consolidation of the green body by sintering. Four main stages are included in the fabrication process: choice of inorganic powder, paste/slurry preparation, shaping into green body, and firing into a porous substrate at high temperature. The particle size and morphology of the inorganic powders, the composition and homogeneity of the powder suspension, and the drying and firing conditions have considerable influence on the quality of the porous substrates [8]. Depending on the tubular or flat sheet (or disk) configuration, porous substrates can be prepared by the well-established techniques of slip casting, tape casting, pressing, or extrusion [4]. Figure 1.9 shows schematically the extrusion apparatus for shaping mono- or multi-channel tubular substrates. Different shapes are obtained by changing the geometry of the die (e.g., number of channels, diameter of channels, and external diameter of tubes).

Figure 1.9 Schematic view of the extrusion apparatus for the fabrication of tubular membranes (porous substrates): (1) endless screw; (2) paste inlet; (3) compression; (4) vacuum; (5) pressure gauge; (6) vacuum chamber; (7) die.

Reproduced from [8]. With permission from Elsevier.

Porous substrates should have a smooth surface with constant and homogeneous characteristics (wettability) and a narrow pore size distribution. Pores much larger than average and grains broken out of the surface, or irregularities in the porous substrate, may result in defects in the separation layer applied on it. Therefore, surface modification or formation of intermediate layer(s) is necessary to prepare a thin and defect-free membrane.

The preparation of intermediate layers is actually a process to produce a porous layer with smaller pores than those in the bulk support. Since it is difficult to have thermostable powder particles smaller than 5–6 nm, an intermediate layer with pore diameters below 2 nm cannot be produced by packing of spherical or plate-shaped particles. Sometimes, more than one intermediate layer has to be produced to form a graded structure with gradually decreasing layer thickness and pore size between the bulk support and the separation layer.

The separation layer, either porous or dense, can be formed using different methods such as sol-gel and template routes, hydrothermal synthesis, chemical vapor deposition (CVD), or physical sputtering, depending on the membrane material and its application. These membrane preparation methods will be described in the following chapters of this book for different membranes and membrane reactors. We note that the preparation of inorganic membranes involves a multi-step high-temperature treatment process. Therefore, inorganic membranes are much more expensive than polymeric ones.

1.3.3 Characterization of Inorganic Membranes

Inorganic membrane performances are determined by the membrane structure and the material properties. Information on pore size, shape, distribution, connectivity, and porosity for porous membranes and gas tightness, crystal structure, and surface properties for dense ceramic membranes is of importance to predict the separation performances of the membranes. The membranes developed have to undergo a series of characterization tests using techniques based on adsorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and so on. The characterization of inorganic membranes generally refers to three aspects: evaluation of porous features (porosity, pore size and distribution, tortuosity, etc.); microstructure and morphology (pore shape, surface, cross-section); and transport or reaction properties (permeability, selectivity, reactivity). Table 1.2 summarizes the common characterization methods for inorganic membranes.

Table 1.2 Characterization methods for inorganic membranes

Properties

Methods

Pore size

Bubble point

Porosity

Archimedes; Burnauer, Emmett, and Teller (BET)

Pore size distribution

Mercury porosimetry; thermoporometry

Tortuosity of pores

Permeation of pure water

Surface morphology

SEM, TEM, atomic force microscopy (AFM), scanning transmission microscopy (STM)

Cross-sectional morphology/thickness

SEM, STM

Crystalline phase

XRD

Grain structure/boundary

SEM, TEM

Mechanical strength

Three-point-bending method

Thermal expansion

Thermal dilatometer

Permeation rate

Pure gas or liquid permeation test

Selectivity

Separation factor or retention curves

Reactivity/catalytic activity

Reaction test

1.3.4 Applications of Inorganic Membranes

Compared with their polymeric counterparts, inorganic membranes are characterized by high chemical and thermal resistances and high mechanical stability, and thus can be applied in a harsh environment. However, inorganic membranes also exhibit the shortcoming of high cost, because of their long and complicated production route in which multi-step high-temperature treatment is required. Therefore, inorganic membrane applications should preferably be found in areas where polymer membranes cannot or do not perform well. The application areas of inorganic membranes mainly include [8]:

separation in food, beverage, and biotechnology fields;

purification in environmental protection;

energy conversion in solid oxide fuel cells;

separation and reaction in petroleum and chemical industries.

1.4 Inorganic Membrane Reactors

1.4.1 Basic Principles of Membrane Reactors

In a conventional design of chemical production process, the reaction and separation functions are carried out by two different processing units, as illustrated in Figure 1.10(a), where a membrane separator is used for product separation. If the membrane is placed inside the reactor to carry out the separation function as shown in Figure 1.10(b), it then becomes a membrane reactor. Since the reaction and separation proceed simultaneously, the separation of products can be accomplished in the reactor unit itself, or at least the downstream separation load can be reduced. As a result, the chemical process will become much simpler and the operational costs will thereby be reduced drastically. Moreover, the reaction can be enhanced significantly due to the combination of membrane functions. Based on the above discussions, an MR is a device integrating a membrane with a reactor in which the membrane functions as a separator or a reaction interface to enhance the reaction process.

Figure 1.10 (a) Conventional reactor and membrane separator; (b) membrane reactor.

Both organic (polymeric) and inorganic membranes have been used in MRs. Since organic membranes cannot withstand high temperature, organic MRs are applied mainly in biochemical processes (thus called membrane bioreactors), such as for the production of fine chemicals via the use of enzymes and for large-scale biogas production from waste and environmental clean-up. Most chemical reactions of interest operate at temperatures well in excess of the limitation of polymeric membranes; inorganic membranes with inherent high-temperature structural and chemical stability are appropriate candidates for use in catalytic MRs. The main requirement is to produce membranes with the desired properties of good separation and selectivity and enough robustness to withstand the severe operating conditions often encountered in industrial practice.

Membrane reactors promote a reaction process based on the following three routes, with the membranes having different effects:

The membrane serves as a product extractor (

Figure 1.11

(a,b)). For thermodynamically limited equilibrium reactions, the removal of at least one of the products by the membrane from the reaction zone makes the reaction equilibrium shift to the product side with the single-pass conversion increased (

Figure 1.11

(a)). On the contrary, if the intermediate product is taken out through the membrane, the undesired side-reactions or the secondary reaction of products can be suppressed, leading to improved selectivity (

Figure 1.11

(b)).

The membrane serves as a reactant distributor (

Figure 1.11

(c,d)). A reactant is added to the reaction zone in a controlled manner through the membrane. As a consequence, the side reactions are limited, leading to increased selectivity and yield. In addition, it is possible to use low-purity feed instead of pure reactant to obtain higher selectivity and reduce capital investment and operation costs.

The membrane serves as an active contactor (

Figure 1.11

(e,f)). Reactants are supplied to the catalyst by the controlled diffusion in the membrane, hence a well-defined reaction interface (or region) between two reactant streams is created. The reactants can be provided from one side or from opposite sides of the membrane. Furthermore, more reactive sites can be provided due to the easy access of reactants to the catalyst, and thus the catalyst’s efficiency can be increased greatly.

Figure 1.11 Principles of membrane reactors to enhance the reaction process: (a,b) membrane as a product extractor; (c,d) membrane as a reactant distributor; (e,f) membrane as an active contactor.