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Handbook of membrane reactors


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Woodhead Publishing Series in Energy: Number 55

Handbook of membrane reactors

Volume 1: Fundamental materials science, design

and optimisation

Edited by Angelo Basile

Oxford Cambridge Philadelphia New Delhi


Published by Woodhead Publishing Limited, 80 High Street, Sawston, Cambridge CB22 3HJ, UK www.woodheadpublishing.com www.woodheadpublishingonline.com

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Contents

Contributor contact details xiii Woodhead Publishing Series in Energy xix Preface xxv

Part I Polymeric, dense metallic and composite

membranes for membrane reactors 1

1 Polymeric membranes for membrane reactors 3

J. VITAL, Universidade Nova de Lisboa, Portugal and J. M. SOUSA, Universidade de Tr á s-os-Montes e Alto Douro, Portugal and Universidade do Porto, Portugal

1.1 Introduction: polymer properties for membrane reactors 3

1.2 Basics of polymer membranes 6 1.3 Membrane reactors 12 1.4 Modelling of polymeric catalytic membrane reactors 27 1.5 Conclusions 31 1.6 References 32 1.7 Appendix: nomenclature 40

2 Inorganic membrane reactors for hydrogen

production: an overview with particular emphasis

on dense metallic membrane materials 42

A. BASILE, ITM-CNR, Italy, J. TONG, Colorado School of Mines, USA and P. MILLET, University of Paris (11), France

2.1 Introduction 42 2.2 Development of inorganic membrane reactors (MRs) 46 2.3 Types of membranes 69 2.4 Preparation of dense metallic membranes 99 2.5 Preparation of Pd-composite membranes 104

v

vi Contents


2.6 Preparation of Pd–Ag alloy membranes 115 2.7 Preparation of Pd–Cu alloy composite membranes 119 2.8 Preparation of Pd–Au membranes 121 2.9 Preparation of amorphous alloy membranes 123 2.10 Degradation of dense metallic membranes 126 2.11 Conclusions and future trends 130 2.12 Acknowledgements 133 2.13 References 133 2.14 Appendix: nomenclature 146

3 Palladium-based composite membranes for

hydrogen separation in membrane reactors 149

P. PINACCI, Research on the Energetic System (RSE) S.p.A., Italy and A. BASILE, ITM-CNR, Italy

3.1 Introduction 149 3.2 Development of composite membranes 151 3.3 Palladium and palladium-alloy composite membranes

for hydrogen separation 155 3.4 Performances in membrane reactors 170 3.5 Conclusions and future trends 174 3.6 Acknowledgements 174 3.7 References 175 3.8 Appendix: nomenclature 181

4 Alternatives to palladium in membranes for

hydrogen separation: nickel, niobium and vanadium

alloys, ceramic supports for metal alloys and porous

glass membranes 183

A. SANTUCCI and S. TOSTI, ENEA, Italy and A. BASILE, ITM-CNR, Italy

4.1 Introduction 183 4.2 Materials 185 4.3 Membrane synthesis and characterization 190 4.4 Applications 208 4.5 Conclusions 211 4.6 References 212 4.7 Appendix: nomenclature 217

Contents vii


5 Nanocomposite membranes for membrane reactors 218

A. GUGLIUZZA, ITM-CNR, Italy

5.1 Introduction 218 5.2 An overview of fabrication techniques 219 5.3 Examples of organic/inorganic nanocomposite membranes 222 5.4 Structure-property relationships in nanostructured

composite membranes 225 5.5 Major application of hybrid nanocomposites in membrane

reactors 230 5.6 Conclusions and future trends 235 5.7 References 236 5.8 Appendix: nomenclature 241

Part II Zeolite, ceramic and carbon membranes and

catalysts for membrane reactors 243

6 Zeolite membrane reactors 245

C. ALGIERI, ITM-CNR, Italy and A. COMITE and G. CAPANNELLI, University of Genoa, Italy

6.1 Introduction 245 6.2 Separation using zeolite membranes 250 6.3 Zeolite membrane reactors 254 6.4 Modeling of zeolite membrane reactors 260 6.5 Scale-up and scale-down of zeolite membranes 262 6.6 Conclusion and future trends 264 6.7 References 264 6.8 Appendix: nomenclature 269

7 Dense ceramic membranes for membrane reactors 271

X. TAN, Tianjin Polytechnic University, China and K. LI, Imperial College London, UK

7.1 Introduction 271 7.2 Principles of dense ceramic membrane reactors 274 7.3 Membrane preparation and catalyst incorporation 282 7.4 Fabrication of membrane reactors 288

viii Contents


7.5 Conclusion and future trends 291 7.6 Acknowledgements 292 7.7 References 292 7.8 Appendices 294

8 Porous ceramic membranes for membrane reactors 298

S. SMART, The University of Queensland, Australia, S. LIU, Curtin University, Australia, J. M. SERRA, Universidad Polit é cnica de Valencia, Spain, J. C. DINIZ DA COSTA, The University of Queensland, Australia and A. IULIANELLI and A. BASILE, ITM-CNR, Italy

8.1 Introduction 298 8.2 Preparation of porous ceramic membranes 301 8.3 Characterisation of ceramic membranes 313 8.4 Transport and separation of gases in

ceramic membranes 319 8.5 Ceramic membrane reactors 322 8.6 Conclusions and future trends 326 8.7 Acknowledgements 328 8.8 References 328 8.9 Appendix: nomenclature 335

9 Microporous silica membranes: fundamentals and

applications in membrane reactors for hydrogen

separation 337

S. SMART, J. BELTRAMINI, J. C. DINIZ DA COSTA, The University of Queensland, Australia and A. HARALE, S. P. KATIKANENI and T. PHAM, Saudi Aramco, Saudi Arabia

9.1 Introduction 337 9.2 Microporous silica membranes 338 9.3 Membrane reactor function and arrangement 343 9.4 Membrane reactor performance metrics and

design parameters 346 9.5 Catalytic reactions in a membrane reactor

confi guration 348 9.6 Industrial considerations 358 9.7 Future trends and conclusions 361 9.8 Acknowledgements 363 9.9 References 363 9.10 Appendix: nomenclature 368

Contents ix


10 Carbon-based membranes for membrane reactors 370

K. BRICE Ñ O, Universitat Rovira i Virgili, Spain, A. BASILE, ITM-CNR, Italy, J. TONG, Colorado School of Mines, USA and K. HARAYA, National Institute of Advanced Industrial Science and Technology (AIST), Japan

10.1 Introduction 370 10.2 Unsupported carbon membranes 376 10.3 Supported carbon membranes 377 10.4 Carbon membrane reactors (CMRs) 381 10.5 Micro carbon-based membrane reactors 393 10.6 Conclusions and future trends 396 10.7 Acknowledgements 397 10.8 References 398 10.9 Appendix: nomenclature 400

11 Advances in catalysts for membrane reactors 401

M. HUUHTANEN, P. K. SEELAM, T. KOLLI, E. TURPEINEN and R. L. KEISKI, University of Oulu, Finland

11.1 Introduction 401 11.2 Requirements of catalysts for membrane reactors 404 11.3 Catalyst design, preparation and formulation 407 11.4 Case studies in membrane reactors 415 11.5 Deactivation of catalysts 419 11.6 The role of catalysts in supporting sustainability 423 11.7 Conclusions and future trends 424 11.8 References 425 11.9 Appendix: nomenclature 432

Part III Membrane reactor modelling, simulation

and optimisation 433

12 Mathematical modelling of membrane reactors:

overview of strategies and applications for the

modelling of a hydrogen-selective membrane reactor 435

M. DE FALCO, University of Rome ‘Campus Bio-Medico’, Italy and A. BASILE, ITM-CNR, Italy

12.1 Introduction 435 12.2 Membrane reactor concept and modelling 437 12.3 A hydrogen-selective membrane reactor application:

natural gas steam reforming 445 12.4 Conclusions 458

x Contents


12.5 Acknowledgements 459 12.6 References 459 12.7 Appendix: nomenclature 461

13 Computational fl uid dynamics (CFD) analysis of

membrane reactors: simulation of single- and

multi-tube palladium membrane reactors for

hydrogen recovery from cyclohexane 464

N. ITOH, Utsunomiya University, Japan and K. MIMURA, Chiyoda Corporation, Japan

13.1 Introduction 464 13.2 Single palladium membrane tube reactor 466 13.3 Multi-tube palladium membrane reactor 483 13.4 Conclusions and future trends 492 13.5 References 493 13.6 Appendix: nomenclature 494

14 Computational fl uid dynamics (CFD) analysis

of membrane reactors: simulation of a

palladium-based membrane reactor in fuel cell

micro-cogenerator system 496

L. ROSES, S. CAMPANARI and G. MANZOLINI, Politecnico di Milano, Italy

14.1 Introduction 496 14.2 Polymer electrolyte membrane fuel cell (PEMFC)

micro-cogenerator systems and MREF 497 14.3 Model description and assumptions 499 14.4 Simulation results and discussion of

modelling issues 508 14.5 Conclusion and future trends 525 14.6 Acknowledgements 526 14.7 References 526 14.8 Appendix: nomenclature 528

Contents xi


15 Computational fl uid dynamics (CFD) analysis of

membrane reactors: modelling of membrane

bioreactors for municipal wastewater treatment 532

Y. WANG, T. D. WAITE and G. L. LESLIE, University of New South Wales, Australia

15.1 Introduction 532 15.2 Design of the membrane bioreactor (MBR) 534 15.3 Computational fl uid dynamics (CFD) 539 15.4 CFD modelling for MBR applications 541 15.5 Model calibration and validation techniques 556 15.6 Future trends and conclusions 559 15.7 Acknowledgement 562 15.8 References 562 15.9 Appendix: nomenclature 567

16 Models of membrane reactors based on artifi cial

neural networks and hybrid approaches 569

S. CURCIO and G. IORIO, University of Calabria, Italy

16.1 Introduction 570 16.2 Fundamentals of artifi cial neural networks 571 16.3 An overview of hybrid modeling 575 16.4 Case study: prediction of permeate fl ux decay

during ultrafi ltration performed in pulsating conditions by a neural model 578

16.5 Case study: prediction of permeate fl ux decay during ultrafi ltration performed in pulsating conditions by a hybrid neural model 581

16.6 Case study: implementation of feedback control systems based on hybrid neural models 587

16.7 Conclusions 594 16.8 References 594 16.9 Appendix: nomenclature 596

xii Contents


17 Assessment of the key properties of materials used

in membrane reactors by quantum computational

approaches 598

G. DE LUCA, ITM-CNR, Italy

17.1 Introduction 598 17.2 Basic concepts of computational approaches 601 17.3 Gas adsorption in porous nanostructured materials 606 17.4 Adsorption and absorption of hydrogen and small gases 611 17.5 Conclusions and future trends 617 17.6 References 618 17.7 Appendix: nomenclature 621

18 Non-equilibrium thermodynamics for the description

of transport of heat and mass across a zeolite

membrane 627

S. K. SCHNELL and T. J. H. VLUGT, Delft University of Technology, The Netherlands and S. KJELSTRUP, Norwegian University of Science and Technology, Norway

18.1 Introduction 627 18.2 Fluxes and forces from the second law and transport

coeffi cients 632 18.3 Case studies of heat and mass transport across the zeolite

membrane 638 18.4 Conclusions and future trends 643 18.5 Acknowledgement 643 18.6 References 644 18.7 Appendix: nomenclature 645

Index 647


xiii

Contributor contact details

(* = main contact)

Editor

Prof. Angelo Basile Institute on Membrane

Technology ITM-CNR c/o University of Calabria Via P. Bucci Cubo 17/C 87030 Rende (CS) Italy

Email: [email protected]

and

AST Engineering S.p.A. via Adolfo Rav à 30 00142 Rome Italy

Chapter 1

Joaquim Vital* REQUIMTE, CQFB,

Departamento de Qu í mica FCT, Universidade

Nova de Lisboa Campus da Caparica 2829-516 Caparica Portugal


Jos é M. Sousa Escola de Ciências da Vida e do

Ambiente – Departamento de Química

Universidade de Tr á s-os-Montes e Alto Douro

Apartado 1013, 5001-801-Vila Real Codex

Portugal


and

LEPAE – Departamento de Engenharia Química

Faculdade de Engenharia da Universidade do Porto

Rua Roberto Frias S/N 4200-465 Porto Portugal


Chapter 2

Prof. Angelo Basile* Institute on Membrane Technology ITM-CNR c/o University of Calabria Via P. Bucci Cubo 17/C 87030 Rende (CS) Italy


xiv Contributor contact details


Prof. Jianhua Tong Metallurgical and Materials

Engineering Colorado School of Mines 1500 Illinois Street Golden, CO 80401 USA

Prof. Pierre Millet Institut de Chimie Moléculaire et

des Matériaux d’Orsay UMR 8182 - Université

Paris sud Centre d’Orsay, Bâtiment 410 91405 Orsay Cedex France

Chapter 3

Pietro Pinacci* Research on the Energetic System

(RSE) S.p.A. Via Rubattino 54 20134 Milano Italy





Chapter 4

Alessia Santucci and Silvano Tosti*

Italian National Agency for New Technologies, Energy and Sustainable Economic Development (ENEA)

Unit à Tecnica Fusione C.R. Frascati Via E. Fermi 45 00044 Frascati (RM) Italy





Chapter 5

Annarosa Gugliuzza Institute on Membrane



Contributor contact details xv


Chapter 6

C. Algieri* Institute on Membrane



Dr Antonio Comite and Prof. Gustavo Capannelli

Dipartimento di Chimica e Chimica Industriale

Università degli Studi di Genova Via Dodecaneso, 31 16146 Genoa Italy

Chapter 7

Dr X. Tan Department of Chemical

Engineering Tianjin Polytechnic University 399, Bingshui West Raod Xiqing District, Tianjin, 300397 China

Kang Li* Department of Chemical

Engineering and Technology Imperial College London South Kensington London SW7 2AZ UK


Chapter 8

Simon Smart* and João C. Diniz da Costa

School of Chemical Engineering The University of Queensland Brisbane Queensland 4072 Australia


Jose M. Serra Instituto de Tecnología Química Consejo Superior de

Investigaciones Cientifi cas Universidad Politécnica de Valencia Campus UPV - Building 6C av. los

Naranjos s/n E-46022 Valencia Spain


Shaomin Liu Department of Chemical

Engineering Curtin University Perth, WA 6845 Australia


A. Iulianelli and Prof. Angelo Basile

Institute on Membrane Technology ITM-CNR c/o University of Calabria Via P. Bucci Cubo 17/C 87030 Rende (CS) Italy


xvi Contributor contact details


Chapter 9

Simon Smart, J. Beltramini and Jo ã o C. Diniz da Costa*

School of Chemical Engineering The University of Queensland Brisbane Queensland 4072 Australia


A. Harale, S. P. Katikaneni and T. Pham

Saudi Aramco Saudi Arabia

Chapter 10

Dr Kelly Brice ñ o* Department d’Enginyeria Quimica Universitat Rovira i Virgili Av. Pasos Catalans, 26 43007 Tarragona Spain

Email: [email protected]; [email protected]

Prof. Angelo Basile Institute on Membrane Technology ITM-CNR c/o University of Calabria Via P. Bucci Cubo 17/C 87030 Rende (CS) Italy


Prof. Jianhua Tong Metallurgical & Materials

Engineering Colorado School of Mines 1500 Illinois Street Golden, CO 80401 USA

Dr Kenji Haraya National Institute of Advanced

Industrial Science and Technology (AIST)

Research Institute for Innovation in Sustainable Chemistry Membrane Separation Processes Group

AIST Tsukuba Central 5 Tsukuba 305-8565 Japan

Chapter 11

Mika Huuhtanen*, P. K. Seelam, T. Kolli, E. Turpeinen and R. L. Keiski

Mass and Heat Transfer Process Laboratory

Department of Process and Environmental Engineering

P.O. Box 4300 FI-90014 University of Oulu Finland


Chapter 12

Marcello De Falco* Faculty of Engineering University Campus Bio-Medico of

Rome via Alvaro del Portillo 21 00128 Rome Italy


Contributor contact details xvii





Chapter 13

Prof. Naotsugu Itoh* Department of Material and

Environmental Chemistry Utsunomiya University 7-1-2, Yoto Utsunomiya 321–8585 Japan

Email: itoh-n@ cc.utsunomiya-u.ac.jp

Prof. K. Mimura Engineering Solution Unit Chiyoda Corporation 4-6-2 Minatomirai, Nishi-ku Yokohama 220-8765 Japan

Chapter 14

Leonardo Roses, Stefano Campanari* and Giampaolo Manzolini

Politecnico di Milano Dipartimento di Energia Via Lambruschini 4 20156 Milano Italy


Chapter 15

Y. Wang and Gregory L. Leslie* UNESCO Centre for Membrane

Science and Technology School of Chemical Engineering University of New South Wales Kensington 2052 Australia


T. D. Waite Water Research Centre School of Civil and Environmental

Engineering University of New South Wales Kensington 2052 Australia

Chapter 16

Stefano Curcio* and Prof. Gabriele Iorio

Department of Engineering Modeling

University of Calabria Ponte P. Bucci Cubo 36/C 87036 Rende (CS) Italy


Chapter 17

G. De Luca Institute on Membrane Technology ITM-CNR c/o University of Calabria Via P. Bucci Cubo 17/C 87030 Rende (CS) Italy


xviii Contributor contact details


Chapter 18

S. K. Schnell* and T. J. H. Vlugt Process & Energy Department Delft University of Technology Leeghwaterstraat 44 2628CA Delft The Netherlands


Signe Kjelstrup Department of Chemistry Norwegian University of Science

and Technology Høgskoleringen 5 7491 Trondheim Norway


xix

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xxv

Preface

This handbook is dedicated in particular to those readers interested in emerging applications of membrane reactors in the fi eld of energy and envi-ronment. The main motivation for this handbook is to give to the reader a panorama of the various aspects of research related to membrane reactors and their applications. The utilisation of membrane reactor technology on a larger scale could constitute a relevant enhancement of conventional sys-tems already in existence. For example, in the fi eld of reforming processes, the main benefi t of a membrane reactor is the selective removal of a com-pound such as hydrogen from the reaction side, which may allow the ther-modynamic equilibrium restrictions of the conventional fi xed bed reactors to be overcome.

To this end, I invited an international team of expert scientists from the fi eld of membrane science and technology to write about: the state-of-the-art of the various kind of membranes (polymeric, Pd- and non Pd-based, carbon, zeolite, perovskite, composite, ceramic, etc.) used in membrane reactors; modelling aspects related to all kinds of membrane reactors, the various applications of membrane reactors and, fi nally, economic aspects.

Due to the large amount of material available in the specialised literature, the handbook is composed of two volumes. It should also be mentioned that all the chapters are strictly interconnected. However, for practical use of the handbook, each volume is composed of different parts. In particular, in this fi rst volume, the various arguments are conceptually split into three different parts.

In Part I the various aspects related to polymeric, dense metallic and com-posite membranes for membrane reactors are extensively considered. The volume starts with Chapter 1 , in which the authors (Vital and Sousa) give an overview of the polymeric membranes used in membrane reactors. After introducing some basic concepts of polymer science and polymer mem-branes, two different types of polymeric membrane reactors (inert and cata-lytic) are discussed. Various examples of the main reactor types (extractors, forced-fl ow or contactors) are also given. Finally, the modelling aspects of membrane reactors with dense polymeric catalytic membranes are also pre-sented in detail. It is followed by Chapter 2 (Basile, Tong and Millet), which

xxvi Preface


provides an extensive overview of the inorganic membrane reactors related to the hydrogen production. Almost all the reactions used by scientists for this purpose are summarised and, for the ones considered of practical value, a deeper analysis of both catalysts and membranes is also undertaken. The characteristics as well as the preparation of dense Pd-based membranes, non Pd-based membranes, and also amorphous membranes are discussed, having also in mind both the governing equations and the laws of sorp-tion, diffusion and permeation. The fi nal part of the chapter is dedicated to the analysis of the degradation of dense metallic (pure, alloy, amorphous) membranes: embrittlement, oxidation, polarisation effect, interaction with support (composite membranes) and degradation due to interactions with catalysts, coke, sulphur and morphology changes. Chapter 3 (Pinacci and Basile) focuses attention on preparation methods for thin dense palladium layer deposition onto microporous supports in the fi eld of inorganic com-posite membrane reactors. In particular, special emphasis is paid to electro-less plating and magnetron sputtering techniques, followed by an analysis of the chemical and physical stability of the prepared composite membranes. The most important and recent performances and developments of these membranes are also discussed.

Chapter 4 (Santucci, Tosti, Basile) is mainly focused on the develop-ment of membranes based on metals other than Pd, such as Ni, Nb, V and Ti, which are considered today promising substitutes for the Pd-alloys. Particular attention is given to the synthesis of these membranes as well as to the effect of alloying on their chemical–physical properties. The chapter also provides a description of two porous (ceramic and glass) membranes used as a support for the new metal alloys, in gas separation and in mem-brane reactors, respectively. The objective of Chapter 5 (Gugliuzza) is to document what is known about nanocomposite polymeric membranes and the procedures of fabrication. Their potentialities in catalytic membrane reactors, bioreactors and membrane operations for alternative power pro-duction are highlighted.

After this chapter, Part II is dedicated to zeolite, ceramic and carbon membranes and catalysts used in membrane reactors. In Chapter 6 (Algieri, Comite and Capannelli) the remarkable properties of zeolite membranes are illustrated. Moreover, the key role of zeolite membrane reactors to improve the yield and the selectivity of reactions is particularly emphasised. Furthermore, the possibility of using zeolite membranes as micro-reactors and sensors is also discussed. Chapter 7 (Tan and Li) deals with dense ceramic membrane reactors, which are made from composite oxides usu-ally having perovskite or fl uorite structures with appreciable mixed ionic (oxygen ion and/or proton) and electronic conductivity. This chapter mainly describes the principles of various confi gurations (disc/fl at-sheet, tubular and hollow fi bre membranes) of dense ceramic membrane reactors and the

Preface xxvii


fabrication of the membranes and membrane reactors. The commercialisa-tion of dense ceramic membrane reactor technology is also discussed.

After the dense ceramic membranes, Chapter 8 (Smart, Liu, Serra, da Costa, Iulianelli and Basile) is entirely dedicated to the porous ceramic membranes used in membrane reactors. To summarise, this chapter dis-cusses the most commonly used preparation techniques as well as the var-ious characterisation procedures for porous ceramic membranes and their application as membrane reactors for gas and liquid phase reactions, per-meation and separation. Chapter 9 (Smart, Beltramini, da Costa, Harale, Katikaneni and Pham) introduces silica membrane reactors by discussing the research and development of membrane reactors which incorporate microporous silica-based membranes specifi cally for hydrogen production. A discussion of relevant gas transport mechanisms, membrane performance parameters, membrane reactor designs and membrane reactor performance metrics is followed by an in-depth analysis of the various research investiga-tions where silica membrane reactors are used to produce hydrogen and/or syngas from hydrocarbon reforming reactions.

Chapter 10 (Brice ñ o, Basile, Tong and Haraya) provides an introduction to carbon-based membrane reactors, which contain new and very interest-ing membrane materials that can be integrated in a compact confi guration. Even if carbon membranes are still in an infant stage, they are today con-sidered promising candidates for porous membranes in membrane reactors because of their ease of use, low raw material cost, low fabrication cost, molecular sieve separation effect and relatively high gas permeance val-ues. Some interesting applications of carbon membranes for both macro- and micro-reactors are also reviewed. This Part II ends with Chapter 11 (Huuhtanen, Seelam, Kolli, Turpeinen and Keiski) dedicated to the new catalysts used in membrane reactors. Since the catalyst is one of the main components of a membrane reactor, it is also important to understand its function in these systems. The chapter discusses the different ways in which the catalyst can be introduced or incorporated in the reactor as a catalytic membrane wall. Due to the need also for new catalysts for membrane reac-tors, the development of some new materials that can be used as novel cat-alyst supports is also presented.

Part III is dedicated to the modelling, simulation and optimisation of membrane reactors. Modelling of reactors is a crucial topic in process design. The development of reliable and powerful tools for the specifi c design of particular reactors allows both the optimal dimensions and opti-mal operating conditions to be defi ned. Some general aspects of inor-ganic membrane reactor modelling start to be considered in Chapter 12 (De Falco and Basile), where the main guidelines for membrane reactor modelling are also reported. After presenting the model categories and the procedures for the development of the reactor model, a natural gas

xxviii Preface


steam reforming Pd-based membrane reactor is completely modelled as a case study. Chapter 13 (Itoh and Mimura), in which a computational fl uid-dynamics analysis of membrane reactors is presented, follows in the same vein. In particular, the results of the simulation of single- and multi-tube palladium membrane reactors for hydrogen recovery are shown and discussed. The model developed takes into account the concentration, temperature and velocity distributions due to mass, heat transfer and fl ow resistances in the membrane reactor, and it is verifi ed for the dehydro-genation of cyclohexane in a shell-and-tube type of palladium membrane reactor as well as a multi-tube type. It is demonstrated that the multi-tube model developed is applicable for the reactor design. Using the same tool, i.e. the same computational fl uid-dynamics analysis, Chapter 14 (Roses, Campanari and Manzolini) presents a bi-dimensional simulation of a steam methane reformer coupled with a palladium-based hydrogen-permeable membrane. The simulation predicts the system performances by modelling the combined phenomena taking place in the reactor. The chapter shows a detailed analysis of various parameters (temperature, and so on) and dis-cusses their impact on reactor performances. Furthermore, the same mod-elling technique is used in Chapter 15 (Wang, Waite and Leslie) to provide an overview of membrane bioreactor design for two-phase and three-phase fl ows. Various effects (reactor geometry, etc.) are discussed and particular emphasis is given to the importance of model calibration, results validation and the outlook for future work.

In Chapter 16 (Curcio and Iorio) it is shown how various kinds of advanced models, based either on artifi cial neural networks or on a hybrid approach, could be used to predict the behaviour of some typical membrane process. The obtained results demonstrate that the proper combination of a theoret-ical model with a straightforward neural model is capable of widening the applicability of pure neural models outside the training range, thus paving the way for the exploitation of hybrid neural models for process optimisa-tion purposes and for the implementation of effi cient on-line controllers operating in different kinds of membrane processes. Chapter 17 (De Luca) starts from the consideration that several nanostructured materials are used in the preparation of membrane reactors. For this reason, the evaluation of their key properties is very important. Quantum mechanics is seen as a reliable tool for obtaining these fundamental properties, avoiding the use of empirical parameters. The assessment of some fundamental quantities, such as the adsorption energies of gases in nano-porous materials or on metallic surfaces, is reviewed. Moreover, the calculation of hydrogen solubilisation in metal alloys is also presented. Chapter 18 (Schnell, Vlugt and Kjelstrup) considers that non-equilibrium thermodynamics offer a better and more precise way to describe transport of heat and mass over membranes than the simple Fick’s and Fourier’s laws. In deriving the equations for single

Preface xxix


component transport (of n- butane) across a zeolite membrane, the authors use non-equilibrium molecular dynamics data to show how phenomena are strictly related. The transport models across a zeolite membrane are shown to be in agreement with the second law of thermodynamics.

I wish to take this opportunity to thank all the authors of the chapters for their expert contributions.

A. Basile ITM-CNR, Italy

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