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Enrico Drioli

Lidietta Giorno
Editors

Encyclopedia of
Membranes

1 3Reference
Encyclopedia of Membranes
Enrico Drioli Lidietta Giorno
Editors

Encyclopedia of
Membranes

With 968 Figures and 185 Tables


Editors
Enrico Drioli Lidietta Giorno
University of Calabria Institute on Membrane Technology
Rende, Italy National Research Council of Italy
ITM-CNR
Rende, Italy

ISBN 978-3-662-44323-1 ISBN 978-3-662-44324-8 (eBook)


ISBN 978-3-662-44325-5 (print and electronic bundle)
DOI 10.1007/978-3-662-44324-8
Library of Congress Control Number: 2016944015

# Springer-Verlag Berlin Heidelberg 2016


This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or
part of the material is concerned, specically the rights of translation, reprinting, reuse of
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and transmission or information storage and retrieval, electronic adaptation, computer software, or
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The use of general descriptive names, registered names, trademarks, service marks, etc. in this
publication does not imply, even in the absence of a specic statement, that such names are exempt
from the relevant protective laws and regulations and therefore free for general use.
The publisher, the authors and the editors are safe to assume that the advice and information in this
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authors or the editors give a warranty, express or implied, with respect to the material contained
herein or for any errors or omissions that may have been made.

Printed on acid-free paper

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The registered company is Springer-Verlag GmbH Berlin Heidelberg
Preface

The Encyclopedia of Membranes is a reference work that covers all aspects of


membrane science and technology, from basic phenomena to the most
advanced applications and future perspectives. It is aimed at students, graduate
students, academic and industrial researchers, and practitioners.
The Encyclopedia of Membranes is organized around a list of searchable
Entries or Terms, in alphabetical order, giving the user fast and easy access to
terminology, description, theory, and application of membrane science.
Entries range from one to several printed pages and are written by one or
multiple authors.
Authors are both from academic institutions, research agencies, and
industries.
The development of the Encyclopedia is undertaken by the Chief Editors,
Prof. Enrico Drioli and Dr. Lidietta Giorno, responsible for the selection of the
topics, the terms, and the quality of the contributions. An Advisory Board was
identied to discuss major items and promote holistic vision of the work. An
Editorial Board assisted the Chief Editors in their activities.
The Encyclopedia of Membranes is a landmark work covering the science,
technology, and application of membranes, membrane operations, and related
elds.
A membrane is a nanostructured/functionalized thin barrier that controls the
exchange phenomena (matter and energy) between two different phases, both
through the external forces and under the effect of uid properties, and also
through the intrinsic characteristics of the membrane material itself.
Membranes are used in various applications. They differ widely in their
structure, in their function, and the way they are operated. Membranes may be
biological or synthetic, solid or liquid, homogeneous or heterogeneous, iso-
tropic or anisotropic, and it can be a fraction of a micrometer or various
millimeters thick. The application of different membrane structures and driv-
ing forces caused a number of rather different membrane processes such as
micro-, ultra-, and nanoltration, reverse osmosis, dialysis and electrodialysis,
pervaporation, gas separation, membrane contactors (membrane distillation,
membrane crystallizer, membrane strippers, membrane scrubbers, membrane
condenser, membrane emulsier), membrane reactors, catalytic membrane
reactor, etc.
In various elds, membrane operations are already dominant technologies.
Interesting examples are in the seawater desalination, in wastewater treatment

v
vi Preface

and reuse, and in biomedical applications. They are of interest in all sectors
strategic for a sustainable development. They are clean, safe, require low
energy input, and suitable to promote process intensication. Practically all
typical unit operations of process engineering might be redesigned as mem-
brane unit operations.
Membrane operations are largely present, for example, in the following
elds:

Water treatment and purication


Energy
Gas separation
Solvent treatment and purication
Petrochemical industry (where the integration
of different membrane operations has promising applications)
Environment
Agro-food and packaging
Biotechnology
Tissue engineering and regenerative medicine
Biorenery
Pharmaceutical and cosmetic
Microelectronics (OLEDS) (which is becom-
ing an area of interesting applications)

Other elds that will exploit more and more membranes unique features
include:

Sensors
Micromanufacturing
Responsive materials
Safety and security
Space

The large spectrum of challenges membrane operations contribute to face


today and their strong multidisciplinary character suggested to develop this
work on membrane science and membrane engineering.

Enrico Drioli
Lidietta Giorno
Acknowledgments

We are very pleased to acknowledge the important help and contribution


received by our colleagues Adele Brunetti, Enrica Fontananova, Francesca
Macedonio, and Rosalinda Mazzei, in the preparation of this Encyclopedia.
Their continuous collaboration in keeping all necessary contacts with hun-
dreds of colleagues from all around the world, in discussing on the various
unexpected problems for nalizing this work, has been signicant. Thank you!
We also wish to express grateful thanks to the members of the advisory
board for their kind availability as well as to all authors for their invaluable
contribution to the work.

Enrico Drioli
Lidietta Giorno

vii
Editors Biography

Enrico Drioli Emeritus Professor, University of Calabria, Rende, Italy

Career
Distinguished Visiting Professor, Faculty of Engineering and Information
Technology, University of Technology Sydney, Australia (January 2016)
Distinguished Adjunct Professor, Center of Excellence in Desalination Tech-
nology, King Abdulaziz University, Jeddah, Saudi Arabia (2012)
WCU (World Class University) Distinguished Visiting Professor, Department
of Energy Engineering, Hanyang University, Seoul Korea (2009)
Emeritus Professor, School of Engineering of the University of Calabria
(2012)
Professor of Chemistry and Electrochemistry at the School of Engineering of
the University of Naples (since 19681982)
Professor at the School of Engineering of the University of Calabria
(19812011)
Dean of the School of Engineering of the University of Calabria (19821985)
Founding Director of the Institute on Membrane Technology (ITM) of CNR
(from 2011)
Director of the Institute on Membranes and Chemical Reactors of the National
Research Council (19932001)
Director of the Institute on Membrane Technology (ITM) of CNR
(20022008)

Research Interest
Membranes in articial organs, integrated membrane processes, membrane
preparation transport phenomena, membrane distillation and membrane
contactors, catalytic membrane, and catalytic membrane reactors.

ix
x Editors Biography

Biography
Coordinator of the European Erasmus Mundus Doctorate in Membrane Engi-
neering (EUDIME).
Scientic Coordinator of various international contracts/agreements:
ITM-CNR-KACST, Hydrophobic membrane preparation for membrane
contactors application; ITM-CNR-KISR (Kuwait Institute for Scientic
Research), Evaluation of the potentialities of the membrane distillation tech-
nology for desalting de-oiled ltered high concentrated saline waters;
RHODIA; etc.

Member of the Scientic Advisory Panel (SAP) for the KAUST Water Desa-
lination and Reuse (WDR) Center from 2010
MIAC International Award for International Collaboration and Promotion
(October 2015)
Award with the Academician Semenov Medal of Russian Academy of Engi-
neering Science (2014)
Honorary Membership of the Czech Society of Chemical Engineering (2012)
2011, Richard Maling Barrer Prize of the EMS, for his outstanding contri-
butions to membrane science and technology
2009, Doctorate Honoris Causa from University of Paul Sabatier of Toulouse,
France
2005, International Cooperation Honor Award, Membrane Industry Associa-
tion of China (MIAC) for special dedication to International Cooperation
between China and Europe in the eld of membrane science and technology
2005Present, Guest Professor, Jiangsu Polytechnic University, China
1999, Honorary President, European Membrane Society
1992, Doctorate Honoris Causa in Chemistry and Chemical Technology,
Russian Academy of Science
1991, Honorary Professor, China Northwest University in Xian, Shaanxi,
China
19821998, President, European Society of Membrane Science and Technol-
ogy (European Membrane Society)

Advisory Board of Journal of Membrane Science, Polish Journal of Chem-


ical Technology; Editorial Board of various other international scientic
journals.
Executive Editor: Applied Water Science Journal, Springer Berlin Heidel-
berg (Germany) and Membrane Water Technology, Techno Press (Korea).
Editor of more of 750 scientic papers, 22 patents, and 24 books
Editors Biography xi

Lidietta Giorno is serving as the Director of the Institute on Membrane


Technology of the National Research Council of Italy, ITM-CNR, since 2009.
Her research expertise include membrane bioengineering, biocatalytic
membrane reactors, integrated membrane systems for bioseparations and bio-
conversions, downstream processing based on molecular separation, mem-
brane chirotechnology, membrane emulsier, and integrated membrane
operations for water treatment. She has been involved in membrane science
and engineering research and development for some 25 years, and in research
cooperations at European and international levels.
She was awarded the international Guido Dorso Award for research in
2011, sponsored by the Italian Senate and the University of Naples Federico
II. She was awarded the Sapio Red Carpet Award in 2016 among female
scientists of highest scientic prole who are engaged for the development of
the country.
She worked abroad in the USA at Sepracor Inc. in 1992, in the Netherlands
at ATO-DLO in 1994, and in France at The University of Compiegne in
19972000. She is Visiting Professor at Tianjin University of Science and
Technology, China, since 2008.
Lidietta Giorno is coeditor of 8 books, over 110 peer-reviewed scientic
papers in international journals, and coeditor of the Encyclopedia of Mem-
branes, Springer, 2016. She is member of the editorial board of scientic
journals, member of the referee pool of scientic journals and research agen-
cies, and member of international committees and several scientic societies.
She has served as member of the Board of Directors of the European
Membrane House (EMH, Belgium), formed to continue the activity of the
NanoMemPro Network of Excellence funded by the European Commission
within the FP6.
She has served on the European Membrane Society Council as the Presi-
dent of the EMS Council and the Editor of the EMS Membrane Newsletter.
She was nominated Honorary Member of the European Membrane Society
in 2014.
Advisory Board

Bhattacharyya Dibakar University Alumni Professor, Lexington, KY


Tony Fane Nanyang Technological University 18, Nanyang Drive,
Singapore, Singapore
Michel Y. Jaffrin Department of Biological Engineering, Technological
University of Compiegne, UMR CNRS 6600, Compiegne Cedex, France
Ora Kedem Emeritus Professor of Desalination and Water Treatment
Research at Ben, Gurion University and also professor at the Weizmann
Institute of Science, Ben-Gurion University of the Negev, Beer Sheva, Israel
William J. Koros Georgia Institute of Technology-School of Chemical and
Biomolecular Eng., Atlanta, GA, USA
Kew-Ho Lee National Research Laboratory for Functional Membranes,
Environment and Resources, Research Center, Yuseong, Daejeon, South
Korea
Young Moo Lee Hanyang University, Seoul, Republic of Korea
Donald R. Paul Department of Chemical Engineering and Texas Materials
Institute University of Texas at Austin, Austin, Texas, TX, USA
Heiner Strathmann Institut fur Chemische Verfahrenstechnik, Universitt
Stuttgart, Stuttgart, Germany
Yuri Yampolskii A.V. Topchiev Institute of Petrochemical Synthesis,
Moscow, Russia

xiii
Editorial Board

Adele Brunetti ITM-CNR c/o University of Calabria, Rende, Italy


Enrica Fontananova ITM-CNR c/o University of Calabria, Rende, Italy

Francesca Macedonio ITM-CNR c/o University of Calabria, Rende, Italy


Rosalinda Mazzei ITM-CNR c/o University of Calabria, Rende, Italy

xv
Contributors

A. Achilli Environmental Resources Engineering Department, Humboldt


State University, Arcata, CA, USA
Pejman Ahmadiannamini Biomedical Engineering, University of Arkan-
sas, Fayetteville, AR, USA
Catia Algieri Institute on Membrane Technology, National Research Council
of Italy, ITM-CNR, Rende, Italy
Aamer Ali Department of Environmental and Chemical Engineering,
University of Calabria, Rende, Italy
Institute on Membrane Technology, National Research Council of Italy,
ITM-CNR, Rende, Italy
Sacide Alsoy Altinkaya Department of Chemical Engineering, Izmir Insti-
tute of Technology, Urla, Izmir, Turkey
Vitor D. Alves LEAF Linking Landscape, Environment, Agriculture and
Food, Instituto Superior de Agronomia, Universidade de Lisboa, Lisboa,
Portugal
Shota Ando Department of Applied Chemistry, Meiji University, Tama-ku,
Kawasaki, Japan
Muhammad Waqas Anjum School of Chemical and Materials Engineering,
National University of Science and Technology, Islamabad, Pakistan
Alice Antony School of Chemical Engineering, The University of New
South Wales, UNESCO Centre for Membrane Science and Technology, Syd-
ney, NSW, Australia
Mario Aparicio Instituto de Ceramica y Vidrio (CSIC), Madrid, Spain
Adriana Arca-Ramos Department of Chemical Engineering, Institute of
Technology, University of Santiago de Compostela, Santiago de Compostela,
Spain
Pietro Argurio Department of Environmental and Chemical Engineering,
University of Calabria, Arcavacata di Rende, Italy
Antonino Salvatore Arico CNR-ITAE Institute, Messina, Italy
Marco Avataneo RD&T, Solvay Specialty Polymers, Bollate (MI), Italy

xvii
xviii Contributors

He Bai Momentive Performance Materials Inc, Friendly, WV, USA

Renbi Bai Department of Civil and Environmental Engineering, National


University of Singapore, Faculty of Engineering, Singapore, Singapore

Malini Balakrishnan The Energy and Resources Institute (TERI), New


Delhi, India

Joerg Balster Application Technology, Evonik Fibres GmbH, Schoering,


Austria

Mohamed Abou El-Fetouh Barakat Department of Environmental Sci-


ences, Faculty of Meteorology, Environment and Arid Land Agriculture,
King Abdulaziz University, Jeddah, Saudi Arabia
Central Metallurgical R & D Institute, Helwan, Cairo, Egypt

Giuseppe Barbieri Institute on Membrane Technology, National Research


Council of Italy, ITM-CNR, Rende, Italy

Onita D. Basu Department of Civil and Environmental Engineering, Carle-


ton University, Ottawa, Canada

Arnaud Baudot Physics and Analysis Division, IFP Energies Nouvelles,


Solaize, France

Laurent Bazinet Department of Food Sciences, Universit Laval, Quebec,


QC, Canada

Fabio Bazzarelli Institute on Membrane Technology, National Research


Council of Italy, ITM-CNR, Rende, Italy

Katalin Bela-Bako Research Institute of Bioengineering, Membrane Tech-


nology and Energetics, University of Pannonia, Veszprem, Hungary

Marie-Pierre Belleville Institut Europen des Membranes (IEM): UMR


CNRS 5635, Universit de Montpellier II, Montpellier, France

Benny Danilo Belviso Istituto di Cristallograa, Consiglio Nazionale delle


Ricerche (C.N.R), Bari, Italy

Juana Benavente Departamento de Fisica Aplicada I, Universidad de


Malaga, Facultad de Ciencias, Malaga, Spain

Nilay Bereli Department of Chemistry, Biochemistry Division, Hacettepe


University, Ankara, Turkey

Samuel Bernard Institut Europen des Membranes, ENSCM-UM2-CNRS,


(UMR 5635), Universit de Montpellier 2, Montpellier, France

A. Moura Bernardes Universidade Federal do Rio Grande do Sul


(PPGE3M-UFRGS), RS, Porto Alegre, Brazil

Paola Bernardo Institute on Membrane Technology, National Research


Council of Italy, ITM-CNR, Rende, Italy
Contributors xix

Richard Bernewitz Food Process Engineering, Karlsruhe Institute of Tech-


nology (KIT), Karlsruhe, Germany
Anna Maria Bertasa Solvay Specialty Polymers, Bollate (MI), Italy
Dmitri Bessarabov Faculty of Engineering, DST HySA Infrastructure Cen-
ter of Competence, North-West University, Potchefstroom, South Africa
Chiranjib Bhattacharjee Department of Chemical Engineering, Jadavpur
University, Kolkata, West Bengal, India
Maarten Biesheuvel Wetsus, European Centre of Excellence for Sustainable
Water Technology, Leeuwarden, The Netherlands
M. R. Bilad Centre for Surface Chemistry and Catalysis, KU Leuven, Leu-
ven, Heverlee, Belgium
ngeles Blanco Department of Chemical Engineering, Universidad
Complutense de Madrid, Madrid, Spain
Carlo Boaretti Department of Industrial Engineering, University of Padova,
Padova, Italy
Cristiana Boi Dipartimento di Ingegneria Civile, Chimica, Ambientale e dei
Materiali, Universit di Bologna, Bologna, Italy
Przemysaw Borys Department of Physical Chemistry and Technology of
Polymers, Silesian University of Technology (SUT), Gliwice, Poland
Karel Bouzek Faculty of Chemical Technology, University of Chemistry and
Technology Prague, Technick 5, Prague 6, Czech Republic
Rune Bredesen Sustainable Energy Technology, SINTEF Materials and
Chemistry, Oslo, Norway
Eugenio Bringas Department of Chemical and Biomolecular Engineering,
University of Cantabria, Santander, Cantabria, Spain
D. J. Broer Department of Chemical Engineering and Chemistry, Group
Functional Organic Materials and Devices (SFD), Eindhoven University of
Technology, Eindhoven, The Netherlands
Stephan Brosillon Institut Europen des Membranes, ENSCM-UM-CNRS,
(UMR 5635), Universit de Montpellier, Montpellier Cedex 5, France
Adele Brunetti Institute on Membrane Technology, National Research
Council of Italy, ITM-CNR, Rende, Italy
Peter M. Budd Organic Materials Innovation Centre, School of Chemistry,
University of Manchester, Manchester, UK
Vasilis Burganos Institute of Chemical Engineering Sciences, Foundation
for Research and Technology Hellas, FORTH/ICE-HT, Patras, Hellas
Tomas Bystron Faculty of Chemical Technology, University of Chemistry
and Technology, Prague, Technick 5, Prague 6, Czech Republic
xx Contributors

Rajnish Kaur Calay Institute for Building, Energy and Material Technol-
ogy, University of Troms, Navrik, Norway
Energy Technology Research Group, Narvik University College, Lodve
Langes gt 2, Navrik, Norway
Rocco Caliandro Institute of Crystallography, CNR, Bari, Italy
Anja Car Department of Chemistry, University of Basel, Basel, Switzerland
Alessio Caravella National Institute of Advanced Industrial Science and
Technology Research Institute for Innovation in Sustainable Chemistry,
ISC-AIST, Tsukuba, Ibaraki, Japan
Juergen Caro Institute of Physical Chemistry and Electrochemistry, Leibniz
University, Hannover, Germany
Mariolino Carta School of Chemistry, The University of Edinburgh, Edin-
burgh, Scotland, UK
Alfredo Cassano Institute on Membrane Technology, National Research
Council of Italy, ITM-CNR, Rende, Italy
Alberto Cassetta Istituto di Cristallograa CNR UOS di Trieste, Italy
Sophie Cerneaux UMR 5635 ENSCM, CNRS, UM, Institut Europen des
Membranes, Montpellier, France
S. K. Chakarvarti Manav Rachna International University, Faridabad, India
Department of Physics, National Institute of Technology, Kurukshetra, Hary-
ana, India
Catherine Charcosset Universit Lyon 1, Lyon, Villeurbanne, France
Tzyy Haur Chong Singapore Membrane Technology Centre, Nanyang
Environment and Water Research Institute; School of Civil and Environmental
Engineering, Nanyang Technological University, Singapore, Singapore
Kwang-Ho Choo Department of Environmental Engineering, Kyungpook
National University, Daegu, Republic of Korea
Benjamin Chu Department of Chemistry, Stony Brook University, Stony
Brook, NY, USA
Liang-Yin Chu Membrane Science and Functional Materials Group, School
of Chemical Engineering, Sichuan University, Chengdu, Sichuan, China
Jose Coca Department of Chemical and Environmental Engineering, Uni-
versity of Oviedo, Oviedo, Spain
Isabel Coelhoso LAQV-REQUIMTE, Departamento de Qumica, Faculdade
de Ciencias e Tecnologia, Universidade Nova de Lisboa, Caparica, Portugal
Carmela Conidi Institute on Membrane Technology, National Research
Council of Italy, ITM-CNR, Rende, Italy
Contributors xxi

Marc Cretin Institut Europen des Membranes, ENSCM-UM-CNRS (UMR


5635), Universit de Montpellier, Montpellier Cedex 5, France
National School of Chemistry of Montpellier, University of Montpellier,
Montpellier, France
Alessandra Criscuoli Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, Rende, Italy
Zhaoliang Cui State Key Laboratory of Materials-Oriented Chemical Engi-
neering, College of Chemistry and Chemical Engineering, Nanjing Tech
University, Nanjing, China
Efrem Curcio Department of Environmental and Chemical Engineeering,
University of Calabria, Rende, Italy
Napoleone DAgostino Institute on Membrane Technology, National
Research Council (ITM-CNR), University of Calabria, Rende, Italy
Naser Dalali Phase Separation and FIA Lab, Department of Chemistry,
Faculty of Science, University of Zanjan, Zanjan, Iran
Nguyen Phuoc Dan Faculty of Environment and Natural Resources,
University of Technology, Vietnam National University, Ho Chi Minh City,
Viet Nam
Ranjana Das Chemical Engineering Department, Jadavpur University,
Kolkata, West Bengal, India
Maria Grazia De Angelis Dipartimento di Ingegneria Civile, Chimica,
Ambientale e dei Materiali, Universit di Bologna, Bologna, Italy
Frederico de Araujo Kronemberger COPPE Chemical Engineering Pro-
gram, Federal University of Rio de Janeiro (UFRJ), Rio de Janeiro, RJ, Brazil
Loredana De Bartolo Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, Rende, Italy
Johannes De Bruijn Department of Agroindustry, Food Engineering Group,
Universidad de Concepcion, Chillan, Chile
Giovanni De Filpo Dipartimento di Chimica e Tecnologie Chimiche,
Universit della Calabria, Arcavacata di Rende, Italy
Giorgio De Luca Institute on Membrane Technology, National Research
Council of Italy, ITM-CNR, Rende, Italy
Mario De Rosa Department of Experimental Medicine, Section of Biotech-
nology, Medical Histology and Molecular Biology, Second University of
Naples, Napoli, Italy
Maria Norberta De Pinho Chemical Engineering, Instituto Superior
Tcnico, Universidade de Lisboa, Lisbon, Portugal
xxii Contributors

Winnie Dejonghe Separation and Conversion Technology, Flemish Institute


of Technological Research (VITO), Mol, Belgium
Baolin Deng Department of Civil and Environmental Engineering, Univer-
sity of Missouri-Columbia, Columbia, MO, USA
Adil Denizli Department of Chemistry, Biochemistry Division, Hacettepe
University, Ankara, Turkey
Renzo Di Felice University of Genova, Genova, Italy
Gianluca Di Proo Institute on Membrane Technology, National Research
Council of Italy, ITM-CNR, Rende, Italy
Maria Luisa Di Vona Dip. Di Scienze Technologie Chimiche, University of
Rome Tor Vergata, Rome, Italy
Nazely Diban Department of Chemical and Biomolecular Engineering,
University of Cantabria, Santander, Cantanbria, Spain
George Dibrov A.V. Topchiev Institute of Petrochemical Synthesis, Russian
Academy of Sciences, Moscow, Russia
Laura Donato Institute on Membrane Technology, National Research Coun-
cil of Italy, ITM-CNR, Rende, Italy
Marijana M. Dragosavac Chemical Engineering Department, Loughbor-
ough University, Loughborough, Leicestershire, UK
Enrico Drioli Institute on Membrane Technology, National Research Coun-
cil of Italy, ITM-CNR, Rende, Italy
Department of Environmental and Chemical Engineering, University of
Calabria, Rende, Italy
WCU Energy Engineering Department, Hanyang University, Seoul, S. Korea
Center of Excellence in Desalination Technology, King Abdulaziz University,
Jeddah, Saudi Arabia
Martin Drobek Institut Europen des Membranes, Universit de Montpel-
lier, Montpellier, France
Gabriela Dudek Department of Physical Chemistry and Technology of
Polymers, Silesian University of Technology (SUT), Gliwice, Poland
Mikel Duke Institute for Sustainability and Innovation, College of Engineer-
ing and Science, Victoria University, Melbourne, VIC, Australia
Hoang Hanh Phuoc Duong King Abdullah University of Science and Tech-
nology (KAUST), Biological and Environmental Science and Engineering
Division (BESE), Thuwal, Saudi Arabia
Sravya Duvvuri Membrane Separations Group, Chemical Engineering Divi-
sion, CSIR-Indian Institute of Chemical Technology, Hyderabad, India
Contributors xxiii

Piotr Dydo Silesian University of Technology, Gliwice, Poland


Ehiaze Augustine Ehimen Separation and Conversion Technology, Flemish
Institute of Technological Research (VITO), Mol, Belgium
Gemma Eibes Department of Chemical Engineering, Institute of Technol-
ogy, University of Santiago de Compostela, Santiago de Compostela, Spain
M. S. Mohy Eldin Polymer Materials Research Department, Advanced
Technologies and New Materials Research Institute (ATNMRI), City for
Scientic Research and Technology Applications (CSRTA), New Borg
El-Arab City, Alexandria, Egypt
Isabel C. Escobar University of Kentucky, Lexington, KY, USA
Anthony Gordon Fane Singapore Membrane Technology Centre, Nanyang
Environment and Water Research Institute, Nanyang Technological Univer-
sity, Singapore, Singapore
Tony Fane School of Chemical Engineering, The University of New South
Wales, Sydney, NSW, Australia
Singapore Membrane Technology Centre, Nanyang Technological University,
Singapore, Singapore
Mnica Faria Chemical Engineering, Columbia University, New York, NY,
USA
Gumersindo Feijoo Department of Chemical Engineering, Institute of Tech-
nology, University of Santiago de Compostela, Santiago de Compostela, Spain
Ekain Fernandez Energy and Environment, TECNALIA, Donostia-San
Sebastian, Gipuzkoa, Spain
Frederico Castelo Ferreira Department of Bioengineering, Instituto Supe-
rior Tcnico, Institute for Bioengineering and Biosciences, Universidade de
Lisboa, Lisbon, Portugal
Patrick Fievet Institut UTINAM, University of Franche-Comt, Besanon,
France
Alberto Figoli Institute on Membrane Technology, National Research
Council of Italy, ITM-CNR, Rende, Italy
Gustavo Fimbres Weihs Ctedras CONACYT, Instituto Tecnolgico de
Sonora, Cd. Obregn, Sonora, Mexico
Greg Foley School of Biotechnology, Dublin City University, Dublin,
Ireland
Enrica Fontananova Institute on Membrane Technology, National Research
Council of Italy, ITM-CNR, Rende, Italy
Patrizia Formoso Dipartimento di Farmacia e Scienze della Salute e della
Nutrizione, Universit della Calabria, Arcavacata di Rende, Italy
xxiv Contributors

Filomena Freitas UCIBIO-REQUIMTE, Departamento de Qumica,


Faculdade de Cincias e Tecnologia, Universidade Nova de Lisboa, Caparica,
Portugal

Karel Friess Department of Physical Chemistry, University of Chemistry


and Technology Prague, Prague, Czech Republic

Francesco Galiano Institute on Membrane Technology, National Research


Council of Italy, ITM-CNR, Rende, Italy

Claudia F. Galinha REQUIMTE-CQFB, Chemistry Dept. Faculdade de


Cincias e Tecnologia, FCT-Universidade Nova de Lisboa, Campus da
Caparica, Caparica, Portugal

Fausto Gallucci Chemical Process Intensication, Department of Chemical


Engineering and Chemistry, Eindhoven University of Technology, Eindhoven,
The Netherlands

Volker Gaukel Food Process Engineering, Karlsruhe Institute of Technology


(KIT), Karlsruhe, Germany

Abaynesh Yihdego Gebreyohannes Institute on Membrane Technology,


National Research Council of Italy, ITM-CNR, Rende, Italy

Geoffrey Geise Department of Chemical Engineering, University of


Virginia, Charlottesville, VA, USA

Lidietta Giorno Institute on Membrane Technology, National Research


Council of Italy, ITM-CNR, Rende, Italy

Zbigniew J. Grzywna Department of Physical Chemistry and Technology of


Polymers, Silesian University of Technology (SUT), Gliwice, Poland

Annarosa Gugliuzza Institute on Membrane Technology, National Research


Council of Italy, ITM-CNR, Rende, Italy

Gemma Gutirrez Department of Chemical and Environmental Engineer-


ing, University of Oviedo, Oviedo, Spain

May-Britt Hgg Department of Chemical Engineering, Norwegian Univer-


sity of Science and Technology, Trondheim, Norway

Vu Pha Hai Greentech Environment Joint Stock Company, Ho Chi Minh


City, Vietnam

Nobuo Hara Research Institute for Chemical Process Technology, National


Institute of Advanced Industrial Science and Technology, Tsukuba, Japan

Tao He Lab for Membrane Materials and Separation Technology, Shanghai


Advanced Research Institute CAS, Shanghai, China

Xuezhong He Department of Chemical Engineering, Norwegian University


of Science and Technology, Trondheim, Sr-Trndelag, Norway
Contributors xxv

Arash Helmi Department of Chemical Engineering and Chemistry, Chemi-


cal Process Intensication, Technische Universiteit Eindhoven, Eindhoven,
The Netherlands
Sanne Hermans Centre for Surface Chemistry and Catalysis, Department of
M2S, Faculty Bioscience Engineering, KU Leuven, Leuven, Belgium
Daphne Hermosilla Department of Chemical Engineering, Universidad
Complutense de Madrid, Madrid, Spain
Mitsuru Higa Graduate School of Science and Engineering, Yamaguchi
University, Ube, Yamaguchi, Japan
A. Higuchi Department of Chemical and Materials Engineering, National
Central University, Chung-Li, Taoyuan, Taiwan
Nidal Hilal Centre for Water Advanced Technologies and Environmental
Research (CWATER), College of Engineering, Swansea University, Swansea,
Wales, UK
W. S. Winston Ho Department of Chemical and Biomolecular Engineering,
The Ohio State University, Columbus, OH, USA
Richard G. Holdich Department of Chemical Engineering, Loughborough
University, Loughborough, Leicestershire, UK
R. W. Holloway Department of Civil and Environmental Engineering,
Colorado School of Mines, Golden, CO, USA
Benjamin S. Hsiao Department of Chemistry, Stony Brook University,
Stony Brook, NY, USA
Shu-Hau Hsu Department of Materials Science and Engineering, University
of Florida, Gainesville, FL, USA
Department of Energy Engineering, Hanyang University, Seoul, Republic of
Korea
Yan Huang State Key Laboratory of Materials-Oriented Chemical Engineer-
ing, College of Chemical Engineering, Nanjing Tech University, Nanjing,
China
Alessandra Imbrogno Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, Rende, Italy
University of Calabaria, Rende, Italy
Christophe Innocent Institut Europen des Membranes, ENSCM, CNRS,
Universit de Montpellier, Montpellier, France
Angel Irabien Departamento de Ingeniera Qumica y Qumica Inorgnica,
Universidad de Cantabria, Santander, Spain
Ahmad Fauzi Ismail Faculty of Chemical and Energy Engineering,
Universiti Teknologi Malaysia, Advanced Membrane Technology Research
Centre (AMTEC), Johor Bahru, Johor, Malaysia
xxvi Contributors

Juhana Jaafar Faculty of Chemical and Energy Engineering, Universiti


Teknologi Malaysia, Advanced Membrane Technology Research Centre
(AMTEC), Johor Bahru, Johor, Malaysia
Marijke Jacobs Sustainable Materials Management, Flemish Institute for
Technological Research VITO, Mol, Belgium
Michel Jaffrin Department of Biological Engineering, Technological Uni-
versity of Compiegne, BP 20529, Compiegne Cedex, France
Johannes Carolus Jansen Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, Rende, Italy
Lan Ying Jiang School of Metallurgy and Environment, Central South
University, Changsha, China
Zhongyi Jiang School of Chemical Engineering and Technology, Tianjin
University, Nankai, Tianjin, China
Wanqin Jin State Key Laboratory of Materials-Oriented Chemical Engineer-
ing, Nanjing University of Technology, Nanjing, China
Daniel Johnson Centre for Water Advanced Technologies and Environmen-
tal Research (CWATER), College of Engineering, Swansea University,
Swansea, Wales, UK
D. M. Jovanovi Institute of Chemistry, Technology and Metallurgy
(I.Ch.T.M.), Center of Catalysis and Chemical Engineering, University of
Belgrade, Belgrade, Republic of Serbia
Anne Julbe Institut Europen des Membranes, Universit de Montpellier,
Montpellier, France
Nora Jullok School of Bioprocess Engineering, Universiti Malaysia Perlis
(UniMAP), Arau, Perlis, Malaysia
Mari Kallioinen Lappeenranta University of Technology, Lappeenranta,
Finland
Shinji Kanehashi Department of Applied Chemistry, Meiji University,
Tama-ku, Kawasaki, Japan
H. Kawakita Department of Applied Chemistry, Saga University, Saga,
Japan
A. P. Kharitonov Talrose Branch of the Institute of Energy Problems of
Chemical Physics of the Russian Academy of Sciences, Moscow Region,
Russia
Jeong F. Kim Department of Energy Engineering, Hanyang University,
Seoul, South Korea
Benjamin F. K. Kingsbury Imperial College London, London, UK
Vladimir S. Kislik Campus Givat Ram, Casali Institute of Applied Chemis-
try, The Hebrew University of Jerusalem, Jerusalem, Israel
Contributors xxvii

Chalida Klaysom Centre for Surface Chemistry and Catalysis, KU Leuven,


Leuven, Heverlee, Belgium

P. Knauth Madirel UMR 7246, Aix Marseille University-CNRS, Marseille


Cedex, France

Isao Kobayashi National Food Research Institute, National Agriculture and


Food Research Organization, Tsukuba, Ibaraki, Japan

N. M. Kocherginsky Biomime, Urbana, IL, USA

G. Kolb Product Sector Energy and Chemistry, Fraunhofer ICT-IMM,


Mainz, Germany

A. B. Koltuniewicz Biotechnology and Bioprocess Engineering Division,


Faculty of Chemical and Process Engineering, Warsaw University of Tech-
nology, Warsaw, Poland

Andras Koris Corvinus University of Budapest, Budapest, Hungary

Zoltn Kovcs Department of Food Engineering, Institue of Bioengineering


and Process Engineering, Szent Istvan University, Budapest, Hungary

Boguslaw Kruczek Department of Chemical and Biological Engineering,


University of Ottawa, Ottawa, ON, Canada

Ashwani Kumar Institute of Chemical Process and Environmental Technol-


ogy, National Research Council Canada, Ottawa, ON, Canada

Kripal S. Lakhi Australian Institute for Bioengineering and Nanotechnol-


ogy, The University of Queensland, Brisbane, QLD, Australia

Doriano Lamba Institute of Crystallography, National Research Council,


Trieste, Italy

Marek Lan University of Chemistry and Technology Prague, Prague 6,


Czech Republic

W. J. Lau Advanced Membrane Technology Research Centre (AMTEC),


Universiti Teknologi Malaysia, Skudai, Johor, Malaysia

Thi Xuan Huong Le Vanlang University, Ho Chi Minh City, Vietnam

Pierre Le-Clech School of Chemical Engineering, The University of New


South Wales, UNESCO Centre for Membrane Science and Technology,
Sydney, NSW, Australia

Kew-Ho Lee Center for Membranes, Korea Research Institute of Chemical


Technology (KRICT), Yuseong-gu, Daejeon, South Korea

Cecile Legallais UMR CNRS 7338 Biomechanics and Bioengineering,


Universit de Technologie de Compiegne (UTC), Compiegne, France

Raymond L. Legge Department of Chemical Engineering, University of


Waterloo, Waterloo, ON, Canada
xxviii Contributors

Juan M. Lema Department of Chemical Engineering, Institute of Technol-


ogy, University of Santiago de Compostela, Santiago de Compostela, Spain
Gerardo Len Departamento de Ingeniera Qumica y Ambiental,
Universidad Politcnica de Cartagena, Cartagena, Spain
Geoffroy Lesage Institut Europen des membranes, IEM, UMR-5635,
Universit de Montpellier, ENSCM, CNRS, Montpellier, France
Baoqiang Liao Department of Chemical Engineering, Lakehead University,
Thunder Bay, ON, Canada
Hongyu Li UNESCO Centre for Membrane Science and Technology, The
University of New South Wales, Sydney, Australia
Jianxin Li State Key Laboratory of Separation Membranes and Membrane
Processes, School of Materials Science and Engineering, Tianjin Polytechnic
University, Tianjin, Peoples Republic of China
Na Li Department of Chemical Engineering, School of Chemical Engineer-
ing and Technology, Xian Jiaotong University, Xian City, China
Xianhui Li State Key Laboratory of Separation Membranes and Membrane
Processes, School of Materials Science and Engineering, Tianjin Polytechnic
University, Tianjin, Peoples Republic of China
Yanshuo Li State Key Laboratory of Catalysis, Dalian Institute of Chemical
Physics, CAS, Dalian, China
Yifan Li School of Chemical Engineering and Technology, Tianjin Univer-
sity, Nankai, Tianjin, China
Haiqing Lin Department of Chemical and Biological Engineering, Univer-
sity at Buffalo, The State University of New York, Buffalo, NY, USA
Frank Lipnizki Alfa Laval Copenhagen, Sborg, Copenhagen, Denmark
Fu Liu Ningbo Institute of Materials Technology and Engineering, Chinese
Academy of Sciences, Ningbo, China
Wei Liu Energy and Environment Technology Directorate, Pacic Northwest
National Laboratory, Richland, WA, USA
Jordi Llorca Institute of Energy Technologies, Universitat Politcnica de
Catalunya, Barcelona, Spain
Lucia Lloret Chemical and Environmental Engineering Department,
Federico Santa Maria Technical University, Santiago, Chile
Juan Manuel Lpez-Romero Departamento de Quimica Organica,
Universidad de Malaga, Facultad de Ciencias, Malaga, Spain
Alessandra Lorenzetti Department of Industrial Engineering, University of
Padova, Padova, Italy
Contributors xxix

Thelmo Lu-Chau Department of Chemical Engineering, Institute of Tech-


nology, University of Santiago de Compostela, Santiago de Compostela, Spain
Diego Luna Department of Organic Chemistry, University of Cordoba,
Cordoba, Spain
Herb Lutz EMD Millipore Corporation, Playa del Rey, CA, USA
Hongyang Ma Department of Chemistry, Stony Brook University, Stony
Brook, NY, USA
Angela C. Macedo LEPABE Laboratory of Engineering of Processes,
Environment, Biotechnology and Energy, University of Porto, Porto, Portugal
Francesca Macedonio Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, Rende, Italy
Department of Environmental and Chemical Engineering, University of
Calabria, Rende, Italy
Sayed S. Madaeni Membrane Research Center, Chemical Engineering
Department, Razi University, Kermanshah, Iran
Hacene Mahmoudi Science and Technology, Faculty of Technology,
University Hassiba Benbouali of Chlef, Chlef, Algeria
Swachchha Majumdar Ceramic Membrane Division, CSIR-Central Glass
and Ceramic Research Institute, Kolkata, West Bengal, India
F. Xavier Malcata DEQ Department of Chemical Engineering and LEPABE
Laboratory of Engineering of Processes, Environment, Biotechnology and
Energy, University of Porto, Porto, Portugal
Mario Malinconico Research Director, Institute for Polymers, Composites
and Biomaterials (IPCB-CNR), Pozzuoli, Naples, Italy
Reyes Mallada Department of Chemical and Environmental Engineering
and Aragon Nanoscience Institute, Universidad de Zaragoza, Zaragoza, Spain
Mara Matos Department of Chemical and Environmental Engineering,
University of Oviedo, Oviedo, Spain
Davide Mattia Department of Chemical Engineering, University of Bath,
Bath, UK
Rosalinda Mazzei Institute on Membrane Technology, National Research
Council of Italy, ITM-CNR, Rende, Italy
Beatriz Mello UFSCar, Federal University of Sao Carlos, Buri, SP, Brazil
Adelio Mendes Faculty of Engineering, University of Porto, Porto, Portugal
Julie Mendret Institut Europen des Membranes, ENSCM-UM-CNRS
(UMR 5635), Universit de Montpellier, Montpellier Cedex 5, France
xxx Contributors

Miguel Menendez Department of Chemical and Environmental Engineer-


ing, University of Zaragoza, Zaragoza, Spain
Antonietta Messina Institute on Membrane Technology, National Research
Council of Italy, ITM-CNR, Rende, Italy
Bart Michielsen Sustainable Materials Management, Flemish Institute for
Technological Research VITO, Mol, Belgium
Vesna Middelkoop Flemish Institute for Technological Research VITO,
Mol, Belgium
Martine Mietton-Peuchot Vine and Wine Sciences Institute, Universite de
BORDEAUX, Villenave dOrnon, France
Antonella Milella Department of Chemistry, University of Bari Aldo
Moro, Institute of Nanotechnology (CNR-NANOTEC), Bari, Italy
Francesca Militano Institute on Membrane Technology, National Research
Council of Italy, ITM-CNR, Rende, Italy
University of Calabria, Rende, Italy
Ubavka B. Mio Faculty of Physical Chemistry, University of Belgrade,
Belgrade, Republic of Serbia
Ilaria Mirabelli HyGear B.V. Westervoortsedijk, AV, Arnhem, The
Netherlands
Hossein Mirsaeedghazi Department of Food Technology, Abouraihan
College, University of Tehran, Pakdasht, Iran
Michele Modesti Department of Industrial Engineering, University of
Padova, Padova, Italy
Khayet Mohamed Department of Applied Physics, Universidad
Complutense de Madrid, Madrid, Spain
P. K. Mohapatra Radiochemistry Division, Bhabha Atomic Research
Centre, Mumbai, Maharashtra, India
Z. D. Mojovi Institute of Chemistry, Technology and Metallurgy
(I.Ch.T.M.), Center of Catalysis and Chemical Engineering, University of
Belgrade, Belgrade, Republic of Serbia
Raffaele Molinari Dipartimento di Ingegneria per lAmbiente e il Territorio
e Ingegneria Chimica (DIATIC), Universit della Calabria, Rende, Italy
M. Concepcin Monte Department of Chemical Engineering, Universidad
Complutense de Madrid, Madrid, Spain
Seung-Hyeon Moon School of Environmental Science and Engineering,
Gwangju Institute of Science and Technology (GIST), Gwangju, South Korea
Contributors xxxi

Mara. T. Moreira Department of Chemical Engineering, School of Engi-


neering, University of Santiago de Compostela, Santiago de Compostela,
Spain
Sabrina Morelli Institute on Membrane Technology, National Research
Council of Italy, ITM-CNR, Rende, Italy
Carlos Moreno Department of Analytical Chemistry, Faculty of Marine and
Environmental Sciences, University of Cdiz, Puerto Real, Spain
Siddhartha Moulik Membrane Separations Group, Chemical Engineering
Division, CSIR-Indian Institute of Chemical Technology, Hyderabad, India
Philippe Moulin Laboratoire de Mcanique, Modlisation et Procds
Propres (M2P2-UMR 7340), Equipe Procds Membranaires (EPM), Aix
Marseille Universit, AIX en PROVENCE, France
Z. V. P. Murthy Department of Chemical Engineering, S.V. National Insti-
tute of Technology, Surat, Gujarat, India
Kazukiyo Nagai Department of Applied Chemistry, Meiji University, Tama-
ku, Kawasaki, Japan
Harsha Nagar Membrane Separations Group, Chemical Engineering Divi-
sion, CSIR-Indian Institute of Chemical Technology, Hyderabad, India
Hiroki Nagasawa Department of Chemical Engineering, Hiroshima Univer-
sity, Higashi-Hiroshima, Japan
Endre Nagy Research Institute of Chemical and Process Engineering,
University of Pannonia, Veszprem, Hungary
Mitsutoshi Nakajima Faculty of Life and Environmental Sciences, Univer-
sity of Tsukuba, Tsukuba, Ibaraki, Japan
Zoran P. Nedi Faculty of Physical Chemistry, University of Belgrade,
Belgrade, Republic of Serbia
Carlos Negro Department of Chemical Engineering, Universidad
Complutense de Madrid, Madrid, Spain
Fiore Pasquale Nicoletta Dipartimento di Farmacia e Scienze della Salute e
della Nutrizione, Universit della Calabria, Arcavacata di Rende, Italy
Johanna Niemist Helsinki Region Chamber of Commerce, Enterprise
Europe Network, Helsinki, Finland
Suzana Pereira Nunes Division of Biological and Environmental Sciences
and Engineering, Nanostructured Polymeric Membranes Lab, King Abdullah
University of Science and Technology (KAUST), Thuwal, Saudi Arabia
Darren Oatley-Radcliffe College of Engineering, Swansea University,
Swansea, UK
xxxii Contributors

Osvaldo N. Oliveira Jr. Sao Carlos Institute of Physics IFSC, University of


Sao Paulo USP, Sao Paulo, Brazil
B. S. Ooi School of Chemical Engineering, Universiti Sains Malaysia,
Nibong Tebal, Pulau Pinang, Malaysia
Immaculada Ortiz Department of Chemical and Biomolecular Engineering,
University of Cantabria, Santander, Cantabria, Spain
M. H. D. Othman Advanced Membrane Technology Research Centre
(AMTEC), Universiti Teknologi Malaysia, Skudai, Johor, Malaysia
Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia,
Skudai, Johor, Malaysia
N. Othman Faculty of Chemical and Energy Engineering, Universiti
Teknologi Malaysia, Skudai, Johor, Malaysia
Mehmet A. Oturan Laboratory of Earth Materials and Environment,
University Paris-Est, Marne La valle, Champs-sur-Marne, France
David A. Pacheco Tanaka Energy and Environment, TECNALIA,
Donostia-San Sebastian, Gipuzkoa, Spain
Leonardo Palmisano Dipartimento di Energia, Ingegneria
dellInformazione e Modelli Matematici (DEIM), Universit di Palermo,
Palermo, Italy
Fabio Palumbo Department of Chemistry, University of Bari Aldo Moro,
Institute of Nanotechnology (CNR-NANOTEC), Bari, Italy
Chi Hoon Park Gyeongnam National University of Science and Technology
(GNTECH), Jinju-si, Gyeongsangnam-do, Republic Of Korea (South Korea)
Donald R. Paul Department of Chemical Engineering, Texas Materials Insti-
tute, Austin, TX, USA
Radoslav Paulen Department of Biochemical and Chemical Engineering,
Technische Universitt Dortmund, Dortmund, Germany
Carmen Pazos Department of Chemical and Environmental Engineering,
University of Oviedo, Oviedo, Spain
Graeme K. Pearce Membrane Consultancy Associates Limited, Reading,
RG8 7EJ, UK
Ludmila Georgieva Peeva Imperial College London, London, UK
Jinming Peng Key Laboratory for Green Chemical Technology of Ministry
of Education, School of Chemical Engineering and Technology, Tianjin Uni-
versity, Tianjin, Peoples Republic of China
Francois Perreault School of Sustainable Engineering and the Built Envi-
ronment, Arizona State University, Tempe, AZ, USA
Thijs Peters SINTEF Materials and Chemistry, SINTEF, Oslo, Norway
Contributors xxxiii

Emma Piacentini Institute on Membrane Technology, National Research


Council of Italy, ITM-CNR, Rende, Italy

Monica Pica University of Perugia, Department of Pharmaceutical Sciences,


Perugia, Italy

Antonella Piscioneri Institute on Membrane Technology, National Research


Council of Italy, ITM-CNR, Rende, Italy

Teresa Poerio Institute on Membrane Technology, National Research Coun-


cil of Italy, ITM-CNR, Rende, Italy

Carla A. M. Portugal REQUIMTE-LAQV, Chemistry Department, FCT-


Universidade Nova de Lisboa, Campus da Caparica, Caparica, Portugal

Grald Pourcelly Institut Europeen des Membranes, CC 047, Universite


Montpellier II, Place Eugene Bataillon, Montpellier, France

Gonzalo Prieto Max-Planck-Institut fur Kohlenforschung, Mulheim an der


Ruhr, Germany

Pushpinder S. Puri PuriMem, LLC, Emmaus, PA, USA

Saren Qi Singapore Membrane Technology Centre, Nanyang Technological


University, Singapore, Singapore
Department of Civil Engineering, The University of Hong Kong, Hong Kong,
Hong Kong SAR

Xianghong Qian Department of Biomedical Engineering, University of


Arkansas, Fayetteville, AR, USA

Damien Quemener Institut Europen des Membranes, Montpellier, France

Cejna Anna Quist-Jensen Institute on Membrane Technology, National


Research Council of Italy, ITM-CNR, Rende, Italy
Department of Environmental and Chemical Engineering, University of
Calabria, Rende, Italy

Mukhlis bin A. Rahman Faculty of Chemical and Energy Engineering,


Advanced Membrane Technology Research Centre (AMTEC), Universiti
Teknologi Malaysia, Skudai, Johor, Malaysia
Department of Energy Engineering, Faculty of Chemical and Energy Engi-
neering, Universiti Teknologi Malaysia, Johor Bahru, Johor Darul Takzim,
Malaysia

Fen Ran School of Material Science and Engineering, State Key Laboratory
of Advanced Processing and Recycling of Non-ferrous Metals, Lanzhou
University of Technology, Lanzhou, P. R. China

Giuseppe Ranieri Institute on Membrane Technology, National Research


Council of Italy, ITM-CNR, Rende, Italy
xxxiv Contributors

Maria A. M. Reis UCIBIO-REQUIMTE, Departamento de Qumica,


Faculdade de Cincias e Tecnologia, Universidade Nova de Lisboa, Caparica,
Portugal

Gilbert M. Rios Place Eugene Bataillon, IEM European Membrane Insti-


tute, Montpellier, France

Tania Rodenas Max Planck Institute fur Chemische Energiekonversion,


Mulheim an der Ruhr, Germany

Denis Roizard Laboratoire Ractions et Gnie des Procds, CNRS-


Universit de Lorraine, Nancy, France

Virginia Romero Departamento de Fisica Aplicada I, Universidad de


Malaga, Facultad de Ciencias, Malaga, Spain

Martina Roso Department of Industrial Engineering, University of Padova,


Padova, Italy

Stephanie Roualdes IEM/UM II CC 047, Place Eugene Bataillon, Mont-


pellier, France

Ren Ruby-Figueroa Institute on Membrane Technology, National


Research Council of Italy, ITM-CNR, Rende, Italy

Aleksandra Rybak Department of Physical Chemistry and Technology of


Polymers, Silesian University of Technology (SUT), Gliwice, Poland

Jose Sabate Department dEnginyeria Agroalimentaria i Biotecnologia,


Universitat Politecnica de Catalunya, Castelldefels, Spain

Keiji Sakaki National Institute of Advanced Industrial Science and Technol-


ogy (AIST), Research Institute for Sustainable Chemistry, Tsukuba, Ibaraki,
Japan

Simona Salerno Institute on Membrane Technology, National Research


Council of Italy, ITM-CNR, Rende, Italy

Marius Sandru Polymer Particles and Surface Chemistry, Materials and


Chemistry, SINTEF, Trondheim, Norway

Tsuneji Sano Department of Applied Chemistry, Hiroshima University,


Graduate School of Engineering, Higashi-Hiroshima, Japan

Giulio C. Sarti Department of Chemical Engineering, Mining and Environ-


mental Technology, University of Bologna, Bologna, Italy

Shuichi Sato Department of Applied Chemistry, Meiji University, Tama-ku,


Kawasaki, Japan

Yamini Satyawali Separation and Conversion Technology, Vlaamse


Instelling voor Technologisch Onderzoek (VITO), Boeretang 200, Belgium
Contributors xxxv

Thomas Schfer Institute for Polymer Materials (Polymat), University of the


Basque Country (UPV/EHU), Donostia-San Sebastin, Spain
A. P. H. J. Schenning Department of Chemical Engineering and Chemistry,
Group Functional Organic Materials and Devices (SFD), Eindhoven Univer-
sity of Technology, Eindhoven, The Netherlands
Chiara Schiraldi Department of Experimental Medicine, Section of Bio-
technology, Medical Histology and Molecular Biology, Second University of
Naples, Napoli, Italy
Colin A. Scholes Department of Chemical and Biomolecular Engineering,
University of Melbourne, Parkville, VIC, Australia
Marco Scholz Aachener Verfahrenstechnik Chemical Process Engineering,
RWTH Aachen University, Aachen, Germany
Karin Schroen Laboratory of Food Process Engineering, Wageningen
University and Research Centre, Wageningen, The Netherlands
Anna Schuch Food Process Engineering, Karlsruhe Institute of Technology
(KIT), Karlsruhe, Germany
Heike Schuchmann Food Process Engineering, Karlsruhe Institute of
Technology (KIT), Karlsruhe, Germany
Dwaipayan Sen Department of Chemical Engineering, Heritage Institute of
Technology, Kolkata, West Bengal, India
Laurentia Setiawan Singapore Membrane Technology Centre, Nanyang
Environment and Water Research Institute, Nanyang Technological Univer-
sity, Singapore, Singapore
Jiahui Shao School of Environmental Science and Engineering, Shanghai
Jiao Tong University, Shanghai, Peoples Republic of China
Cameron Shearer School of Chemical and Physical Sciences, Flinders
University, Adelaide, South Australia, Australia
Institute of Physical Chemistry, University of Muenster, Muenster, North
RhineWestphalia, Germany
Tauqir A. Sherazi Department of Chemistry, COMSATS Institute of Infor-
mation Technology, Abbottabad, Pakistan
Jiafu Shi School of Environment Science and Engineering, Tianjin Univer-
sity, Tianjin, China
Ryohei Shindo Department of Applied Chemistry, Meiji University, Tama-
ku, Kawasaki, Japan
Barbara Siembida-Lsch Centre for Alternative Wastewater Treatment,
Fleming College, Lindsay, ON, Canada
xxxvi Contributors

Wolfgang M. Sigmund Department of Materials Science and Engineering,


University of Florida, Gainesville, FL, USA
Department of Energy Engineering, Hanyang University, Seoul, Republic of
Korea
Veronica Silva Dow Water and Process Solution Division at The Dow
Chemical Company, Boulevard Cecilia Grierson 355, Buenos Aires,
Argentina
S. T. V. Sim Singapore Membrane Technology Centre, Nanyang Environ-
ment and Water Research Institute, Nanyang Technological University,
Singapore, Singapore
Silvia Simone Institute on Membrane Technology, National Research Coun-
cil of Italy, ITM-CNR, Rende, Italy
Eugene Skouras Institute of Chemical Engineering Sciences, Foundation for
Research and Technology, Hellas, Patras, Hellas
Jose M. Sousa Chemistry Department, School of Life and Environment
Sciences, University of Tras-os-Montes e Alto Douro, Vila Real, Portugal
LEPABE Laboratory for Process Engineering, Environment, Biotechnology
and Energy, Chemical Engineering Department, Faculty of Engineering,
University of Porto, Rua Roberto Frias, Porto, Portugal
S. Sridhar Membrane Separations Group, Chemical Engineering Division,
CSIR-Indian Institute of Chemical Technology, Hyderabad, India
Heiner Strathmann Universitt Stuttgart, Institute of Chemical Process
Engineering Stuttgart, Baden-Wurttemberg, Germany
Anna Strzelewicz Faculty of Chemistry, Silesian University of Technology,
Gliwice, Poland
Yanlei Su School of Chemical Engineering and Technology, Tianjin Univer-
sity, Nankai, Tianjin, Peoples Republic of China
Shing-Yi Suen Department of Chemical Engineering, National Chung Hsing
University, Taichung, Taiwan
Guofei Sun Chemical and Biomolecular Engineering, Aquaporin Asia Pte.
Ltd, Singapore, Singapore
Sridhar Sundergopal Membrane Separations Group, Chemical Engineering
Division, CSIR-Indian Institute of Chemical Technology, Hyderabad, India
Stanislaus Raditya Suwarno Singapore Membrane Technology Centre,
Nanyang Technological University, Singapore, Singapore
Petr Sysel Department of Polymers, Institute of Chemical Technology,
Prague, Czech Republic
Guttorm Syvertsen-Wiig Ceramic Powder Technology AS, Tiller, Norway
Contributors xxxvii

Gyorgy Szekely School of Chemical Engineering and Analytical Science,


The University of Manchester, Manchester, UK
Roberto Taboada-Puig Department of Chemical Engineering, Institute of
Technology, University of Santiago de Compostela, Santiago de Compostela,
Spain
Chung Tai-Shung Neal National University of Singapore, Singapore,
Singapore
Yoshinobu Tanaka IEM Research, Ushiki-shi, Ibaraki, Japan
Chuyang Y. Tang Department of Civil Engineering, The University of Hong
Kong, Hong Kong, Hong Kong SAR
Department of Civil Engineering The University of Hong Kong, Hong Kong,
Hong Kong SAR
Franco Tasselli Institute on Membrane Technology, National Research
Council of Italy, ITM-CNR, Rende, Italy
Bui Xuan Thanh Faculty of Environment and Natural Resources, University
of Technology, Vietnam National University, Ho Chi Minh City, Vietnam
Kalsang Tharpa Department of Chemistry, University of Mysore, Mysore,
India
Elena Tocci Institute on Membrane Technology, National Research Council
of Italy, ITM-CNR, Rende, Italy
Maria Tomaszewska Faculty of Chemical Technology and Engineering,
West Pomeranian University of Technology, Szczecin, Poland
Carles Torras Font Bioenergy and Biofuels, Catalonia Institute for Energy
Research (IREC), Tarragona, Catalonia, Spain
Bijay P. Tripathi Department of Nanostructured Materials, Leibniz Institute
of Polymer Research Dresden, Dresden, Germany
Francesco Trotta Department of Chemistry, University of Torino, Torino,
Italy
Toshinori Tsuru Department of Chemical Engineering, Hiroshima Univer-
sity, Higashi-Hiroshima, Japan
Marian Turek Faculty of Chemistry, Silesian University of Technology,
Gliwice, Poland
Deniz T urkmen Department of Chemistry, Biochemistry Division,
Hacettepe University, Ankara, Turkey
Tadashi Uragami Organization for Research and Development of Innova-
tive Science and Technology (ORDIST), Kansai University, Suita, Osaka,
Japan
xxxviii Contributors

Mohamad Hekarl Uzir School of Chemical Engineering, Universiti Sains


Malaysia, Penang, Malaysia

B. Aakruthi Vaishnavi Membrane Separations Group, Chemical Engineer-


ing Division, CSIR-Indian Institute of Chemical Technology, Hyderabad,
India

Csar Valderrama Department of Chemical Engineering, Universitat


Politcnica de Catalunya-Barcelona Tech (UPC), Barcelona, Catalonia, Spain

Bart Van der Bruggen Department of Chemical Engineering, Process Engi-


neering for Sustainable Systems (ProcESS), KU Leuven, Leuven, Belgium

P. C. van H. Kuringen Department of Chemical Engineering and Chemistry,


Group Functional Organic Materials and Devices (SFD), Eindhoven Univer-
sity of Technology, Eindhoven, The Netherlands

Ivo Vankelecom Centre for Surface Chemistry and Catalysis, KU Leuven,


Leuven, Heverlee, Belgium

Todor Vasiljevic Advanced Food Systems Research Unit, College of Health


and Biomedicine, Victoria University, Melbourne, VIC, Australia

C. V. Vedavyasan Department of Technology, Annamalai University,


Chidambaram, Tamil Nadu, India

Tanja Vidakovic-Koch Max Planck Institute for Dynamics of Complex


Technical Systems, Magdeburg, Germany

Loreen O. Villacorte FMC Technologies, Separation Innovation and


Research Center, Arnhem, The Netherlands

Giuseppe Vitola Institute on Membrane Technology, National Research


Council of Italy, ITM-CNR, Rende, Italy

Goran T. Vladisavljevi Department of Chemical Engineering, Loughbor-


ough University, Loughborough, Leicestershire, UK

Alexey Volkov A.V. Topchiev Institute of Petrochemical Synthesis Russian


Academy of Sciences (TIPS RAS), Moscow, Russia

V. V. Volkov A.V. Topchiev Institute of Petrochemical Synthesis Russian


Academy of Sciences (TIPS RAS), Moscow, Russian Federation

Diogo Volpati Sao Carlos Institute of Physics IFSC, University of Sao


Paulo USP, Sao Paulo, Brazil

Bo Wang Department of Chemical Engineering, Imperial College London,


London, UK

Honglei Wang Department of Chemical and Biomolecular Engineering,


jMedtech Pte Ltd, Singapore, Singapore
Contributors xxxix

Rong Wang Singapore Membrane Technology Centre, Nanyang Environ-


ment and Water Research Institute; School of Civil and Environmental Engi-
neering, Nanyang Technological University, Singapore, Singapore
Shaofei Wang School of Chemical Engineering and Technology, Tianjin
University, Nankai, Tianjin, China
Xiaoli Wang School of Chemical Engineering and Technology, Tianjin
University, Nankai, Tianjin, China
Zhi Wang Chemical Engineering Research Center, School of Chemical
Engineering and Technology, Tianjin University, Tianjin, China
Zhiwei Wang Department of Environmental Engineering, College of Envi-
ronmental Science and Engineering, Tongji University, Shanghai, China
S. Ranil Wickramasinghe Ralph E Martin Department of Chemical
Engineering, University of Arkansas, Fayetteville, AR, USA
Dianne Wiley School of Chemical and Biomolecular Engineering, The
University of Sydney, Sydney, NSW, Australia
Paul Melvyn Williams College of Engineering, Swansea University,
Swansea, UK
Daniel Winter Fraunhofer Institute for Solar Energy Systems (ISE),
Freiburg, Germany
Chunrui Wu State Key Laboratory of Hollow Fiber Membrane Materials
and Membrane Processes, Institute of Biological and Chemical Engineering,
Tianjin Polytechnic University, Tianjin, China
Hong Wu School of Chemical Engineering and Technology, Tianjin Univer-
sity, Nankai, Tianjin, Peoples Republic of China
Yvan Wyart CNRS, Centrale Marseille, M2P2 UMR 7340, Equipe Procds
Membranaires (EPM), Aix Marseille Universit, Aix en Provence Cedex,
France
Tongwen Xu Collaborative Innovation Centre of Chemistry for Energy
Materials, School of Chemistry and Material Science, University of Science
and Technology of China, Hefei, P.R. China
Yuri Yampolskii A.V. Topchiev Institute of Petrochemical Synthesis,
Russian Academy of Sciences, Moscow, Russia
Dong Yang School of Chemical Engineering and Technology, Tianjin
University, Nankai, Tianjin, China
Handan Yavuz Department of Chemistry, Biochemistry Division, Hacettepe
University, Ankara, Turkey
Jun Yin Department of Civil and Environmental Engineering, University of
Missouri-Columbia, Columbia, MO, USA
xl Contributors

Masakazu Yoshikawa Department of Biomolecular Engineering, Kyoto


Institute of Technology, Kyoto, Japan
Miki Yoshimune Research Institute for Chemical Process Technology,
National Institute of Advanced Industrial Science and Technology (AIST),
Tsukuba, Japan
S. M. Javaid Zaidi Australian Institute for Bioengineering and Nanotech-
nology, The University of Queensland, Brisbane, QLD, Australia
King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia
Grayna Zakrzewska-Kotuniewicz Institute of Nuclear Chemistry and
Technology Instytut Chemii i Techniki Jdrowej, Warszawa, Poland
Li-Zhi Zhang Key Lab of Enhanced Heat Transfer and Energy Conserva-
tion, South China University of Technology, Guangzhou, China
Chen Zhang School of Chemical and Biomolecular Engineering, Atlanta,
GA, USA
Jianhua Zhang Department of Polymer Science and Engineering, School of
Chemical Engineering and Technology, Tianjin University, Tianjin, China
Tianjin Key Laboratory of Membrane Science and Desalination Technology,
Tianjin University, Tianjin, China
Yuzhong Zhang School of Material Science and Engineering, Tianjin Poly-
technic University, Tianjin, China
Jing Zhao School of Chemical Engineering and Technology, Tianjin Uni-
versity, Nankai, Tianjin, China
Xueting Zhao School of Chemical Engineering and Technology, Tianjin
University, Nankai, Tianjin, Peoples Republic of China
Pei Shan Zhong Functionalized Materials and Nanostructures/Global
Research Centre Singapore (GMM/F), BASF South East Asia Pte Ltd.,
Singapore, Singapore
Li-Ping Zhu MOE Key Laboratory of Macromolecular Synthesis and
Functionalization, Department of Polymer Science and Engineering, Zhejiang
University, Hangzhou, Zhejiang, Peoples Republic of China
Xiaoying Zhu Department of Civil and Environmental Engineering, National
University of Singapore, Faculty of Engineering, Singapore, Singapore
Andrew L. Zydney Department of Chemical Engineering, The Pennsylvania
State University, University Park, PA, USA
A

Ab Initio Calculation it is an ab initio theory, but various potentials


dening the quantum system are obtained by
Giorgio De Luca using empirical data. For example, hybrid poten-
Institute on Membrane Technology, National tials are linear combinations of pure potentials.
Research Council of Italy, ITM-CNR, Rende, The coefcients of the linear combinations are
Italy obtained using experimental data. Nevertheless,
other potentials are obtained from the thermody-
namic theory of electron gas (statistical thermo-
Although the term ab initio usually indicates cal- dynamics); thus the latter can be considered ab
culations based on rst principles, either they are initio. For this reason also the density functional
related to classical or to quantum mechanics, this theory is considered an ab initio methodology.
term is generally used when it refers to calcula- Summarizing, two broad theoretical methods can
tions based on quantum mechanics rst principles be identied: those that make use of adjustable
(Szabo and Ostlund 1994). Thus, if the parameters that should be to be dened each time,
dAlembert equation is used to describe a force ad hoc, depending on the system studied and those
balance, in which the expression of the forces is that do not use ad hoc parameters which only refer
only expression of chemical-physical average to the rst principles and are known as the ab
properties (values obtained as average of micro- initio methods.
scopic properties) without any use of empirical Particular attention should be given on
adjustable parameters, the calculation can also be multiscale simulations in which paramters
dened ab initio. As mentioned, in general, the provided by sub and nanoscales are used in
term ab initio is used when the calculations are meso and macro scales without resort of empiri-
performed by using the Schrdinger equation or cal-adjustable parameters. Even these types
rather an eigenvalue equation for the quantum of calculations can be dened ab initio. (De Luca
system. However, attention must be paid to the et al. 2014) recently, have used different
quantities or potential operators that dene the approaches, ranging from quantum mechanics to
eigenvalue equations. In fact, if the operators in macroscopic models, to simulate the formation of
the Hamiltonians are dened using experimental the protein cake on a membrane surface and the
data or by means of tting procedure, then the conseguent decay of water ux. Although various
calculation should not be dened ab initio but parameters were calculated ab-initio others have
semiempirical (Clementi and Corongiu 1995). not yet been assessed in this way; however, this
The density functional theory (Parr and Yang work represents one of the rst attempts of an ab-
1989) is a controversial case, since in principle, initio simulation of a membrane process.
# Springer-Verlag Berlin Heidelberg 2016
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-662-44324-8
2 Acetic Acid Dehydration by PV

References membrane surface, (2) liquid diffusion through


the membrane matrix, (3) vaporization, (4) vapor
Clementi E, Corongiu G (eds) (1995) Methods and tech- diffusion, and (5) vapor desorption (Van der
niques in computational chemistry METECC-95.
Bruggen 2009). Several studies have been under-
STEF, Cagliari
De Luca G, Bisignano F, Paone F, Curcio S (2014) Multi- taken on dehydration of acetic acid-water mix-
scale modeling of protein fouling in ultraltration pro- tures using organic, inorganic, and composite
cess. J Membr Sci 452:400414 membranes. It has been shown that inorganic
Parr RG, Yang W (1989) Density functional theory of
membranes, in most cases, are capable to provide
atoms and molecules. Oxford University Press, New
York a very high selectivity of water, which penetrates
Szabo A, Ostlund NS (1994) Modern quantum chemistry. through the membrane, but with a very low per-
Macmillan Publishing Co., New York meate ux, e.g., using zeolites. In an acid-proof
silicalite-1 zeolite study, it was found that the
separation factor was near innite (Masuda
et al. 2003). A study using free-radical graft poly-
Acetic Acid Dehydration by PV merization of 1-vinylimidazole (VI) onto the
as-synthesized mordenite zeolite membrane in
Nora Jullok acetic acid dehydration has been conducted by
School of Bioprocess Engineering, Universiti (Chen et al. 2010). It was found that by applying
Malaysia Perlis (UniMAP), Arau, Perlis, this membrane in pervaporation at higher temper-
Malaysia ature, it yields a higher ux and also a higher
selectivity. Another interesting study was the
investigation by Teli et al. (2007) on applying a
Acetic acid is an important organic chemical used silicotungstic acid incorporated sodium alginate
in a wide range of applications worldwide. (STA-NaAlg-5). This study gave an excellent sep-
Among others, it is used as a raw material in the aration factor and ux, ranging from 0.194 to
synthesis of vinyl acetate monomer (VAM) for the 0.489 kg/m2 h. However, the membrane perfor-
production of a wide variety of polymers. These mance decreased when applied at high tempera-
include polyvinyl acetate, polyvinyl alcohol, ture and in a more dilute feed solution. As the
polyacetals, and ethylene vinyl acetate copoly- temperature and water content in the feed solution
mers (Minardi et al. 2002). A regular distillation are increased, the ux increases and selectivity
process to dewater acetic acid is known to be decreases. Other than inorganic membranes, poly-
energy intensive and to incur high operational meric membrane shows promising solution.
costs. Since the separation of acetic acid from Pervaporation up to 90 wt.% acetic acid using
water using distillation is far from being the best polyphenylsulfone membranes at temperature
process, any cost-efcient method to dehydrate range from 30 to 80  C exhibited high ux, good
acetic acid is in demand. Among these alternative separation factor, and membrane stability (Jullok
methods, pervaporation has been suggested as a et al. 2011). The plasticizing effect was postulated
promising solution to separate acetic acid aqueous to result in a special sieving property, which
solutions (Alghezawi et al. 2005; Durmaz- assisted the water molecules to be transported
Hilmioglu et al. 2001; Huang et al. 1988). across the membrane matrix.
Pervaporation is a membrane-based process that
can be potentially applied to purify acetic acid
(i.e., via acetic acid dehydration). It requires
the availability of a system with a vacuum down- References
stream to enable separation by partial vaporization
Alghezawi N, Sanli O, Aras L, Asman G (2005) Separation
through a dense, selective membrane. The perme-
of acetic acid-water mixtures through acrylonitrile
ation of a permeating component can be described grafted poly (vinyl alcohol) membranes by
in ve consecutive steps: (1) sorption on the pervaporation. Chem Eng Proc 44:5158
Acetic Acid Dehydration by Pervaporation with Charged Membranes 3

Chen Z, Yang J, Yin D, Li Y, Wu S, Lu J, Wang J (2010) as methanol carbonylation for acetic acid synthe-
Fabrication of poly (1-vinylimidazole)/mordenite sis. About 75 % of acetic acid in the chemical
grafting membrane with high pervaporation perfor-
mance for the dehydration of acetic acid. J Membr Sci industry is produced by this process, in which A
349:175182 carbon monoxide reacts with methanol under
Durmaz-Hilmioglu N, Yildirim AE, Sakaoglu AS, inuence of a rhodium complex catalyst at
Tulbentci S (2001) Acetic acid dehydration by 180  C and pressure of 3040 atm (Shen
pervaporation. Chem Eng Proc 40
Huang RYM, Moreira A, Notarfonzo R, Xu YF et al. 2011). The main challenges in acetic acid
(1988) Pervaporation separation of acetic acid water and water separation are (1) cost minimization and
mixtures using modied membranes. I. Blended (2) optimizing separation efciency. In acetic acid
polyacrylic acid (Paa) nylon 6 membranes. J Appl Pol aqueous solutions, there is a dynamic equilibrium
Sci 35:11911200
Jullok N, Darvishmanesh S, Luis P, Van der Bruggen between neutral molecules and the acetate and
B (2011) The potential of pervaporation for separation hydronium ions. It was observed that acetic acid
of acetic acid and water mixtures using dissociation is not only driven by the breaking of
polyphenylsulfone membranes. Chem Eng H-bonds connecting the ions but also triggered by
J 175:306315
Masuda T, Otani S, Tsuji T, Kitamura M, Mukai SR a solvent reorganization around the proton-
(2003) Preparation of hydrophilic and acid-proof accepting water (Park et al. 2006), as illustrated
silicalite-1 zeolite membrane and its application to in Scheme 1. Water molecule forms four hydrogen
selective separation of water from water solutions of bonds, whereas a hydronium ion only forms three.
concentrated acetic acid by pervaporation. Sep Pur
Tech 32:181189 Due to the proximity of the boiling point between
Minardi F, Belpoggi F, Soffritti M, Ciliberti A, Lauriola M, acetic acid and water, separation using conven-
Cattin E, Maltoni C (2002) Results of long term carci- tional methods may not be the best choice to
nogenicity bioassay on vinyl acetate monomer in consider. Dehydration of acetic acid by
Sprague Dawley rats. Ann N Y Acad Sci 982:106122
Teli SB, Gokavi GS, Sairam M, Aminabhavi TM pervaporation with charged membranes can
(2007) Highly water selective silicotungstic acid potentially be applied. Ion exchange membranes
(H4siw12o40) incorporated novel sodium alginate are pictured as porous with charges lining the pore
hybrid composite membranes for pervaporation dehy- walls. An example of ion exchange membrane
dration of acetic acid. Sep Pur Tech 54:178186
Van der Bruggen B. Fundamentals of membrane solvent used for this specic application is Naon
separation and pervaporation. In: I. o. M. T. I.-C. Uni- 117, which has been modied to form Naon
versity of Calabria, Via P. Bucci, 17/C, 87030 Rende (C8H17)4N+. Other ion exchange membranes
(CS), Italy and D. o. C. E. a. M. University of Calabria, which have been evaluated include sulfonated
Via P. Bucci, cubo 44/A, 87030 Rende (CS), Italy eds.,
Memb Oper. (Italy, 2009), pp 4561 polysulfone (PSF(SO3)-H+) and crossed-linked
styrene-co-butadiene base. They are mechanically
stabilized with poly(vinyl chloride) baking and
contain quaternary ammonium and sulfonic acid
moieties, respectively (AMV-CH3OO and
Acetic Acid Dehydration by CMV-H+). The interaction of polymers with
Pervaporation with Charged water is strongly inuenced by the xed ion and
Membranes counterion. Hydrogen-bonding, dipole-dipole,
and ion-dipole are the three possible interactions
Nora Jullok between water molecules and membrane surface.
School of Bioprocess Engineering, Universiti As the interaction between xed ion and counter-
Malaysia Perlis (UniMAP), Arau, Perlis, ion with water increases, the sorption selectivity
Malaysia to water increases. A polymer having H+ as coun-
terion has a lower water sorption and lower water
sorption selectivity compared to a polymer having
Acetic acid is produced both synthetically and metal counterion. Besides, H+-containing poly-
biologically. The synthetic production typically mer also has a high permeability but low separa-
uses the Monsanto process, which is also known tion factor. On the other hand, for a similar
4 Acetic Acid Dehydration by Pervaporation Zeolite Membranes

Acetic Acid Dehydration


by Pervaporation with
O O
1/2
Charged Membranes, H3C + H 2O H3C + H OH2+
Scheme 1 Dissociation of
acetic acid in water OH O
1/2

polymer, which has a metal counterion, removed continuously using a water permeable
pervaporation shows lower permeability but acid resistant membrane.
higher separation factor (Semenova et al. 1997). The most promising results concerning separa-
tions in acid medium have been obtained with zeo-
lites with a moderate Si/Al ratio such as zeolite
References T with Si/Al = 4 or mordenite with Si/Al ratio
from 7 to 20. Both zeolites have been tested in
Park JM, Laio A, Iannuzzi M, Parrinello M (2006) Disso- water/acetic acid mixture (50/50 wt.%) showing
ciation mechanism of acetic acid in water. J Am Chem
stability after the exposure to this mixture at mild
Soc 128:1131811319
Semenova SI, Ohya H, Soontarapa K (1997) Hydrophilic temperature around 70  C for several days.
membranes for pervaporation: an analytical review. Although the performance of these zeolites in
Desalination 110:251286 pervaporation for water dehydration are lower
Shen Z, Zhou J, Zhou X, Zhang Y (2011) The production
compared to zeolite A (Arruebo et al. 2008), the
of acetic acid from microalgae under hydrothermal
conditions. Appl Energy 88:34443447 acid stability of these zeolites is higher than that of
zeolite A and makes them good candidates for the
separation of acid mixtures. The researchers of
Mitsubishi studied the technical feasibility
of mordenite membranes for dehydration of
Acetic Acid Dehydration by acetic acid aqueous solution with a feed rate of
Pervaporation Zeolite Membranes 1000 kg h1. Their results suggested that the
developed mordenite membrane deserved to the
Reyes Mallada further technically developments of up-scale and
Department of Chemical and Environmental mass-production (Sato et al. 2011). The mem-
Engineering and Aragon Nanoscience Institute, brane performance in pervaporation was mea-
Universidad de Zaragoza, Zaragoza, Spain sured in a feed mixture of water (50 wt.%)/AAc
(50 wt.%) to be 10.9 kg m2/h for permeate ux
and to be 0.77  10  6 mol m2/sPa for water
The best performance in pervaporation for water permeance with separation factor of 500 at
dehydration corresponds to zeolite A, which is the 130  C.
zeolite with the lowest Si/Al ratio (equal to 1) and
therefore the highest hydrophilicity. However, the
high aluminum content of this zeolite makes it References
unstable under acidic conditions and it dissolves
at low pH. Arruebo M, Mallada R, Pina MP (2008) Zeolite membranes:
synthesis, characterization, important applications, and
The separation of water in the presence of acetic
recent advances, Chapter 10. In: Handbook of mem-
acid or other acids could be important in the case of brane separations, 1st edn. CRC Press, Boca Raton,
membrane reactors, active zeolite membrane reac- pp 233323
tors (AZMRs), for equilibrium displacement (see Sato K, Sugimoto K, Kyotani T, Shimotsuma N, Kurata
T (2011) Synthesis, reproducibility, characterization,
also Membrane reactor equilibrium conversion and
pervaporation and technical feasibility of preferentially
Pervaporation membrane reactor). The esterication b-oriented mordenite membranes for dehydration of
reaction using acid produces water that could be acetic acid solution. J Membr Sci 385386:2029
A-CNT 5

even though both H2S and CO2 have smaller


Acid Gas: Effect on Membrane kinetic diameters than CH4. In the natural gas
Properties sweetening industry, both cellulose acetate- and A
polyimide-based membranes have been
Colin A. Scholes commercialized.
Department of Chemical and Biomolecular Prolonged exposure to both H2S and CO2 can
Engineering, University of Melbourne, Parkville, lead to plasticization and degradation of the poly-
VIC, Australia meric membrane over time. This is because the
acidic nature of the gases means they will readily
interact with the polymeric chains, disrupting
Acidic gas removal is the largest application of chain packing and lubricating polymer chain
gas separation membranes and a vital process in motion, resulting in more rubbery behavior. Mem-
the natural gas processing industry. Membranes brane degradation by these gases is greatly
used in this process are designed to separate H2S enhanced if water is present, because of the
and CO2, and this process is known as natural gas weak acidic dissociation of these gases (Scholes
sweetening. This is readily required for et al. 2009).
low-quality natural gas reserves, which need to For inorganic and metallic membranes, H2S is
be processed to achieve pipeline specications of of particular concern, because of the effect sulfur
CO2 <2 mol% and H2S <4 ppm (Baker 2001). can have on the membrane material
The removal of acidic gases is also required for (Lu et al. 2007). A good example of this is in H2
biogas and gasication, where H2S and CO2 are separation with Pd-based membranes. The pres-
separated from CH4, CO, and H2. For natural gas ence of H2S leads to membrane brittlement and
sweetening, the membrane must exhibit high per- performance degradation because of lattice
meability for H2S and CO2, with a large selectiv- expansion on the formation of Pd-S. Hence, in
ity relative to methane. applications such as gasication, it is necessary
In general, nonporous polymeric membranes for the gas to have H2S removed prior to the gas
are applied in acidic gas removal, taking advan- separation membrane, use sacricial layers, or add
tage of the solution-diffusion mechanism and the sulfur-resistant materials.
high solubility of H2S and CO2, compared to CH4.
Also polymeric membranes almost always dem-
onstrate selectivity for H2S over CO2, again References
because of the higher condensability of H2S com-
pared to CO2, as demonstrated by the difference in Baker R (2001) Future directions of membrane
gas-separation technology. Membr Technol 138:510
critical temperature. Table 1 provides the H2S
Lu GQ, da Costa D, Duke JC, Giessler M, Socolow R,
permeability and H2S/CO2 selectivity for a range Williams RH, Kreutz TG (2007) Inorganic membranes
of polymeric membranes. The study of porous for hydrogen production and purication: a critical
membranes for acidic gas removal is limited, review and perspective. J Colloid Interface Sci
314:589603
Scholes CA, Kentish SE, Stevens GW (2009) Effect of
minor components in carbon dioxide capture using
Acid Gas: Effect on Membrane Properties, polymeric gas separation membranes. Sep Purif Rev
Table 1 H2S permeabilities (barrier) and H2S/CO2 selec- 38:144
tivity in a range of polymeric membranes
H2S permeability H2S/CO2
Ethyl cellulose 320 3.8
Nylon 0.34 3.86
PDMS 5,100 1.6 A-CNT
Polyethylene 36 2.84
PTMSP 21,400 1.2 Aligned Carbon Nanotube
6 Activity Coefficient

cathodic overpotential (Zhang 2008). In this case,


Activity Coefficient overpotential is dened as the extra potential over
the equilibrium value that must be applied to cause
Dmitri Bessarabov an electrode reaction at a certain rate. Thus, an
Faculty of Engineering, DST HySA Infastructure electrocatalyst with high activity is required to
Center of Competence, North-West University, minimize the overpotential.
Potchefstroom, South Africa According to the Sabatier principle (Bligaard
et al. 2004), a volcano-shaped curve is obtained
when the activity of a catalyst for ORR is plotted
Chemical Thermodynamics as a function of a variable that relates to the ability
of the electrocatalyst surface to form chemical
Depending on a specic area of fundamental sci- bonds with oxygen, reaction intermediates,
ence and technology, the term activity may have and/or products (Nrskov et al. 2004). For exam-
a different meaning. For example, in chemical ple, it was shown that the catalytic activity of a
thermodynamics, activity (a) is well known as a single Pt-based electrocatalyst toward ORR
convenient variable to represent data, obtained depends strongly on such variables as the O2
experimentally or calculated theoretically, for the adsorption energy, the dissociation energy of the
values of chemical potentials of components in OO bond, and the binding energy of OH on the
real chemical solutions. For the i  th component catalyst surface. The electronic structure of the Pt
of a mixture, activity ai is dened as follows: catalyst (Pt d-band vacancy) and the PtPt
mi m0i RTlnai , where mi is the chemical interatomic distance (geometric effect) can
potential of a component and m0i is the chemical strongly affect these variables. Theoretical calcu-
potential of that component in standard state. lations on O2 and OH binding energy on several
R is the gas constant and T is the thermodynamic metals have predicted that Pt should have the
temperature. The numerical value of the highest electrocatalytic activity among other
activity depends on the choice of a standard metals with the ORR activity of Pt > Pd > Ir >
state, as it describes the difference between an Rh, which is in agreement with experimental
actual chemical potential and a standard chemical results. Calculations have also predicted that
potential. PtM (M = Fe, Co, Ni, etc.) bimetallic alloys
should have higher catalytic activity than pure
Pt, which has again been proven by experiments
Fuel Cells and Electrocatalysis (Nrskov et al. 2004).

In hydrogen fuel cell science and technology, activ-


ity is often referred to as the measure of efciency Practical Measurements
of electrocatalysts. Electrocatalytic processes in
fuel cells occur on the surface of electrodes, and Practically, electrocatalytic activity of various
one of the main challenges is to explain, predict, electrocatalysts can be compared by measuring
and improve electrocatalytic activity of various electrical currents produced at a given
electrode materials. In the area of low temperature overpotential. The electrocatalyst that generates
PEM (proton exchange membrane, also called higher current at lower overpotential is generally
polymer electrolyte membrane) fuel cells, catalytic a better electrocatalyst.
activity is often used to compare efciency of The rotating disk electrode (RDE) technique is
electrocatalysts toward kinetics of the oxygen often used to measure ORR activity of
reduction reaction (ORR) occurring at the cathode. electrocatalysts for hydrogen PEM fuel cell appli-
ORR is known to have slow kinetics due to the cations. Typically, current density j is measured at
reaction having multiple steps and difculties in 0.9 V at the positive voltage sweep at a certain
breaking the OO bond, which leads to a larger electrode rotating speed. The measured current
Acute Kidney Injury (AKI) 7

density j is expressed by the following equation: Acute kidney injury (AKI) or acute renal failure
j j j j , where jk is kinetic current density,
1 1 1 1 indicates kidney injury from less severe forms of
k d f

jd is hydrodynamic diffusion limiting current den- injury to more advanced injury when acute kidney A
sity, and jf is lm diffusion limiting current den- failure may require renal replacement therapy.
sity. RDE experiments should be designed to Acute kidney failure occurs when kidneys loss
maximize jf. In that case, 1j j1 j1 and after their functions that include excretion of wastes,
rearrangement jk j  jd =jd  j.
k d
acid-base homeostasis, osmolality regulation,
For ORR the value of jd is normally taken at blood pressure regulation, and hormone secretion
0.4 V during RDE experiments. (Waikar et al. 2008). When kidneys lose their
Once jk is known, activity is often reported in ltering ability, dangerous levels of wastes may
practical values as mass activity (A/mg Pt) by accumulate, resulting in an increasingly toxic
normalization to the value of Pt loading of the blood stream and uid overload. Acute kidney
sample on the disk electrode. failure requires replacement therapy that includes:
Another practically important way of reporting hemodialysis, peritoneal dialysis, hemoltration,
the electrocatalyst activity is to use area-specic hemodialtration, and renal transplantation.
activity. The area-specic activity, expressed in Dialysis treatment involves the diffusion of
the following units, uA/cm2 Pt, is reported by solutes through a semipermeable membrane
normalization of jk to the electrochemical surface driven by a concentration gradient. For the
area (ECSA) of the catalyst. treatment of uremic patients, an articial
membrane (hemodialysis) or a biological mem-
brane (peritoneal dialysis) can be utilized. The
References membrane-based treatments involve pumping
patients blood from the body through a mem-
Bligaard T, Nrskov JK, Dahl S, Matthiesen J, Christensen brane device that acts as an articial kidney by
CH, Sehested S (2004) The Brnstedevanspolanyi separating waste products including toxins and
relation and the volcano curve in heterogeneous catal-
ysis. J Catal 224:206217 excess water from the blood. The therapies for
Nrskov JK, Rossmeisl J, Logadottir A, Lindqvist L, the treatment of patients with acute renal failure
Kitchin JR, Bligaard T, Jonsson H (2004) Origin of are not limited to dialysis but rather include other
the overpotential for oxygen reduction at a fuel-cell modalities. Hemoltration has been developed
cathode. J Phys Chem B 108:1788617892
Zhang J (ed) (2008) PEM fuel cell electrocatalysts and to overcome the reduced efcacy of diffusion for
catalyst layers. Springer, London molecules with middle and large MW. In this
process the driving force is a hydrostatic pressure
Further Reading gradient that induces a large ux of water across
Vielstich W, Lamm A, Gasteiger HA (eds) (2003) Handbook the membrane from blood side to the ltrate side.
of fuel cells, vol 2, Electrocatalysis. Wiley, New York As a result the rate of solute removal is propor-
tional to the applied pressure. Hemodialtration
is the combination of hemodialysis and
hemoltration processes. The high rate of ultral-
Acute Kidney Injury (AKI)
tration is combined with the efcient diffusion
overcoming the disadvantages related to each sin-
Loredana De Bartolo
gle treatment.
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, Rende,
Italy
References
Synonyms Waikar SS, Liu KD, Chertow GM (2008) Diagnosis,
epidemiology and outcomes of acute kidney Injury.
Membrane articial organs Clin J Am Soc Nephrol 3:38443861
8 Addition Norbornene Polymer-Based Membrane Materials

et al. 2010): permeability coefcients increase


Addition Norbornene Polymer-Based for penetrants with larger size or molecular mass
Membrane Materials (e.g., butane). This makes them important candi-
dates for membranes for separation of natural and
Yuri Yampolskii associated petroleum gas, especially because their
A.V. Topchiev Institute of Petrochemical gas permeation parameters are relatively stable in
Synthesis, Russian Academy of Sciences, time in comparison with highly permeable
Moscow, Russia polyacetylenes. These polymers are soluble in
various organic solvents, so high-ux composite
membranes (permeance of about 515 m3(STP)/
Substituted norbornenes and tricyclononenes can m2 h bar) can be prepared from them.
be polymerized according to the addition scheme,
that is, via opening of the double bonds of these
cycloolens (Finkelshtein et al. 2011; Yampolskii References
2010).
The resulting glassy polymers have very rigid E. Finkelshtein, M. Bermeshev, M. Gringolts,
L. Starannikova, Y. Yampolskii, Substituted
main chains and high glass transition tempera-
polynorbornenes as promising materials for gas sepa-
tures. The gas permeation parameters of the ration membranes. Russ Chem Rev 80, 341361 (2011)
obtained polymers strongly depend on the M. Gringolts, M. Bermeshev, Y. Yampolskii,
substituents in the monomer molecules. L. Starannikova, V. Shantarovich, E. Finkelshtein,
New high permeable addition poly(tricyclononenes)
Thus, nonsubstituted addition polynorbornene
with Si(CH3)3 side groups. Synthesis, gas permeation
(PNB) is a relatively low-permeability polymer parameters, and free volume. Macromolecules 43,
(P(O2) = 11 Barrer), though when 71657172 (2010)
substituents are introduced permeability Y. Yampolskii, Norbornene polymers as materials for
membrane gas separation, in Comprehensive mem-
increases markedly (Fig. 1). In particular, brane science and engineering, ed. by E. Drioli,
methyl-substituted PNB has P(O2) = 89 Barrer, L. Giorno, vol. 1 (Elsevier, Oxford, 2010), pp. 131146
while for the polymer with bulkier, SiMe3 substit-
uent, the permeability is further strongly enhanced
(P(O2) = 980 Barrer) (Yampolskii 2010). SiMe3-
substituted PNB and poly(tricyclononenes) reveal
large free volume according to the positron anni- Adhesion to Membrane Surfaces
hilation lifetime spectroscopy and solubility-
controlled selectivity in separation of hydrocar- Li-Ping Zhu
bons(Finkelshtein et al. 2011; Gringolts MOE Key Laboratory of Macromolecular
Synthesis and Functionalization, Department of
Polymer Science and Engineering, Zhejiang
R2 University, Hangzhou, China
n
n

R1 Adhesion to membrane surfaces generally


describes the sticking or holding fast of some
substances such as paints, cells, platelets, bacteria,
R1 R2
proteins, etc. on membrane surfaces when they are
Addition Norbornene Polymer-Based Membrane
in contact. Usually, the intermolecular interaction
Materials, Fig. 1 Addition Norbornene Polymer-based is responsible for the adhesion of substances on
Membrane Materials membrane surfaces (Huang et al. 1999). The
Adsorption onto Membrane Surfaces 9

adhesion can be divided into several categories, Cross-References


including mechanical adhesion, chemical adhe-
sion, dispersive adhesion, electrostatic adhesion, Adsorption onto Membrane Surfaces A
and diffusive adhesion according to the forces that Bioadhesion to Membrane Surface
cause adhesion. The adhesion is a stronger inter-
action between unlike substances than adsorption
References
(Jacek et al. 1999). In the ltration operation using
a membrane, the adsorption and adhesion of Huang YC, Zhang ES, Ying K (1999) Progress of bacterial
foulants such as colloids, particles, proteins, bac- adhesion on biomaterials. Foreign Med Sci (Biomed
teria, and microorganisms on membrane surfaces Eng Fascicle) 22(3):148153
result often in membrane fouling that induces the Jacek D, Robert K, Jarosaw K, Hanna MK (1999) Cell
adhesion to polymeric surfaces: experimental study and
severe ux loss and the increase of transmem- simple theoretical approach. J Biomed Mater Res
brane pressure. Membrane fouling can be divided 47(2):234242
into reversible fouling and irreversible fouling. Jonathan AB, Amy EC (2004) Colloidal adhesion to
Reversible fouling is often attributed to the hydrophilic membrane surfaces. J Membr Sci
241:235248
adsorption of foulants on membrane surface, and
it can be recovered by physical or chemical mem-
brane cleaning. While irreversible fouling is usu-
ally generated from the rm adhesion of foulants
on membrane surface, and it is difcult to be Adsorption onto Membrane Surfaces
removed even if a thorough membrane cleaning
is done (Jonathan and Amy 2004). Therefore, the Li-Ping Zhu
adhesion of foulants on membrane surface often MOE Key Laboratory of Macromolecular
brings a permanent deterioration of membrane Synthesis and Functionalization, Department of
performance. In such a case, the fouled membrane Polymer Science and Engineering, Zhejiang
modules have to be replaced to continue a normal University, Hangzhou, Zhejiang, China
ltration operation.
In blood-contact membrane separation, for the
blood incompatible membrane materials, the plate- Adsorption onto membrane surface is the accu-
lets in blood tend to accumulate and adhere onto mulation of gases, liquids, or solutes to form a thin
membrane surface due to a biological immune lm on membrane surface. In adsorption, the
reaction. As a result, thrombus formation may adsorbate is attracted to the surface of adsorbent,
form and further result in some serious complica- but does not enter its molecular spaces. As a
tions. Therefore, the blood-contact membranes surface phenomenon, adsorption is a consequence
such as hemodialysis membranes often need be of surface energy. Adsorption is similar to adhe-
modied to prevent the adhesion of platelets on sion and absorption, but there exist differences
membrane surface during blood ltration. In mem- between them. Generally, compared to adhesion,
brane science, the experiment of platelet adhesion adsorption is looser interaction between unlike
on membrane surface is usually employed to eval- substances. Adsorption is a surface-based pro-
uate the hemocompatibility of a blood-contact cess, while absorption involves the whole volume
membrane. In biomedical application, the adhesion of the material. The exact bonding nature of
of microbes on membrane surface often leads to the adsorption depends on the details of the species
bacterial infection of patients and the deterioration involved, but the adsorption process is generally
of membrane materials. Therefore, the control of classied as physical adsorption and chemical
microbial infection is a very important issue in adsorption. The physical adsorption is attributed
biomedical membrane separation. to the non-covalent interaction such as van der
10 Advanced Oxidation Process (AOP) by Membrane Reactors

Waals force, electrostatic attraction, etc. The


chemical adsorption features the formation of Advanced Oxidation Process (AOP)
covalent bonding between adsorbate and adsor- by Membrane Reactors
bent (Ferrari et al. 2010).
Commonly, in liquid ltration using a mem- Kwang-Ho Choo
brane, adsorptions onto membrane surface Department of Environmental Engineering,
describe the accumulation and attachment of sol- Kyungpook National University, Daegu,
utes in liquid on membrane surface driven by the Republic of Korea
minimization of interfacial energy. In water phase
ltration, the adsorption of foulants such as pro-
teins, colloids, microorganisms, etc., on mem- Advanced oxidation process (AOP) by membrane
brane surfaces and membrane pore walls is often reactors is a synergistic hybrid of hydroxyl radical
responsible to membrane fouling that induces a reaction and membrane ltration in a single reac-
severe loss of membrane permeability and a tor. Advanced oxidation process (AOP) is the
change in membrane separation characteristics. uncontrolled, destructive action of hydroxyl radi-
The adsorption of foulants can be removed cals generated from ozone, H2O2, ultraviolet radi-
(desorption) by chemical or physical washing if ation, Fenton reaction, electrolysis, sonolysis, and
the interaction between foulants and surfaces is photocatalysis (e.g., TiO2). AOP is most widely
weak. As a result, the membrane performances used for the decomposition of nonbiodegradable
can be recovered partially or fully. In blood- organic contaminants present in industrial and
contact membrane separation, protein municipal wastewaters. It can be also applied for
adsorption on membrane surface often leads to the degradation of micro-contaminants and taste-
the activation of complement system and blood and-odor causing compounds in drinking water
coagulation and further results in serious compli- sources, such as pesticides, pharmaceuticals,
cations of patients. Protein adsorption onto mem- endocrine disruptors, microcystins, geosmin,
brane surface is inuenced by the surface etc. Although micro-/ultraltration membranes
characteristics such as wettability, surface are almost complete barriers for particulate matter
chemistry, morphology, surface charge, and pathogens in water, they are limited in remov-
etc. Therefore, surface modication of the blood- ing dissolved organic compounds. Thus, the cou-
contact membranes to depress the adsorption of pling of membrane ltration with AOP in a reactor
proteins on membrane surface has been a provides multifunctionalities and exibilities for
pursuit of membrane researchers (Rana and water and wastewater treatment systems.
Matsuura 2010). Advanced oxidative membrane reactors are
similar to biological membrane reactors (i.e.,
membrane bioreactors) in their concept except
that biological oxidation is replaced by chemical
Cross-References oxidation. Due to the incompatibility of hydroxyl
radicals and membrane materials (e.g., polymeric
Adhesion to Membrane Surfaces membranes), however, only a few examples of
process congurations are developed and intro-
References duced, such as ozonated membrane reactor (Heng
et al. 2007), photocatalytic membrane reactor
Ferrari L, Kaufmann J, Winnefeld F, Plank J (2010) Inter- (Choo et al. 2008), and electrochemically active
action of cement model systems with superplasticizers ltration device (Vecitis et al. 2011). Figure 1
investigated by atomic force microscopy, zeta potential, shows the schematics of such advanced oxidative
and adsorption measurements. J Colloid Interface Sci
347:1524
membrane reactors. The ozone membrane reactor
Rana D, Matsuura T (2010) Surface modications for consists of ceramic tubular membranes made of
antifouling membranes. Chem Rev 110:24482471 alumina and zeolite which are chemically durable
Advanced Oxidation Processes (AOPs) and Membrane Operations 11

Advanced Oxidation Process (AOP) by Membrane 2007), (b) photocatalytic membrane reactor (Choo et al.
Reactors, Fig. 1 Examples of advanced oxidative mem- 2008), and (c) electrochemically active ltration device
brane reactors: (a) ozone membrane reactor (Heng et al. (Vecitis et al. 2011)

while degrading a fraction of total organic carbon Vecitis CD, Schnoor MH, Rahaman MS, Schiffman JD,
by ozone. The photocatalytic membrane reactor Elimelech M (2011) Electrochemical multiwalled car-
bon nanotube lter for viral and bacterial removal and
with suspended TiO2 particles in aqueous phase inactivation. Environ Sci Technol 45:36723679
enables polymeric membranes to be used because
photocatalysis only occurs on the surface of TiO2
photocatalysts where UV light bombards. The
membrane permeability is enhanced with contin-
uous photocatalysis of organic substances; other-
Advanced Oxidation Processes
wise they can foul the membrane severely. The (AOPs) and Membrane Operations
fabrication and use of TiO2 membranes for
Kwang-Ho Choo
photocatalytic membrane reactors are of great
interest, but UV light radiation is a major huddle Department of Environmental Engineering,
to be resolved. When a direct current of 23 V was Kyungpook National University, Daegu,
Republic of Korea
applied onto multiwall carbon nanotubes loaded
on a 5-mm polytetraoroethylene lter, substantial
viral and bacterial removals are achieved by elec-
Advanced oxidation processes (AOPs) and
trolysis in addition to ltration. Further process
developments on AOP membrane reactors are membrane operations are composed of
expected with novel membrane materials and pro- advanced oxidation followed by membrane ltra-
tion, where the former decomposes dissolved
cess designs.
organic matter and the latter removes particulate
matter. Advanced oxidation process (AOP) is the
uncontrolled, destructive action of hydroxyl radi-
References
cals generated from ozone, H2O2, ultraviolet radi-
Choo K-H, Tao R, Kim M-J (2008) Use of a photocatalytic ation, Fenton reaction, electrolysis, sonolysis, and
membrane reactor for the removal of natural organic photocatalysis (e.g., TiO2). AOP is most widely
matter in water: effect of photoinduced desorption and used for the decomposition of nonbiodegradable
ferrihydrite adsorption. J Membr Sci 322:368374
Heng S, Yeung KL, Djafer M, Schrotter J-C
organic contaminants present in industrial and
(2007) A novel membrane reactor for ozone water municipal wastewaters. It can be also applied
treatment. J Membr Sci 289:6775 for the degradation of micro-contaminants and
12 Advanced Oxidation Processes (AOPs) and Membrane Operations

with ozone dosage (1.7 mgO3/mg TOC) without ozone dosage


1.2
a 220 b without electrolysis
200 1.0 with electrolysis (2.0 V)

Normalized Flux (J/J0)


180 breakdown with electrolysis (4.0 V)
permeability [l/(m2 h bar)]

160 in ozone 0.8


generator
140
120 0.6
100
80 0.4
60
40 0.2
20
0 0.0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 1.0 1.2 1.4 1.6 1.8 2.0
filtration time [h] Concentration Factor

Advanced Oxidation Processes (AOPs) ozonation plus ultraltration (Schlichter et al. 2004); (b)
and Membrane Operations, Fig. 1 Membrane ux electrolysis plus microltration (Park et al. 2013)
enhancement with advanced oxidation pretreatments: (a)

taste- and odor-causing compounds in drinking and ultimately mineralizing organic matter. Mem-
water sources, such as pesticide, pharmaceuticals, brane operations after electrolysis achieve further
endocrine disruptors, microcystins, geosmin, removal of particles that can be hardly oxidized.
etc. This combined process can compensate the A process conguration that consists of advanced
weak point of each process, but the oxidants left oxidation (e.g., Fenton oxidation) followed by a
over should be quenched before their contact with membrane bioreactor is also an attractive option
polymeric membranes. This is because oxidants for the treatment of industrial wastewater
can deteriorate the membrane lifetime or integrity containing recalcitrant organic chemicals (e.g.,
signicantly due to the oxidation of the mem- dyes) (Feng et al. 2010). This combination can
brane. Polyamide membranes can be damaged be applied for the minimization of biological
even by the attack of chlorine and thereby, their sludge generation while disintegrating excessive
physical properties and ltration performance are activated sludge (He and Wei 2010). To take
signicantly impaired. Reducing agents, such as advantage of prolonged oxidation, inorganic
sodium sulte, are mostly used for oxidant membranes (e.g., ZrO2 and Al2O3 membranes),
quenching. which are tolerant to strong oxidants, can be used
A series of oxidation (e.g., ozonation) and instead of polymeric membranes. Particularly,
micro-/ultraltration processes are designed and advanced oxidation treatment prior to membrane
used for the treatment of drinking water which ltration helps to reduce membrane fouling
contains trace organic contaminants as well as caused by organic substances (Fig. 1) (Park
metal species (e.g., Fe2+, Mn2+) (Hyung et al. 2013; Park 2002; Schlichter et al. 2004).
et al. 2000; Choo et al. 2005). Ozone can facilitate
the oxidation of reduced forms of such metal ions
and so help to precipitate out. The precipitates can
References
be readily rejected by porous membranes. Elec- Choo K-H, Lee H, Choi S-J (2005) Iron and manganese
trolysis in combination with microltration is removal and membrane fouling during UF in conjunc-
developed and tested for the treatment of munic- tion with prechlorination for drinking water treatment.
ipal wastewater organic matter with simultaneous J Membr Sci 267:1826
Feng F, Xu Z, Li X, You W, Zhen Y (2010) Advanced
hydrogen production (Park et al. 2013). Electro-
treatment of dyeing wastewater towards reuse by the
chemical oxidation at a voltage of >2.3 V enables combined Fenton oxidation and membrane bioreactor
hydroxyl radicals to be generated while oxidizing process. J Environ Sci 22:16571665
Aerobic Membrane Bioreactor 13

He M-h, Wei C-h (2010) Performance of membrane biore- contaminants (carbon and ammonia) and separate
actor (MBR) system with sludge Fenton oxidation pro- solids from the treated municipal or industrial
cess for minimization of excess sludge production.
J Hazard Mater 176:597601 wastewater. Carbon is removed by microorgan- A
Hyung H, Lee S, Yoon J, Lee C-H (2000) Effect of isms that metabolize the carbon in the presence of
preozonation on ux and water quality in ozonation- dissolved oxygen for microbial growth and respi-
ultraltration hybrid system for water treatment. Ozone ration (organic carbon reduced to carbon dioxide).
Sci Eng 22:637652
Park YG (2002) Effect of ozonation for reducing Ammonia is removed through ammonia oxidation
membrane-fouling in the UF membrane. Desalination (nitrication). Nitrication is a microbially miti-
147:4348 gated reduction process that occurs in an aquatic
Park H, Choo K-H, Park H-S, Choi J, Hoffmann MR environment that contains moderate to high con-
(2013) Electrochemical oxidation and microltration
of municipal wastewater with simultaneous hydrogen centrations of ammonia and dissolved oxygen and
production: inuence of organic and particulate matter. low concentrations of organic carbon.
Chem Eng J 215216:802810 In submerged MBRs (Fig. 1), microporous
Schlichter B, Mavrov V, Chmiel H (2004) Study of a (microltration (MF) or ultraltration
hybrid process combining ozonation and
microltration/ultraltration for drinking water produc- (UF) ( Ultraltration)) membranes are
tion from surface water. Desalination 168:307317 immersed in a bioreactor, and water is ltered
( Permeate) through the membranes using vac-
uum; suspended solids are retained in the system;
and high levels of treatment (including nutrient
removal) can be achieved (Judd 2006). The MBR
Aerobic Membrane Bioreactor replaces the two-stage conventional activated
sludge process (biotreatment and clarication)
A. Achilli1 and R. W. Holloway2 with a single, integrated process ( Wastewater
1
Environmental Resources Engineering Treatment in Membrane Bioreactors). The advan-
Department, Humboldt State University, Arcata, tages of MBRs over conventional treatment
CA, USA have been thoroughly reviewed (Stephenson
2
Department of Civil and Environmental et al. 2000), and they include product consistency,
Engineering, Colorado School of Mines, Golden, reduced footprint, reduced sludge production,
CO, USA and nearly complete suspended solid separation
from the efuent. Additionally, MBR efuent
may be suitable for use as irrigation water, as
Synonyms process water, or as a pretreatment for potable
reuse applications (Membrane Bioreactors for
Cross-ow membrane bioreactor; Membrane bio- Reuse; Potable Water Production) (Lawrence
reactor; Microltration membrane bioreactor; et al. 2002).
Submerged membrane bioreactor; Ultraltration However, the establishment of membrane bio-
membrane bioreactor reactor technology (Anaerobic Membrane Biore-
actor; Attached Growth Membrane Bioreactor;
Membrane Bioreactors (MBR) for Plants; Sub-
Introduction merged Membrane Bioreactor) has been slower
than expected because decision-makers view
Aerobic membrane bioreactors (MBRs) are one of MBRs as high risk and costly compared to
the leading technologies to achieve sustainability conventional technology (Judd 2006). To date,
in wastewater treatment through reuse, decentral- MBRs have been used to treat municipal and
ization, and low energy consumption (Fane and industrial wastewater where water reuse is
Fane 2005; Fawehinmi et al. 2005). In aerobic desired, a small footprint is required, or stringent
MBRs, aerated activated sludge is coupled with discharge standards exist (Kang et al. 2007; Yang
membrane process to remove dissolved et al. 2006).
14 Aerobic Membrane Bioreactor

Aerobic Membrane Membrane


Bioreactor, Cassette
Fig. 1 Schematic Membrane Activated
representation of a Channels Sludge
submerged aerobic MBR
system

Product
Water

Membranes

Current Limitations pumped in the opposite direction through the


membrane, effectively removing most of the
One of the major limitations to widespread appli- reversible fouling ( Backwashing). The ef-
cation of MBR technologies is to control mem- ciency of backwashing has been studied in
brane fouling with modest energy and chemical detail, and the key parameters have been
input ( Irreversible Fouling; Reversible Foul- found to be frequency, duration, and intensity
ing) (Le-Clech et al. 2006). Membrane fouling ( Backwashing Frequency) (Bouhabila
(Biological Fouling; Cake Layer; Inorganic et al. 2001; Psoch and Schiewer 2005, 2006).
Scaling) has been investigated from various per- During membrane relaxation, permeate suction
spectives, including the causes, characteristics, is stopped, and the back transport of foulants is
and mechanisms of fouling and methods, to pre- naturally enhanced as reversibly attached foulants
vent or reduce membrane fouling (Achilli diffuse away from the membrane surface.
et al. 2011; Judd 2005; Le-Clech et al. 2006; Membrane backwashing and relaxation are
Meng et al. 2009; Wang and Wu 2009). Fouling regularly used for tubular and hollow ber mem-
markedly affects membrane cleaning (Membrane branes to control fouling (Bouhabila et al. 2001;
cleaning, 369690) and replacement intervals, sys- Hong et al. 2002; Psoch and Schiewer 2005,
tem productivity, and membrane integrity; all of 2006; Smith et al. 2005). This is not the case for
which are factors that affect energy requirements at-sheet membranes that cannot be backwashed
and costs (Judd 2006; Le-Clech et al. 2006). due to their inability to withstand pressure in the
opposite direction of the operating ow; for this
reason, relaxation is used to control the fouling of
Operation these membranes (Le-Clech et al. 2006). Regard-
less of the membrane conguration, chemicals
In order to operate conventional MBRs at constant must be used at regular intervals to enhance phys-
ux, physical membrane-cleaning techniques are ical cleaning (Le-Clech et al. 2005).
utilized; they include air scouring, backwashing,
relaxation, or a combination of the three,
depending on the membrane conguration Cross-References
(hollow bers, at sheet, or tubular). Air scouring
is required for submerged MBR congurations to Backwashing
gas lift fresh sludge through the membrane bundle Backwashing Frequency
or cassette and to scour solids from the membrane Industrial/Tannery Wastewater Treatment
surface. During backwashing, permeate is Using Membrane Bioreactors
Affinity Membranes 15

Inorganic Scaling Smith PJ, Vigneswaran S, Ngo HH, Ben-Aim R, Nguyen H


Irreversible Fouling (2005) Design of a generic control system for optimising
back ush durations in a submerged membrane hybrid
Permeate reactor. J Membr Sci 255:99106 A
Reversible Fouling Stephenson T, Judd S, Jefferson B, Brindle K (2000) Mem-
Submerged Membrane Bioreactor brane bioreactors for wastewater treatment. IWA Pub-
Ultraltration (UF) lishing, London
Wang ZW, Wu ZC (2009) A review of membrane fouling
in MBRs: characteristics and role of sludge cake
formed on membrane surfaces. Sep Sci Technol
References 44(15):35713596
Yang W, Cicek N, Ilg J (2006) State of the art of membrane
Achilli A, Marchand EA, Childress AE bioreactors: worldwide research and commercial appli-
(2011) A performance evaluation of three membrane cations in north America. J Membr Sci 270:201211
bioreactor systems: aerobic, anaerobic, and attached-
growth. Water Sci Technol 63:29993005
Bouhabila EH, Ben-Aim R, Buisson H (2001) Fouling
characterisation in membrane bioreactors. Sep Purif
Technol 2223:123132
Fane AG, Fane SA (2005) The role of membrane technol- Affinity Membranes
ogy in sustainable decentralized wastewater systems.
Water Sci Technol 51(10):317325
Fawehinmi F, Lens P, Stephenson T, Rogalla F, Jefferson
Francesca Militano1,2 and Lidietta Giorno1
1
B (2005) The inuence of operating conditions on Institute on Membrane Technology, National
extracellular polymeric substances (EPS), soluble Research Council of Italy, ITM-CNR, Rende,
microbial products (SMP) and bio-fouling in anaerobic Italy
membrane bioreactors. In: IWA specialized conference 2
on water environment
Univeristy of Calabria, Rende, Italy
Hong SP, Bae TH, Tak TM, Hong S, Randall A (2002)
Fouling control in activated sludge submerged
hollow ber membrane bioreactors. Desalination Introduction
143:219228
Judd S (2005) Fouling control in submerged membrane
bioreactors. Water Sci Technol 51(67):2734 Afnity separation methods rely on a molecular
Judd S (2006) The MBR book: principles and applications recognition phenomenon between species.
of membrane bioreactors in water and wastewater treat- A molecule, known as the ligand, is permanently
ment. Elsevier Science, Oxford
Kang Y-T, Cho Y-H, Chung E-H (2007) Development of
bounded onto an inert matrix and specically
the wastewater reclamation and reusing system with a recognizes the molecule of interest, known as
submerged membrane bioreactor combined the ligate, that can be separated. The ligand can
bio-ltration. Desalination 202:6876 be a naturally occurring molecule, an engineered
Lawrence P, Adham S, Barro L (2002) Ensuring water
re-use projects succeed institutional and technical
macromolecule, or a synthetic molecule linked to
issues for treated wastewater re-use. Desalination the matrix by covalent coupling. The ligand-ligate
152:291298 interaction is selective and reversible, enabling
Le-Clech P, Fane A, Leslie G, Childress A (2005) MBR the separation and ne purication of biological
focus: the operators perspective. Filtr Sep 42(5):2023
Le-Clech P, Chen V, Fane TAG (2006) Fouling in mem- substances such as proteins, peptides, and nucleic
brane bioreactors used in wastewater treatment. acids on the basis of its individual chemical struc-
J Membr Sci 284:1753 ture or biological function (Wilson and Poole
Meng FG, Chae SR, Drews A, Kraume M, Shin HS, Yang 2009).
FL (2009) Recent advances in membrane bioreactors
(MBRs): membrane fouling and membrane material.
Among the separation techniques based on the
Water Res 43(6):14891512 afnity method, afnity chromatography is the
Psoch C, Schiewer S (2005) Critical ux aspect of air most widely used. Due to the limitation associated
sparging and backushing on membrane bioreactors. to the traditional afnity chromatography with
Desalination 175:6171
Psoch C, Schiewer S (2006) Resistance analysis for
porous bead-packed columns (i.e., limited ow
enhanced wastewater membrane ltration. J Membr rate by pore diffusion), the membrane-based sep-
Sci 280:284297 aration technique is gaining an increasing
16 Affinity Membranes

importance. Indeed, afnity membranes combine density of functional groups and increase the
the specicity of afnity adsorption (of the com- mechanical strength, composite cellulose mem-
mon afnity resins) with the high productivity branes have been also prepared by chemical
associated with ltration membranes. They pro- grafting with acrylic polymers.
vide low pressure separation systems without dif- Another suitable membrane material is polyvi-
fusional limitation, as the mass transfer is mainly nyl alcohol, thanks to its hydrophilicity and bio-
governed by convection (Klein 2000). Micropo- compatibility. Like cellulose, it contains hydroxyl
rous membranes, both in at sheet and hollow groups that can be easily activated.
ber conguration, coupled with biological or Polyamide and nylon have been also used for
biomimetic ligands have been used as afnity the preparation of afnity membranes, thanks to
membrane chromatography supports (Zou their good mechanical and chemical stability.
et al. 2001). Nylon membranes have a low concentration of
amino groups to serve as functional groups for
ligand coupling. Also, due to the hydrophobic
Affinity Membrane Preparation surface, the membrane presents a high nonspecic
adsorption of biomolecules during afnity sepa-
The realization of afnity membranes usually ration process. Therefore, the hydrolysis of the
involves three steps: (1) preparation of the basic membrane is generally performed to increase the
membrane, (2) activation (functionalization) of density of reactive groups and to prevent electro-
the basic membrane, and (3) coupling of afnity static interaction with proteins. To overcome these
ligands to the activated membrane. problems, composite nylon membranes have been
also prepared.
Membrane Material Other materials that have been used for afnity
The membrane materials should possess some membranes are poly(methyl methacrylate),
characteristics: (i) hydrophilicity to minimize the polysulfone and its derivative, polycaprolactam,
nonspecic adsorption of bioactive species, polyvinylidene diuoride, poly(ether-urethane-
(ii) chemical and physical stability under harsh urea), and inorganic materials such as glass.
conditions used during ligand coupling and
ligand-ligate complex formation, (iii) large sur- Membrane Activation and Ligand Coupling
face area relative to membrane volume, If the basic membrane does not possess the func-
(iv) biocompatibility when the membrane is used tional groups for ligand coupling, it can be
for blood treatment, and (v) presence of functional activated.
groups required for the coupling of the ligands In Table 1 are reported the commonly used
(such as OH, NH, SH, COOH). activation agents with respect to the functional
The commercially available materials used for groups present on the basic membrane.
afnity membrane preparation include organic The coupling of the ligand directly on the
(natural or synthetic polymer), inorganic, and activated membranes may result in low binding
composite materials. specicity due to the low steric availability
Among the rst materials used for afnity (in particular when the ligand is a small molecule).
membrane preparation, cellulose and its deriva- This problem is generally overcome by the
tives (regenerated cellulose, cellulose acetate) introduction of a spacer molecule to the mem-
were the most common. These present a hydro- brane prior to attaching the ligand, improving
philic and biocompatible surface, low nonspecic the ligand accessibility for the molecule to
adsorption, and abundant reactive hydroxyl be separated. Spacer arms are bifunctional mole-
groups that can be easily activated by different cules able to react with both the membrane and
strategies for the ligand coupling. To improve the ligand.
Affinity Membranes 17

Affinity Membranes, Table 1 Some commonly used activation agents for affinity membrane preparation
Activation agent Structure Functional groups of the basic membrane
Cyanogen bromide
N C Br
OH A

Carbonyldiimidazole O OH, NH2

N N
N N

2-Amino-4,6-trichloro-s-triazine Cl OH

N N

Cl N NH2

Glutaraldehyde OH, SH, NH2


O O

Divinyl sulfone O OH, SH


CH2
S
H2C O

Epichlorohydrin OH, NH2


O
Cl

Affinity Ligands Although the biospecic ligands possess high


specicity for proteins, they have some limitation
Afnity ligands can be classied into biospecic for large-scale application due to their poor stabil-
and pseudo-biospecic ligands (Klein 1991). ity and high price.
Biospecic ligands are biomolecules such as The alternative approach to biospecic ligands
antibodies, antigens, and proteins A and G that involves the use of pseudo-biospecic ligands.
show specicity for only one complementary These are usually molecules with higher chemical
biomolecule. and physical stability than biomolecules. Pseudo-
Because of their selectivity, biomolecules have biospecic ligands can be distinguished by bio-
been the most widely used afnity ligands on logical (amino acids, specially histidine, lysine,
afnity membrane separation technology. One of tryptophan) or non-biological molecules (dyes,
the most common applications is the use of chelated metal ions).
immobilized monoclonal antibodies for The working principle of pseudo-biospecic
immunoafnity separation. Another important ligands relies on the complementarity of structural
example is membranes with covalently coupled features of ligand and ligate rather than on a
protein A or protein G for immunoglobulin puri- biological function. Immobilized dyes have
cation from plasma, serum, or cell culture been found to act as afnity ligands for a wide
supernatants. variety of biological molecules. For example,
18 Affinity Membranes

Affinity Membranes, Table 2 Some examples of the use of affinity membranes for isolation and purification of
biomolecules
Membrane Ligand Ligate Application
Cellulose and regenerated Cibacron Blue F3GA Alkaline phosphatase Purication
cellulose Protein A/G IgG Purication
Histidine Endotoxin Removal of
endotoxin
Poly(ethylene-co-vinyl Histidine IgG Purication
alcohol)
Nylon Cibacron Blue Glucose-6-phosphate Purication
dehydrogenase
Protein G IgG Purication
Histidine Endotoxin Removal of
endotoxin
Polyvinylidene diuoride Protein A IgG Purication
(PVDF)
Polysulfone (PS) Trypsin Trypsin inhibitor Purication
Iminodiacetic acid Histidine/tryptophan Purication
(IDA)
Glass IDA-Cu2+ Lysozyme, cytochrome c, Purication
ribonuclease A

triazine-linked dyes have been used to mimic are complementary in shape and functionality to
coenzymes that bind a number of dehydroge- the target molecule.
nases, hexokinases, and alkaline phosphatases;
the reactive triazine groups can be linked to any
matrix containing hydroxyl groups by mixing the Applications of Affinity Membranes
two together. Cibacron Blue F3GA (a textile dye)
has been employed as ligand in afnity mem- Afnity membranes are used for several
branes for the purication of over 80 enzymes different applications such as purication of bio-
and proteins. molecules, removal of unwanted substances from
Another important example of pseudo- biological uids, and also small-scale analytical
biospecic afnity ligands is chelated metal ions separations.
used for the purication of histidine-tagged fusion The most common application is the separation
proteins. and purication of biomolecules and especially
proteins for large-scale production.
In Table 2 are reported some typical examples
Molecular Imprinted Membranes of their use for the separation and purication of
biomolecules.
A different approach for the preparation of afnity
membranes is the use of molecularly imprinted
polymeric materials. These are produced by
entrapping a template molecule (the molecule to References
be separated) in a polymer matrix during poly-
Klein E (ed) (1991) Afnity membranes: their chemistry
merization and subsequent extraction. In this way, and performance in adsorptive separation processes.
binding sites are introduced in the polymer that Wiley, New York
Affinity Membranes for Adsorptive Separation Process 19

Klein E (2000) Afnity membranes: a 10-year review. Adsorptive membranes are mainly applied in
J Membr Sci 179:127 separation of biomolecules (proteins, DNA, endo-
Wilson ID, Poole CF (2009) Handbook of methods and
instrumentation in separation science, vol 1. Academic, toxins, etc.). Their application has been extended A
Boston to the removal of toxic contaminants from waste-
Zou H, Luo Q, Zhou D (2001) Afnity membrane chro- water (Wu et al. 2008). The interactions between
matography for the analysis and purication of pro- adsorbates and adsorptive membranes are identi-
teins. J Biochem Biophys Methods 49:199240
cal to those using particulate adsorbents. They
could be categorized into four modes: afnity,
ion exchange, hydrophobic interaction, and
reverse phase (Roper and Lightfoot 1995;
Charcosset 1998). Afnity mode provides strong
Affinity Membranes for Adsorptive specic binding, such as biospecic,
Separation Process immunoafnity, dye afnity, immobilized metal
ion afnity, and pseudo afnity. Ion exchange
Shing-Yi Suen adsorption, including weak and strong, cation
Department of Chemical Engineering, National and anion exchange, is based on electrostatic
Chung Hsing University, Taichung, Taiwan interaction so that fast binding and high recovery
are easily attained to increase its popularity in
commercial products. The last two modes are
Afnity membrane (also called adsorptive mem- both induced by van der Waals force and hydro-
brane, membrane adsorber, or membrane chro- phobic interaction, with a difference that the
matography) is a design using membrane for strength of reverse phase mode is larger. The
adsorptive separation. The traditional shape for applications of these two modes are limited due
adsorbents is particle. In batch process, particulate to the probable inactivation of biomolecules.
adsorbents need to be suspended uniformly in Several methods could be employed to prepare
liquid bath by agitation for good contact with the adsorptive membranes: (1) polymerization of
adsorbates. After adsorption, centrifugation/ltra- monomers containing special functional groups
tion/precipitation is required to separate solid par- (or ligands), followed by dissolving of polymer
ticles from the liquid. On the other hand, and casting it into a lm; (2) introduction of func-
particulate adsorbents are commonly packed in a tional groups into a polymer in solution and cast-
column/vessel (so-called chromatography or ing it into a lm; (3) immobilization of functional
packed bed) for ow operation, where various groups onto a preformed membrane; and
operational conditions (xed bed, moving bed, (4) blending of particulate adsorbents and poly-
uidized bed, etc.) could be applied. However, mer solution together and casting it into a lm
pressure drop and intraparticle diffusion limita- (so-called mixed matrix membrane) (Avramescu
tions usually restrict the separation effectiveness et al. 2003; Sau and Fee 2009).
of large-scale chromatographic system. An Adsorptive membrane system can be operated
advantageous alternative for adsorptive separa- using commercially available geometries such as
tion is to adopt porous membrane with suitable at sheet, tubular/hollow ber, spiral wound,
functionality (adsorptive membrane), which has etc. (Roper and Lightfoot 1995; Zou et al. 2001;
exhibited better mass transfer effects by convec- Suen et al. 2003). Figure 1 depicts the ow pro-
tive transport of solutes and minimal thickness to cess of adsorptive membrane (i.e., membrane
allow operation at low pressure (Roper and chromatographic system). Similar to a conven-
Lightfoot 1995; Charcosset 1998; Zou tional chromatographic system with particulate
et al. 2001; Ghosh 2002; Suen et al. 2003). adsorbents, a cycle of operation consists of
20 Affinity Membranes for Purification of Enzymes

Affinity Membranes
for Adsorptive
Separation Process,
Fig. 1 Schematic diagram
of ow process for
adsorptive membrane Membrane UV-vis
module detector

Peristaltic
pump
Computer
Feed Effluent
solution

loading (adsorption), washing, elution


(desorption), and/or regeneration. To achieve a Affinity Membranes for Purification
larger-scale adsorptive capacity, it is simple and of Enzymes
convenient to stack at sheet membranes in series
or wind a larger sheet around a cylindrical core. Renbi Bai and Xiaoying Zhu
Department of Civil and Environmental
Engineering, National University of Singapore,
Faculty of Engineering, Singapore, Singapore
References

Avramescu ME, Borneman Z, Wessling M (2003) Mixed- Enzymes and Their Purification
matrix membrane adsorbers for protein separation.
J Chromatogr A 1006:171183
Charcosset C (1998) Purication of proteins by membrane
Enzymes are large biological molecules that cata-
chromatography. J Chem Technol Biotechnol lyze chemical interconversions. Most enzymes are
71:95110 proteins and they are highly selective catalysts.
Ghosh R (2002) Protein separation using membrane chro- Since enzymes are selective for their substrates and
matography: opportunities and challenges.
J Chromatogr A 952:1327
speed up only specic reactions from among many
Roper DK, Lightfoot EN (1995) Separation of biomole- possibilities, the types of enzymes determine the
cules using adsorptive membranes. J Chromatogr pathways and therefore affect the products of reac-
702:326 tions. Hence, there is always the need for enzymes
Sau SM, Fee CJ (2009) Fractionation of beta-
lactoglobulin from whey by mixed matrix membrane
of different types to be separated and puried.
ion exchange chromatography. Biotechnol Bioeng
103:138147
Suen SY, Liu YC, Chang CS (2003) Exploiting Affinity Membranes
immobilized metal afnity membranes for the isolation
or purication of therapeutically relevant species.
J Chromatogr B 797:305319 Conventional membranes generally act like a
Wu JS, Liu CH, Chu KH, Suen SY (2008) Removal of sieve for separation, blocking substances larger
cationic dye methyl violet 2B from water by cation than the membrane pores and passing substances
exchange membranes. J Membr Sci 309:239245
Zou H, Luo Q, Zhou D (2001) Afnity membrane chro-
smaller than the membrane pores. However,
matography for the analysis and purication of pro- afnity membranes operate not only on the siev-
teins. J Biochem Biophys Methods 49:199240 ing mechanism but more importantly have
Affinity Membranes for Purification of Enzymes 21

selective binding capabilities, provided by vari- positively charged or negatively charged


ous binding sites on the external and internal enzymes, respectively. For example, porous
surfaces of the membranes. Thus, afnity mem- nylon membranes were modied with poly A
branes can separate and purify substances with (2-(methacryloyloxy)ethyl succinate) brushes to
the combined advantages of high selectivity due purify positively charged lysozyme from chicken
to the specic binding sites and the high pro- egg white (Jain et al. 2010). Negatively charged
ductivity of conventional ltration membranes. sulfonyl matrices acting like ion exchangers were
Many afnity membranes were developed by prepared on cellulose membranes to purify crude
postmodications of existing microporous ultra- cationic urokinase (plasminogen-activating
ltration and microltration membranes. Due to enzyme) from human urine at pH 4.5 (Hou and
the different membrane materials, various modi- Zaniewski 1990). These afnity membranes can
cation approaches may have to be used to provide trap all positively charged enzymes or negatively
the specic binding sites on the membranes. For charged enzymes at the same time. In other words,
example, polymeric membrane materials with if one needs to have a particular type of enzymes,
functional end-groups can directly react with reac- the concentrated enzymes from the membrane
tive ligands. On the other hand, inert membrane need further purication.
materials, such as aliphatic hydrocarbons without The second type of afnity membranes can
active side chains or end-groups, are usually mod- provide more specic enzyme purication. These
ied by radiation chemistry to incur their reactiv- afnity membranes can bind enzymes through the
ity for ligand immobilization. Premodication of interaction between a Lewis acid (electron pair
membrane materials may be another route to pre- donor), such as a chelated metal ion and an electron
pare afnity membrane. Functional monomers acceptor group, such as histidine or tryptophan
with binding sites were polymerized to have residues on His-tagged recombinant proteins.
functionalized polymers that are subsequently This purication mechanism is the same as
used to fabricate afnity membranes. immobilized metal afnity chromatography
The applications of afnity membranes are (IMAC) which is a commercial protein purication
similar to those of afnity chromatography method targeting His-tagged recombinant proteins.
developed with the bead columns, but afnity For example, poly(2-(methacryloyloxy)ethyl suc-
membranes have the advantage of shorter process cinate) brushes of a porous nylon membrane were
time, increased separation efciency at low further functionalized with nitrilotriacetate (NTA)-
pressures, and greater productivity. Ni 2+ to bind His-tagged ubiquitin (Jain
et al. 2010). These afnity membranes usually
can rapidly get highly puried His-tagged proteins
Purification of Enzymes with Affinity from cell extracts.
Membranes The third type of afnity membranes is
using immobilized ligands to bind complimen-
One of the most important applications of afnity tary enzymes. For example, heparin was cova-
membrane is in purication of proteins or lently linked to a commercial membrane to bind
enzymes. The afnity membranes will trap or antithrombin III which was recovered with 91 %
adsorb specic proteins or enzymes during the purity and 97 % yield (Lutkemeyer et al. 1993).
ltration of their solutions. The trapped proteins
or enzymes are subsequently eluted from the
membranes and concentrated to get the puried
products. In general, there are three types of inter- References
actions between the afnity membranes and the
Hou KC, Zaniewski R (1990) Purication of urokinase by
enzymes. The rst type of interaction is electro-
combined cation exchanger and anity chromato-
static interaction. Anions or cations are covalently graphic cartridges. J Chromatogr-Biomed Appl
immobilized onto the membranes to trap 525(2):297306
22 Affinity Separation and Crystallization of Fc Fragments

Jain P, Vyas MK, Geiger JH, Baker GL, Bruening ML the effector function and biodistribution of the
(2010) Protein purication with polymeric afnity antibody (Beale 1987). Proteolytic digestion pro-
membranes containing functionalized poly(acid)
brushes. Biomacromolecules 11(4):10191026 vides important information to determine an anti-
Lutkemeyer D, Bretschneider M, Buntemeyer H, Lehmann body molecules structure and function. Antibody
J (1993) Membrane chromatography for rapid purica- molecules can be cleaved into fragments and each
tion of recombinant antihrombin-III and monoclonal- of these fragments has a distinct activity.
antibiodies from cell-culture supernatant. J Chromatogr
639(1):5766 A number of enzymes like papain, pepsin, cin,
bromelain, and elastase can be used for this pur-
pose, papain being the most frequently used (Luo
et al. 2002). Because of their smaller size as func-
tional components of the whole molecule, anti-
Affinity Separation body fragments offer several advantages over
and Crystallization of Fc Fragments intact antibodies for use in certain immunochem-
ical techniques and experimental applications. For
Nilay Bereli, Handan Yavuz and Adil Denizli this purpose, researchers have attempted to use
Department of Chemistry, Biochemistry Division, smaller, more stable counterparts of antibodies
Hacettepe University, Ankara, Turkey and have also been searching for alternative
ways to obtain antibody-like receptors (Haupt
et al. 1998). Thus, bioengineered antibody frag-
Immunoglobulins are used by the immune system ments that are smaller than antibodies and have
present in serum and tissue uids to identify and the ability to bind antigen bivalently have been
neutralize foreign targets. Immunoglobulins are promoted by the researchers (Cortese 1995). IgG
Y-shaped molecules comprised of two identical molecule can be digested with papain for gaining
light chains (L) and two identical heavy chains Fab and Fc fragments.
(H) linked via disulde covalent forces and via For the separation of Fab and Fc fragments,
non-covalent interactions. Each chain has con- HiTrap_r Protein A column can be used and col-
stant (CL and CH) and variable (VL and VH) lected the fragments by the fraction unit of the fast
domains (Holt et al. 2003). These form two protein liquid chromatography (FPLC) system
antigen-binding fragments (Fab) that specically (Erturk et al. 2011; Bereli et al. 2013; Aslyuce
recognize and bind to antigen molecule and a et al. 2013). As shown in Fig. 1, a successful
constant fragment (Fc) which is responsible for separation was observed and Fab and Fc fragments

Affinity Separation
and Crystallization of Fc 450
Fragments, Fig. 1 FPLC
chromatogram of IgG after Fab
digestion with papain 350
Absorbance (m/U)

(Erturk et al. 2011)


250

Fc
150

50

50
0 5 10 15 20 25
Time (min)
Aged Carbon Membrane 23

Affinity Separation and Crystallization of Fc Frag-


ments, Table 1 Chromatographic separation data Aged Carbon Membrane
a
Fragment tR N K Rs
A
Fab 3.06 52.39 1.19 6.14 - Miki Yoshimune
Fc 11.16 1089.60 7.31 - 4.70 Research Institute for Chemical Process
Technology, National Institute of Advanced
Industrial Science and Technology (AIST),
were separately collected. The retention times of Tsukuba, Japan
the fragments were achieved at 3.06 and 11.64
min, respectively. The calculated chromato-
graphic parameters such as tR, N, k0 , a, and Rs If the use of high-performance carbon mem-
values are summarized and given in Table 1. Rs branes in gas separations is to be commercial-
value was calculated as 4.70 for Fc fragment. ized, the aging characteristics of such
Because the Rs value should be higher than 1.0 membranes will become important. Little work
for a good resolution of two peaks in such a has been done on studying this aspect of carbon
chromatography system, the results for the reso- membranes, but some researchers have pointed
lution of Fab fragment/Fc fragment can be out that there are signicant problems related to
accepted as good resolution values. the performance stability of carbon membranes
(Jones and Koros 1995a; Lagorsse et al. 2004,
2005; Sau and Ismail 2004). Although they are
chemically and thermally resistant, carbon mem-
References branes generally suffer deterioration in perfor-
mance upon exposure to substances that become
Aslyuce S, Uzun L, Say R, Denizli A (2013) Immuno- strongly adsorbed, such as water vapor or oxygen.
globulin G recognition with Fab fragments imprinted
monolithic cryogels: evaluation of the effects of metal- As carbon membranes have a sharp pore-size dis-
ion assisted-coordination of template molecule. React tribution with a critical size ranging from 0.3 to
Funct Polym 73:813820 0.7 nm, small changes in the effective size of the
Beale D (1987) Molecular fragmentations. Some pore structures can markedly affect their perme-
applications in immunology. Dev Comp Immunol
11:287296 ability toward adsorbing gas molecules. In addi-
Bereli N, Erturk G, Tumer MA, Say R, Denizli A (2013) tion, constrictions in the pore system can occur as a
Oriented immobilized anti-hIgG via Fc fragment- result of chemisorption of oxygen or by strong
imprinted PHEMA cryogel for IgG purication. adsorption of species having very low diffusivity
Biomed Chromatogr 27:599607
Cortese R (1995) Identication of biologically active pep- because of their organophilic nature. Such species
tides using random libraries displayed on phage. Curr will block the pores in the membrane and attenuate
Opin Biotechnol 6:7380 the permeation of other species.
Ert
urk G, Bereli N, Uzun L, Tumer MA (2011) In a study of the effects of air oxidation and
Afnity separation and characterization of IgG
subfragments by fast protein liquid chromatography humidity at room temperature on the aging of
with HiTrap_r Protein A column. Hacet J Biol Chem carbon membranes, Menendez and Fuertes
39:133138 (2001) found the membrane stored in dry or
Haupt K, Mosbach K (1998) Plastic antibodies: humid air underwent a rapid loss of permeability,
developments and applications. Tibtech November
16, 468475 whereas membranes stored under propene or
Holt LJ, Herring C, Jespers LS, Woolven BP, Tomlinson IA nitrogen were protected from damage. The
(2003) Domain antibodies: proteins for therapy. Trends researchers suggested that chemisorption of oxy-
Biotechnol 21:484490 gen rather than physisorption of water is princi-
Luo Q, Mao X, Kong L, Huang X, Zou H (2002) High-
performance afnity chromatography for characteriza- pally responsible for the loss of permeability that
tion of human immunoglobulin G digestion with occurs when a fresh carbon membrane is exposed
papain. J Chromatogr B 776:139147 to air.
24 Air Bubble Geometry

Jones and Koros (1994) found that carbon oxygen. This treatment can be used to restore the
membranes are highly vulnerable to adverse permeation properties to those of fresh
effects of exposure to organic contaminants, membranes.
even at concentrations as low as 0.1 ppm. These studies demonstrated that the effects of
Attempts to regenerate membranes after exposure aging are more pronounced when membranes are
to hydrocarbons by high-temperature (363 K) stored under a high-humidity atmosphere and are
treatment in a vacuum were unsuccessful. Jones exposed to air. The chemisorption of oxygen leads
and Koros (1995a) also studied the effects of to the formation of CO surface groups, thereby
humidity on the O2/N2 selectivity and permeabil- creating a more hydrophilic interface that favors
ity of a carbon membrane by using feeds with increased adsorption of water. Adsorbed species
relative humidities of 2385 %. Some losses in can reduce the pore size of the carbon over time,
performance occurred at all humidity levels, leading to decreases in the permeability and selec-
but this problem could be alleviated by rendering tivity of the membrane. Therefore, studies on the
the surface of the membranes hydrophobic by stability of carbon membranes will be an impor-
coating them with thin layers of Teon AF1600 tant aspect on research on such membranes in the
or AF2400 (Jones and Koros 1995b). The future.
resulting composite carbon membranes were sig-
nicantly protected from the adverse effects of
humidity.
Lagorsse et al. (2008) made a thorough inves- References
tigation on the effects of exposure to air and
Jones CW, Koros WJ (1994) Carbon molecular sieve gas
humidity on the performance of commercialized separation membranes. II. Regeneration following
carbon hollow ber membranes, supplied by Car- organic exposure. Carbon 32:14271432
bon Membranes Ltd. (Israel). The production of Jones CW, Koros WJ (1995a) Characterization of
these membranes involved pyrolysis followed by ultramicroporous carbon membranes with humidied
feed. Ind Eng Chem Res 34:158163
chemical vapor deposition and an activation step Jones CW, Koros WJ (1995b) Carbon composite mem-
(Lagorsse et al. 2004). The researchers found that branes: a solution to adverse humidity effects. Ind
the membrane underwent a loss of permeability Eng Chem Res 34:164167
with time when exposed to pure oxygen or to air; Lagorsse S, Magalhes FS, Mendes A (2004) Carbon
molecular sieve membranes: sorption, kinetic
however, the performance of the membrane ulti- and structural characterization. J Membr Sci
mately stabilized after prolonged exposure. 241:275287
Attempts to regenerate the membranes by expo- Lagorsse S, Campo MC, Magalhes FD, Mendes A (2005)
sure to owing nitrogen at 343 K or by treatment Water adsorption on carbon molecular sieve mem-
branes. Experimental data and Isotherm model. Carbon
with propene and propyne as cleaning agents 43:27692779
resulted in no signicant recovery of permeability. Lagorsse S, Magalhes FD, Mendes A (2008) Aging study
However, no deterioration in permeability of of carbon molecular sieve membranes. J Membr Sci
these membranes was observed when they were 310:494502
Menendez I, Fuertes AB (2001) Aging of carbon mem-
stored under nitrogen. The researchers therefore branes under different environments. Carbon
concluded that aging of carbon membranes is 39:733740
caused exclusively by chemisorption of oxygen Sau SM, Ismail AF (2004) Fabrication of carbon mem-
from air. On the other hand, humidity adversely branes for gas separationa review. Carbon
42:241259
affects the performance of membranes in
multicomponent separation processes because
water is strongly adsorbed, but diffuses relatively
easily through the membranes. Heating under
an atmosphere of hydrogen at 893 K to remove Air Bubble Geometry
surface oxygen groups had some effect on
stable surfaces protected from chemisorption of Honeycomb Membrane Structure
Air Bubbling in Membrane Distillation 25

in direct contact membrane distillation (DCMD)


Air Bubbling in Membrane and the ow sheet is shown in Fig. 1.
Distillation The TCM extract was heated to 4362  C and A
pumped to the module; another pump was used to
Chunrui Wu circulate the permeate water (maintained at 25  C)
State Key Laboratory of Hollow Fiber Membrane at the permeate side of the membrane module. The
Materials and Membrane Processes, Institute of velocity of the feed and permeate ow in the mem-
Biological and Chemical Engineering, Tianjin brane module ranged from 0.07 to 0.13 m/s. To
Polytechnic University, Tianjin, China mitigate membrane fouling, a fan was used to create
gas bubbling at the feed side of the membrane
module. This fan was also utilized to generate gas
Air bubbling is a common method that is used in sparging at the permeate side for gas backwashing
membrane separation process to alleviate mem- of the membrane. The concentration ratio (CR) was
brane fouling and improve ux. It also is a kind of dened as the ratio of the volume of initial extract to
membrane cleaning method. Till now, gas-liquid the volume of concentrated extract to indicate the
two phase ow has been well studied and widely concentrating performance of the experiments.
used in microltration, ultraltration (Cabassud The result showed that a sharp ux decline right
et al. 1997), membrane bioreactor (Psoch and after the air was introduced into the feed circulation,
Schiewer 2005), and other traditional membrane and the ux remained at much lower level when air
separation technologies. was continuously injected. The explanation authors
Based on the above advantages of air bubbling, gave was that the bubbles occupied part of the
it has been introduced into membrane distillation liquid-contacting area in the membrane, thus reduc-
(MD) process to alleviate membrane fouling and ing the effective membrane area, and when gas
improve the heat and mass transfer efciency. entered the membrane pores, this reduced the partial
Researchers have introduced air bubbling into pressure of water vapor within the pores, thus reduc-
MD process and developed several new kinds of ing the driving force. To reduce these effects, inter-
MD process. mittent gas sparging at the feed side at intervals of
The rst application of air bubbling in MD 20 min and lasting only 2 min was applied.
process was rstly reported in 2008 (Ding The effect of gas bubbling on the DCMD per-
et al. 2008) to concentrate the extract of traditional formance was shown in Fig. 2. It could be seen
Chinese medicine (TCM). Air bubbling was used that ux declined rapidly in the beginning of the

Air Bubbling
in Membrane 9
Distillation,
Fig. 1 Schematic of
DCMD apparatus. (1)
Thermostatic bath, (2) tank
of TCM extract, (3) gear
pump for extract
circulation, (4) chiller, (5)
gear pump for permeate, (6)
permeate tank, (7) electric
balance, (8) fan for gas
bubbling, and (9) at sheet
membrane module
3 4 6 8
2 5
7
1
26 Air Bubbling in Membrane Distillation

Air Bubbling 24
in Membrane C0 =1.35g/l, tf=60C, u f=u p=0.102m/s
Distillation, 22 The gas bubbling lasted for 2 min every 20 min
Fig. 2 Performance of 20 1L/min gas flowrate
DCMD using gas bubbling 2L/min gas flowrate
18
on the feed side without gas bubbling
16

N, kg/m2h
14
12
10
8
6
4
2
2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5
CR

Air Bubbling
in Membrane
Distillation,
Fig. 3 Theoretic diagram
of ABMD process Vacuum
Membrane Module
Hollow Fiber

Gas-Liquid two phase


flow

Hot Solution Compressed Air

experiment and then slowly as a result of the very process. Compressed air was pressed into the
low-ux level at this time. The introduction of gas lumen side of the hollow ber membranes
bubbling at the feed side resulted in a higher ux together with the hot feed solution just at the
in the beginning of the experiment and a much inlet of membrane module to form gas-liquid
slower ux decline. Very similar trends were two phase ow, as shown in Fig. 3.
observed with gas bubbling at 1 and 2 L/min The results showed that the permeate ux
which meant that increasing the gas ow rate did increased with the air ow rate and/or feed tem-
not result in further process enhancement. perature increasing. For the VMD process, the
A novel air-bubbling vacuum membrane permeate ux was 22 kg/(m2h) when tested at
distillation (AVMD) process was constructed in 75  C with a feed ow rate of 120 L/h and a
2011 (Wu et al. 2011) to investigate the enhance- vacuum pressure of 0.0085 MPa. While, the ux
ment effect of air bubbling on traditional VMD of AVMD process could reach 40 kg/(m2h)
Air Bubbling in Membrane Distillation 27

Air Bubbling 50 4500


in Membrane N
Distillation, Fig. 4 Effect Re
of feed gas ow prate on the 40
4000
A
performance of AVMD
process

N (kg/m2h)
30

Re
3500
20

3000
10

0 2500
0 10 20 30 40 50 60 70
Gas flow rate (L/h)

Air Bubbling a
in Membrane
Distillation, Fig. 5 (a) Air
inlet connected to the
membrane module; (b) Air
nozzle

Feed

Air

when gas was introduced into feed solution at the J gas


F
rate of 60 L/h, as shown in Fig. 4. For the two J nogas
processes, ux both declined gradually as the feed
concentration increased from 3.5 to 300 g/L, but it where Jgas and Jnogas are the permeate uxes in the
was much slower for AVMD process. SEM pic- DCMD process with and without bubbling,
tures showed that membranes used in AVMD respectively.
process had lighter fouling than that in VMD Gas bubbling is supplied by an air pump. The
process. air inlet at the feed side entrance of the membrane
For elevated salt concentrations in the feed module and the air nozzle for dispersing the air are
steam, gas bubbling was introduced into direct shown in Fig. 5.
contact membrane distillation (DCMD) in 2013 The results showed that the introduction of gas
(Chen et al. 2013) to examine its effect on the MD bubbling could effectively enhance MD ux, and
performance. In the paper, to characterize the per- the ux enhancement ratio could reach 1.72 at an
formance improvement achieved by gas bubbling, optimized gas ow rate. When the condition was
the ux enhancement ratio F is dened: either a high feed operating temperature, low feed
28 Air Bubbling in Membrane Distillation

Air Bubbling 1.8


in Membrane Laminar flow, Ref = 842
Distillation, Fig. 6 Effect Turbulent flow, Ref = 2808
of gas ow rate on F in
laminar and turbulent ows 1.6

1.4

F
1.2

1.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2
Gas flowrate (L.min1)

and permeate Reynolds numbers, or a module still relatively stable with an average value of
with 45 inclined orientation, shorter ber length, 5.16 L/(m2h).
or lower packing density, a higher ux enhance- To sum up, air bubbling was an effective
ment ratio could be achieved. Because air bub- method in membrane distillation to enhance the
bling could enhance the turbulence of feed performance of MD process. Due to the role of
solution, temperature polarization was effectively increasing turbulence of feed solution, air bub-
reduced. However it was not that the bigger the bling could promote the agitation and mix of
gas ow rate, the higher the enhancement ratio. It feed solution to decrease the temperature and con-
was observed that beyond an optimal gas ow centration polarization effect. In addition, the
rate, the enhancement ratio fell, possibly due to enhancing surface shear rate increases the remove
excessive ow bypassing. of foulant from membrane surface at the feed side
The effect of gas ow rate on F in laminar and to inhibit the inuence of membrane fouling.
turbulent ows was shown in Fig. 6. In the gure,
it was observed that these two F curves had a
similar trend. At rst, F increased with increasing References
gas ow rate in the range of 0 Qg 0.2 L min1
for the laminar ow and 0 Qg 0.5 L min1 for Cabassud C, Laborie S, Lain JM (1997) How slug-ow
can improve ultraltration ux in organic hollow bres.
the turbulent ow, while F decreased when gas J Membr Sci 128(1):93101
rate was higher. Furthermore, the value of the Chen GZ, Yang X, Wang R, Fane AG (2013) Performance
laminar condition was much higher than that of enhancement and scaling control with gas bubbling in
direct contact membrane distillation. Desalination
the turbulent ow when other conditions were the
2013(308):4755
same. Ding Z, Liu L, Yu J, Ma R, Yang Z (2008) Concentrating the
In 2009, air bubbling was used in a hybrid extract of traditional Chinese medicine by direct contact
process combining membrane distillation in a membrane distillation. J Membr Sci 310(12):539549
Jirachote P, Fane AG, Pasquier ACS, Wu B (2009) Exper-
submerged membrane bioreactor (MDBR) to
imental study and design of a submerged membrane
mitigate severe fouling and ux decline distillation bioreactor. Chem Eng Technol 32(1):3844
(Phattaranawik et al. 2009). The result showed Psoch C, Schiewer S (2005) Long-term study of an inter-
that adding two inlets for air sparging at mittent air sparged MBR for synthetic wastewater treat-
ment. J Membr Sci 2005(260):5665
2.5 L/min each near the potting at the center of
Wu CR, Yue J, HuaYan C, Xuan W, QiJun G (2011) Study
the membrane bundle induced more turbulence at on air-bubbling strengthened membrane distillation
the membrane surface. Over 15 days, uxes were process. Desalination Water Treat 34(13):25
Air Dehydration by Membrane Technology 29

feed pressure (pF) favor for deep dehumidication,


Air Dehydration by Membrane i.e., allowing low moisture content in feed air (xF).
Technology If no sweep gas is used, the permeate pressure A
has to be decreased by vacuum to obtain a positive
Wei Liu partial pressure gradient of water vapor across the
Energy and Environmental Technology membrane:
Directorate, Pacic Northwest National
Laboratory, Richland, WA, USA pP < x F  pF

Membrane dehydration is commonly used in


Synonym industries for removal of moisture from pressur-
ized air. In these applications, ambient air at atmo-
Membrane air dehydration spheric pressure is often used as sweep gas.
Though moisture content (such as molar fraction)
Air dehydration refers to removal of moisture in the sweep air may be the same as in the process
from humid air and is also termed as air dehumid- air, a signicant partial pressure gradient of water
ication and air drying. Due to the ubiquitous vapor can be managed due to high pressures in
presence of moisture in air, air dehydration repre- the process air. For example, hollow ber mem-
sents one of the largest membrane applications. branes are used for drying of the air pressurized to
Air dehydration through a membrane is essen- about 10 bar (Morgan et al. 1996). Air-sweep
tially a vapor-phase separation process (Fig. 1), dehumidication can also be found in some
which can be carried out in two ways. In one way, laboratory membrane devices, such as Naon
moisture in the feed air diffuses across the mem- membrane tubes for moisture exchange (Ye and
brane and is swept out of the membrane unit with LeVan 2003).
a sweep gas stream (Fig. 1a). In another way, the When humid air is at low or atmospheric pres-
permeated moisture is pulled away from the mem- sures, using ambient air as a sweep stream is no
brane unit by vacuum (Fig. 1b). longer practical, and pulling vacuum in the per-
In the sweeping process, degree of air dehu- meate side becomes necessary. In this case, sev-
midication will be limited by moisture content in eral other pieces of equipment in addition to the
the sweep gas and operation pressures, as membrane separator are required to make an inte-
explained by the following equations: grated dehumidication system (Fig. 2). Such a
membrane dehumidier has been recently pro-
Dp xF  pF  xS  pP > 0
x P  pP posed and is still under development (Xing
xF >
pF et al. 2013). An array of membrane units can be
assembled together that the permeate sides of all
Low molar fraction of moisture in sweep the membrane units are connected to one common
gas (xP), low permeate pressure (pP), and high vacuum line. The vacuum is generated by the use

Air Dehydration by Membrane Technology, Fig. 1 Removal of moisture from humid air through a membrane
30 Air Enrichment, by Polymeric Magnetic Membranes

WATER
VAPOR

LOW
HUMID
HUMIDITY
AIR
DEHUMIDIFICATION AIR
1 UNIT

2 3 CONDENSER 4
COMPRESSOR

5 NON-CONDENSABLE
VACUUM
PUMP GAS

LIQUID LIQUID
RESERVOIR PUMP
LIQUID

Air Dehydration by Membrane Technology, Fig. 2 Process ow diagram of a membrane dehumidication system

of a vacuum pump or gas compressor. The per-


meated moisture is compressed to a pressure Air Enrichment, by Polymeric
above water dew point at environmental Magnetic Membranes
temperature so that water vapor is condensed
into liquid-phase water by rejecting heat of con- Anna Strzelewicz
densation into environment. The condensed water Faculty of Chemistry, Silesian University of
is collected in a reservoir. Water in the reservoir Technology, Gliwice, Poland
may be discharged using a liquid pump, while
residual air noncondensable gas is discharged
into environment using a secondary vacuum The idea of using magnetic membranes for enrich-
pump. ment of air by oxygen is based on the observation
that oxygen and nitrogen have quite different
magnetic properties, i.e., oxygen is paramagnetic
whereas nitrogen diamagnetic. The oxygen mole-
cule is paramagnetic with a magnetic moment of
References
mO2 2:73  1023 JT 1 : Magnetic susceptibil-
Morgan WH, Bleikamp LK, Kalthod DG (1996) Hollow ity of nitrogen is equal to w 150:8  106
ber membrane dryer with internal sweep, US patent mol1 2:5  1028 molecule1 which corre-
no. 5,525,143
sponds only to m 2:5  1028 JT 1 in a mag-
Xing R, Rao Y, TeGrotenhuis W, Caneld N, Zheng F,
Winiarski DW, Liu W (2013) Advanced thin zeolite/ netic eld of 1 T, a value ve orders of magnitude
metal at sheet membrane for energy efcient air dehu- smaller than the O2 magnetic moment (Morrish
midication and conditioning. Chem Eng Sci 1965; Borys et al. 2011).
104:596609
Magnetic membranes are polymeric mem-
Ye X, LeVan MD (2003) Water transport properties of
Naon membranes: part I. Single-tube membrane mod- branes (ethyl cellulose (EC) or poly(2,6-dimethyl-
ule for air drying. J Membr Sci 221:147161 1,4-phenylene oxide) (PPO)) with dispersed
Air Enrichment, by Polymeric Magnetic Membranes 31

Air Enrichment, by
Polymeric Magnetic
Membranes,
Fig. 1 Scheme of the A
experimental setup

magnetic powder (ferrite, praseodymium, and Integration of ux with respect to time allows to
neodymium). The membranes are made by cast- sketch a downstream permeation curve. Typical
ing of appropriate polymer solution with dis- plot of Qa(l,t) versus time is presented in the
persed magnetic powder in an external magnetic Fig. 2.
eld of a specially designed coil (stable magnetic Time-lag method and D1-D8 system allow to
eld with range of induction 040 mT). Removed get some insight into the nature of the considered
from Petri dish membranes are dried in 40  C for transport process. In papers (Strzelewicz and
at least 2 days and then are stored in an exsiccator Grzywna 2007, 2008; Rybak et al. 2009a, b,
under the vacuum conditions (p = 3 mmHg). 2012; Grzywna et al. 2010) a concept of magnetic
Collection of permeation quantities both for indi- membranes for air enrichment is explained. The
vidual gases (O2, N2) and for their mixture (air authors observed an increase in the oxygen ux
21 %O2/79 % N2) is measured in experimental with respect to the nitrogen ux and the enrich-
setup (Fig. 1). ment in the oxygen content of the permeate up to
The measurements are carried out in room 55.6 % for ethyl cellulose magnetic membranes.
temperature for membranes with dispersed mag- Further permeation measurements done in
netic powder before and after magnetization in a polyphenylene oxide (PPO) magnetic membranes
eld magnet with magnetic induction about provided higher enrichments, up to 61.9 %
2.5 T. The setup furnished with a gas chromato- (Table 1).
graph allows to measure the oxygen and the nitro- The transport of the molecules through the
gen concentration in permeate. The main part of magnetic membranes can be modeled by a diffu-
the experimental setup is diffusive chamber, sion with a position-dependent diffusion coef-
where the membrane is put in the form of disk. cient. Such a diffusion coefcient reects the
The setup is used for a low-pressure (from 0.1 to changes in the membrane composition along the
1.0 MPa) analysis of gas permeation. Transport permeation axis. One can observe on the scanning
coefcients can be calculated using ow rate data electron microscope photograph (Borys
and percentage of air enrichment. The ow rate of et al. 2011) of the magnetic membrane cross sec-
the permeate can be recorded using a owmeter. tion that the feed side of the membrane is
32 Air Enrichment, by Polymeric Magnetic Membranes

Air Enrichment, by a
Q
Polymeric Magnetic point for checking
Membranes, oxygen content
stationary state
Fig. 2 Downstream
absorption permeation
curve
a
Q (I, t)

La(L) t

C01
6

Air Enrichment, by Polymeric Magnetic Membranes, the transport of both nitrogen and oxygen by
Table 1 Air enrichment for various membranes prolonging their residence in the channel.
(Strzelewicz and Grzywna 2007)
Oxygen content in The method of air enrichment by magnetic
Membrane B[mT] permeate [%]
membranes seems to be effective and efcient.
EC + 1.38 g Nd 0.79 40.7  1.1
EC + 1.49 g Nd 1.25 43.8  1.1
PPO + 1.80 g Nd 1.70 54.1  1.4
PPO + 1.80 g Nd 2.70 61.9  1.5
References

Borys P, Pawelek K, Grzywna ZJ (2011) On the magnetic


composed of a pure polymer while the output side channels in polymer membranes. Phys Chem Chem
Phys 13:1712217129
consists of the polymer with dispersed magnetic Grzywna ZJ, Rybak A, Strzelewicz A (2010) Air enrich-
granules. When the magnetic eld is too strong, ment by polymeric magnetic membrane. In:
then magnetic aggregates are created, which inu- Yampolskii Y, Freeman B (eds) Membrane gas separa-
ence the permeation of gases. Detailed analysis of tion. Wiley, Chichester, pp 159182
Morrish AH (1965) The physical principles of magnetism,
the available data and microscopy images allowed
1st edn. Wiley, New York
to arrive four conclusions (Borys et al. 2011): Rybak A, Krasowska M, Strzelewicz A, Grzywna ZJ
(2009a) Smoluchowski type equations for modelling
1. There are magnetic channels formed around of air separation by membranes with various structure.
Acta Phys Pol B 40:14471454
the magnetic granules.
Rybak A, Grzywna ZJ, Kaszuwara W (2009b) On the air
2. The channels provide high permeability high- enrichment by polymer magnetic membranes. J Membr
ways for the diffusion of permeating Sci 336:7985
molecules. Rybak A, Strzelewicz A, Krasowska M, Dudek G,
Grzywna ZJ (2012) On the air separation process by
3. The oxygen molecules, due to their paramag- magnetic membranes inuence of various parameters.
netic properties, stick to these highways for a Sep Sci Technol 47:13951404
longer time than nitrogen, which is probably Strzelewicz A, Grzywna ZJ (2007) Studies on the air
based on the interaction with the Weiss molec- membrane separation in the presence of magnetic
eld. J Membr Sci 294:6067
ular eld of the permanent magnet.
Strzelewicz A, Grzywna ZJ (2008) On the permeation time
4. The magnetic eld induces aggregation lag for different transport equations by Frisch method.
between oxygen and nitrogen which enhances J Membr Sci 322:460465
Air Gap Membrane Distillation (AGMD) 33

may be changed from pure conduction and diffu-


Air Gap Membrane Distillation sion to natural convection. The optimum of air
(AGMD) gap width should be determined to achieve the A
best performance of the AGMD system taking
Maria Tomaszewska into account a reduction of the heat loss and the
Faculty of Chemical Technology and value of the permeate ux.
Engineering, West Pomeranian University of Since in AGMD the permeate is condensed on
Technology, Szczecin, Poland the cold surface, the liquid permeate is separated
from the membrane surface, which prevents the
membrane wetting. Thus an important advantage
AGMD is a conguration of membrane distilla- of the process is the ability to remove the organic
tion (MD) in which an air layer is interposed compounds from aqueous solutions.
between a porous hydrophobic membrane and The permeate ux in AGMD can vary from
the condensation surface (Fig. 1). In the process, ca. 0.3 to 26 kg/m2h, depending on the operating
volatile compounds (including water) present in a conditions and feed composition. The rejection
warm feed evaporate at the liquid/vapor interface coefcient of nonvolatile species, e.g., NaCl, usu-
formed at the membrane surface. The vapor is ally amounts close to 100 %. Generally, in AGMD
transferred through the membrane pores and the the nonvolatile species present in a feed are almost
gas gap and nally condenses on a cold surface completely retained, whereas volatile compounds
inside the membrane module. The driving force of are partially transferred through the membrane.
the mass transfer in AGMD is the difference in The separation of compounds present in aqueous
vapor pressure on both sides of the membrane. solutions using AGMD is based not only on the
The air gap signicantly reduces the heat loss vapor/liquid equilibrium, but also the diffusion
by the membrane material, therefore the permeate rate of the feed components through the gas lling
ux could increase. On the other hand air gap the membrane pores and the air gap between the
forms a barrier for the vapor, and due to the membrane and the condensation surface.
mass transfer resistance the permeate ux The air entrapped within the membrane pores
decreases with an increase of the air gap width and in the air gap can be considered as a stagnant
(Table 1) (Alkhudhiri et al. 2012). When the gap lm, thus the mass transfer in AGMD is generally
width is changed, the mechanism of heat transfer described according to the ordinary molecular dif-
fusion including both the air and noncondensable
Feed Tf,in gases in the membrane pores and in the air gap. The
vapor air gap width is usually 10100 times greater than
the membrane thickness; therefore the membrane
characteristics are usually neglected. In AGMD,
Tf,m Tc
Important condition: the heat transfer includes the heat transfer through
Tf,m > Tc the feed boundary layer, through the membrane
and the gas gap, condensation at the cold surface,
air gap

and heat transfer through the condensate liquid


membrane boundary layer and to the cooling water. To opti-
mize the AGMD systems, the effects of operating
Tf,in > Tf,out parameters should be taken into account (Khayet
and Matsuura 2011).
Tf,out cooling liquid The feed temperature strongly affects the per-
Liquid meate ux. Since the vapor pressure of aqueous
permeate
solutions grows exponentially with temperature,
Air Gap Membrane Distillation (AGMD), the driving force increases for both water and
Fig. 1 Schema of AGMD volatile compounds present in a feed. Thus, the
34 Air Gap Membrane Distillation (AGMD), Applications of

Air Gap Membrane Distillation (AGMD), Table 1 Air gap effect on the permeate flux (reprinted from Alkhudhiri
et al. (2012), copyright (2012) with permission from Elsevier)
Membrane Pore size Tin Air gap Permeate ux
Ref material (mm) Feed ( C) (mm) kg/m2.h
[5] PVDF 0.45 Articial seawater 60 1.99.9 52.1
[6] PTFE 0.2 Isopropanol 50 1.620.55 5.16.3
[108] PVDF 0.22 Sucrose 25.8 14 1.70.8 l/m2h
[18] PTFE 0.2 NaCl (3.8 %) 60 0.39 191.5
[120] PTFE 0.22 HNO3 (4 M) 80 0.52 5.34.25 l/m2h
[123] PTFE 0.45 HCl/water 60 47 3.72.4
[123] PTFE 0.2 Propionic acid/ 60 47 7.44.6
water
Comments the references can be found in the original paper

total permeate ux Jt (a sum of the water vapor


ux Jw and the volatile compounds ux Jv) Air Gap Membrane Distillation
increases, but the selectivity of volatile solutes (AGMD), Applications of
decreases with a feed temperature. The heat loss
by conduction through the membrane material is Maria Tomaszewska
lower at higher feed temperature which also Faculty of Chemical Technology and
explains the higher permeate ux. Engineering, West Pomeranian University of
An increase in the concentration of nonvolatile Technology, Szczecin, Poland
compounds in a feed reduces the Jt due to a
decrease in the Jw. In the case of an increase of
concentration of volatile compounds in a feed, the The separation using AGMD is based not only on
Jt and Jv increase, whereas the Jw decreases. It is vapor/liquid equilibrium but also on the diffusion
associated with changes of the partial pressure of rates of the feed components through the gas
dissolved species and water. The selectivity of trapped in the membrane pores and the air gap
volatile compounds can be different depending between the membrane and the condensation sur-
on their properties and concentration in the feed face. Nonvolatile compounds are rejected by a
and can be improved by an increase of their partial membrane in almost 100 %. Therefore, AGMD
pressure by salt addition into a feed. Generally, a can be applied for desalination and production of
higher feed ow rate diminishes the effects of high-purity water. A permeate with electrical con-
both temperature and concentration polarization ductivity as low as 4 mS/cm can be obtained from
and AGMD permeate ux increases. Different a solution with composition similar to seawater.
spacers can be applied to improve the hydrody- Moreover, AGMD can be applied for the separa-
namic conditions. The effect of coolant tempera- tion of volatile compounds. Since the vapor is
ture is not very signicant because the heat condensed on the cold surface and the liquid per-
transfer coefcient in the air gap dominates the meate does not come into contact with a hydro-
overall heat transfer coefcient (Khayet and phobic membrane, even the organic solutes can be
Matsuura 2011). separated without a risk of the membrane wetting.
The air gas reduces considerably the heat loss and
the temperature polarization which improve the
References separation efciency of AGMD; however, this
leads simultaneously to a signicant decrease in
Alkhudhiri A, Darwish N, Hilal N (2012) Membrane distil-
the permeate ux. The decrease depends strongly
lation: a comprehensive review. Desalination 287:218
Khayet M, Matsuura T (2011) Membrane distillation. Prin- on the width of the air gap. The air gap is about
ciples and applications. Elsevier, Amsterdam 10100 times thicker than the membrane, so the
Air Gap Membrane Distillation (AGMD), Applications of 35

Air Gap Membrane Distillation (AGMD), Applications of, Table 1 Application of air gap membrane distillation
Area Membrane material Application
Desalination PTFE, PVDF Water and wastewater treatment, production of pure water, A
Modied ZrO2, modied Al2O3, solar-powered desalination, geothermal wastewater
modied TiO2, modied treatment
aluminosilicate
Food industry PVDF, PTFE Fruit and vegetable juice concentration, milk concentration,
sugar and gelatine solution concentration, ethanol
concentration
Biotechnology PTFE, PVDF Ethanol separation from a broth
Others PTFE, PVDF Methanol, isopropanol concentration, separation of
azeotropic mixtures HCl/water, propionic acid/water,
formic acid/water, separation of radioisotopes 18O and 18F,
concentration of wastewater containing isotopes, HI and
H2SO4 concentration
Separation/removal of HNO3, HCl, formic acid, acetic acid,
propanone from aqueous solutions
PTFE polytetrauoroethylene, PVDF polyvinylidene uoride

effect of air inside the membrane can be feedwater, tness for intermittent energy supply,
neglected. AGMD creates the opportunity for the and the ability to use direct solar heat without heat
separation of species forming the azeotropic solu- storage, the plants have not been commercialized
tions. It is attributed to the difference in the diffu- or implemented in a large scale. This is mainly
sion coefcients of volatile compounds present in because reverse osmosis (RO) is considered as
a feed through the gas gap (Khayet and Matsuura more economical and energy-efcient desalina-
2011). Thus, AGMD can nd the application in tion process (Saffarini et al. 2012). However, the
water and wastewater treatment, biotechnology, AGMD/solar energy systems are still in progress
food industry, etc. (Table 1). and nd a growing interest.
The plate and frame, tubular, capillary, and Another eld of AGMD application is food
very frequently spiral wound modules equipped processing. Figure 2 presents the possibility of
with porous hydrophobic membranes are used juice concentration by AGMD to achieve much
in AGMD. higher feed concentration than using RO. Low
The main area of AGMD application is desali- processing temperature allows to concentrate the
nation. The desalination pilot plants combining solutions sensitive to high temperature and pro-
AGMD with solar energy collectors were devel- vides a good quality of juice concentrate (Kimura
oped, especially for operation in arid and semiarid and Nakao 1987). The concentration of milk dem-
remote regions with a lack of electricity and drink- onstrated that the membranes were easily fouled
able water but with high solar radiation (Table 2). by milk fat and the permeate ux decreased very
The production of potable water, e.g., from plants fast (Khayet and Matsuura 2011).
installed in Jordan was of 100 L/day (utilizing Ethanol preferentially vaporizes from the
brackish water) and 1 m3/day (Fig. 1) (utilizing aqueous feed and is concentrated in the permeate.
untreated seawater from the Red Sea). The instal- Since in AGMD the liquid ethanol does not come
lations were equipped with AGMD spiral wound into contact with a membrane, it can be separated
modules with area of 1040 m2, respectively. from a fermentation broth and concentrated with-
Long-term experiments have demonstrated that out a risk of the membrane wetting. It was found
the average salt rejection was 98 % (Qtaishat and that a salt addition into diluted ethanol increases
Banat 2012; Khayet and Matsuura 2011). Distil- alcohol selectivity (Khayet and Matsuura 2011).
late conductivity of 35 mS/cm can be obtained for AGMD can be useful in breaking the
brackish water feeding. Despite the advantages azeotropic mixtures of water and hydrochloric or
such as the ability to desalinate high saline propionic acids. This phenomenon was associated
36 Air Gap Membrane Distillation (AGMD), Applications of

Air Gap Membrane Distillation (AGMD), Applications of, Table 2 Timeline of solar-powered membrane distillation
systems and their general features (Adapted from Saffarini et al. 2012)
Energy system type Solar
Membrane Feedwater collector
Year Location MD type type/material type Thermal Electrical type
1991 New South DCMD Hollow ber/ N/A Solar Grid N/A
Whales, N/A collector
Australia
1995 New South AGMD Spiral wound/ N/A Solar Grid VPC
Wales, Australia PTFE collector
1997 Tokyo, Japan N/A N/A/N/A N/A Solar PV N/A
collector
1999 Texas, USA AGMD N/A/N/A N/A Solar Grid N/A
pond
1999 Irbid, Jordan DCMD N/A/PTFE Brackish Solar Grid N/A
still
2003 Freiburg, AGMD Spiral wound/ Freshwater Solar Grid FPC
Germany PTFE collector
2004 Texas, USA AGMD N/A/N/A NaCl Solar Grid N/A
solution pond
2007 Irbid, Jordan AGMD Spiral wound/ Brackish Solar PV FPC
PTFE collector
2007 Aqaba, Jordan AGMD Spiral wound/ Seawater Solar PV FPC
PTFE collector
2008 Alexandria, AGMD Spiral wound/ Brackish Solar PV FPC
Egypt PTFE collector
2008 Mexico DCMD Hollow ber/ N/A Solar Grid FPC
N/A collector
2009 Almeria, Spain AGMD Flat sheet/ Seawater Solar Grid CPC
PTFE collector
2009 Hangzhou, China VDM Hollow ber/ Brackish Solar Grid N/A
PP collector
2009 Nevada, Reno, Vacuum N/A/N/A N/A Solar N/A N/A
USA enhanced pond
DCMD
2009 Gran Canaria, AGMD Spiral wound/ Seawater Solar PV Double
Spain PTFE collector glass FPC
2011 Marina Barrage, VMEMD Flat sheet/ Seawater Solar PV N/A
Singapore PTFE collector
DCMD direct contact membrane distillation, VMD vacuum membrane distillation, PP polypropylene, N/A not available,
PV photovoltaic panels, VPC vacuum plate collector, FPC at plate collector, CPC concentrated parabolic collectors,
VMEMD vacuum multi-effect membrane distillation

with the differences in the acid-air and water-air AGMD was successfully used for the concen-
diffusion rates in the air gap. In AGMD the tration of a mixture of HI and H2SO4, compounds
hydrochloric acid/water azeotrope was shifted to of great interest for H2 generation in thermochem-
higher acid concentration, and the azeotrope was ical water-splitting cycle (Khayet and Matsuura
eliminated in the propionic acid/water system. It 2011). AGMD has also a great potential in the
was found that the heavy gases such as SF6 help application in the environment protection area.
more in eliminating the azeotropic point than the Therefore, this technique requires more studies,
lighter ones as air or He (Khayet and Matsuura devoted especially to a long-term performance
2011). and membrane life.
Air Gap Membrane Distillation (AGMD), Applications of 37

Solar
irradiation Brine

A
Collector
feild
Feed
Storage pump
tank
Heat
exchanger

Distillate MD modules

Battery PV
Expansion
vessel
Control
unit DC PV
AC
PV array

Air Gap Membrane Distillation (AGMD), Applications powdered (Reprinted from Qtaishat and Banat (2012),
of, Fig. 1 Schema of the large system (two-loop desali- copyright (2012) with permission from Elsevier)
nation system) of desalination using AGMD solar

Air Gap Membrane 400


Distillation (AGMD),
Applications of, RO, P = 5 MPa
350 AGMD, Tf = 321 K
Permeate flux, J [kg m2d1]

Fig. 2 The comparison of


the permeate ux during
concentration of the 300
mandarin orange juice
using RO and AGMD
(Adapted from Kimura and 250
Nakao 1987)
200

150

100
1 1.5 2 2.5 3
Concentration ratio, CV

References Qtaishat MR, Banat F (2012) Desalination by solar pow-


dered membrane distillation systems. Desalination.
Khayet M, Matsuura T (2011) Membrane distillation. Prin- doi:10.1016/desal2012.01.021
ciples and applications. Elsevier, Amsterdam Saffarini RB, Summers EK, Arafat HA, Lienhard VJH
Kimura S, Nakao SI (1987) Transport phenomena (2012) Technical evaluation of stand-alone solar
in membrane distillation. J Membr Sci 33: powered membrane distillation systems. Desalination
285298 286:332341
38 Air Products

The compressed air at a temperature of


Air Products 80100  C and a pressure of about 1000 kPa
(135150 psi) is puried by the use of coalescing
Pushpinder S. Puri lter and fed to the membrane module. The pro-
PuriMem, LLC, Emmaus, PA, USA ductivity and purity of the nitrogen produced is
controlled by the use of a product pressure valve.
Membrane systems produce nitrogen at a concen-
The majority of air separation is done by cryo- tration ranging from 95 % to 99.9 %. However,
genic distillation; however, for several small due to the modest selectivity (<8) of air separa-
applications a gas separation membrane is desir- tion membranes, production of high purity nitro-
able. The key commercial gaseous products made gen is not economically favorable. Key producers
from air by membranes are nitrogen, oxygen of nitrogen separation membranes are Air Prod-
enriched air, and dry air. Further, gas separation ucts, Air Liquide, and Ube. Other nitrogen mem-
membranes in hybrid system with a cryogenic brane producers are: Generon Systems, Aquillo
process is used to produce Argon (Agrawal and and Parker Henifn.
Xu 1996) and with an adsorption process to pro- Dry air with dew point up to 40  C (40  F)
duce high concentration oxygen enriched air is produced by removing moisture from the atmo-
(Choe et al. 1997). spheric air using a water permeable membrane
In membrane nitrogen production systems which are either made of glassy polymers
(Drioli and Barbieri 2011), the compressed air is (polysulfone, polyimide, etc.) or uorine
fed on one side of the membrane; oxygen, argon, containing ionomers. Schematic of a typical air
carbon dioxide, and water which have higher per- drying system is shown in Fig. 2.
meation than nitrogen, permeate through the In air drying system, clean wet air is fed under
membrane leaving nitrogen behind. A schematic pressure on one side of the membrane module and
of the membrane nitrogen generation system is dry air at slightly reduced pressure is recovered as
shown in Fig. 1. retentate. In some systems, an internal or external

VENT TO AIR
ATMOSPHERE
COMPRESSOR WASTE GAS

NITROGEN

ELECTRIC NITROGEN TO
HEATER CUSTOMER

OXYGEN NITROGEN
CONDENSATE ANALYSER BUFFER
NITROGEN VESSEL
PRODUCTION
X
MEMBRANE

Air Products, Fig. 1 Schematic of nitrogen generation system (Reproduced with permission from Air Products)
Air Separation 39

Purging Valve
Purging Air

A
Drain Filter
Compressor Cooler
Separetor Product
Dry Air

SUNSEP-WTM Dryer
Drain

Air Products, Fig. 2 Typical air drying system (Courtesy: AGC Chemicals Americas)

dry air sweep is used to prevent water buildup on


the membrane in permeate, which retards mem- Air Separation
brane performance (Morgan et al. 1996).
In some instances, membrane systems are used Ahmad Fauzi Ismail1 and M. H. D. Othman2,3
1
to produce oxygen enriched air with oxygen con- Faculty of Chemical and Energy Engineering,
centration <30 % O2. Mostly, rubbery mem- Universiti Teknologi Malaysia, Advanced
branes of modest selectivity (23) and high Membrane Technology Research Centre
oxygen ux are used for this application3. The (AMTEC), Johor Bahru, Johor, Malaysia
2
membrane system used is similar to that used for Advanced Membrane Technology Research
nitrogen production described above. Sometimes, Centre (AMTEC), Universiti Teknologi Malaysia,
use of vacuum on the permeate side is preferred Skudai, Johor, Malaysia
3
over the use of a compressor for the production of Faculty of Chemical and Energy Engineering,
oxygen enriched air. Universiti Teknologi Malaysia, Skudai, Johor,
Malaysia

Air separation technology is used for the produc-


References
tion of oxygen, nitrogen, and rare gases that are
Agrawal R, Xu J (1996) Gas-separation membrane cas- present in air such as argon and neon. There are
cades utilizing limited numbers of compressors. AIChE two fundamental approaches to air separation,
J 42:2141 which are cryogenic and non-cryogenic pro-
Choe JC et al (1997) Process for separating components of
cesses. The cryogenic process which is carried
a gas stream. US Patent 4,701,187
Drioli E, Barbieri G (eds) (2011) Membrane engineering out in distillation column has the capability to
for the treatment of gases. Gas-separation problems deliver large and high purities of products, while
with membranes, vol 1. RSC Publishing, Cambridge. the non-cryogenic which is based on absorption
Chapter 8,
and membrane technologies is more suitable for
Morgan WH, Bleikamp LK, Kalthod DG (1996) Hollow
ber membrane dryers with internal sweep. US Patent on-site production, which is most common for
5,525,143 small and medium throughputs.
40 Air Separation

Air Separation,
Pressurized Oxygen
Fig. 1 Schematic
air feed O 2 + 2e O2 depleted air
representation of the
oxygen transport in MIEC MIEC
ceramic membrane ceramic
O2 - e- O2- e-
membrane

Oxygen rich O2 O 2 + 2e Sweep gas


stream

Membrane technology for air separation has Interestingly, the oxygen separation from air in
developed rapidly in recent years. Polymeric and MIEC ceramic membrane system requires neither
ceramic membranes have been used commercially electrodes nor an external circuit to operate. As
for oxygen production. Polymeric membranes depicted in Fig. 1, the electronic conductivity
operate based on the difference in rates of diffu- itself performs as an internal short circuit that
sion of oxygen and nitrogen through a membrane. involves oxygen partial pressure gradient. The
Due to the smaller size of the oxygen molecule, oxygen molecule permeates from the high oxygen
most membrane materials are more permeable to partial pressure side to the low oxygen partial
oxygen than to nitrogen. Materials such as pressure side, while the overall charge neutrality
polysulfone or acetate membranes make it is maintained by counterbalancing the ux of
possible to permeable oxygen ve times than of electrons (Liu and Gavalas 2005). Several indus-
nitrogen. Membrane units capable of producing trial gas companies are working on developing
nearly 600 tonnes per day nitrogen have been ceramic membranes for oxygen separation from
built (Castle 2002). A major benet of polymeric air at high temperatures. Air Products and
membrane separation is the simple, continuous Chemicals has developed an ion transport mem-
nature of the process and operation at near brane (ITM) system, which is based on patented,
ambient conditions (Smith and Klosek 2001); high-temperature ceramic membranes for the pro-
however, the low separation factor of two to six duction of oxygen from air separation (Hashim
limits the polymeric membrane to produce et al. 2011). Praxair is also working on oxygen-
oxygen-enriched air rather than pure oxygen conducting ceramic membrane systems that are
(Zhu et al. 2008). specially designed to separate oxygen from air at
Production of pure oxygen from air can be elevated temperature environment (Hashim
achieved by using ceramic membrane system at et al. 2011).
elevated temperatures, typically in the range of
800900  C (Hashim et al. 2011). The oxygen
transporting through this type of membrane is in Cross-References
the form of oxygen ions instead of oxygen mole-
cules; therefore, the pure oxygen is obtained. Enor- Oxygen Separation
mous efforts have been directed to ceramic
membranes with mixed ionicelectronic References
conducting (MIEC) characteristics. Among them,
perovskite-type (ABO3) ceramic membranes Castle WF (2002) Air separation and liquefaction: recent
exhibit the highest oxygen permeability due to developments and prospects for the beginning of the
their high ionic and electronic conductivity. The new millennium. Int J Refrig 25:158172
Hashim SS, Mohamed AR, Bhatia S (2011) Oxygen sep-
perovskite oxide based on La1xAxCo1yFeyO3d aration from air using ceramic-based membrane tech-
achieved very high oxygen permeation uxes as nology for sustainable fuel production and power
reported by Teraoka et al. (1985). generation. Renew Sustain Energy Rev 15:12841293
Alamine 336 41

Liu S, Gavalas GR (2005) Oxygen selective ceramic hol- electrodeposition and alumina membrane etching
low ber membranes. J Membr Sci 246:103108 (Burggraaf and Cot 1996; Lee and Pope 1994).
Smith AR, Klosek J (2001) A review of air separation
technologies and their integration with energy conver- The ltration process and therefore the elimi- A
sion processes. Fuel Process Technol 70:115134 nation of different species from polluted water, for
Teraoka Y, Zhang HM, Furukawa S, Yamazoe N (1985) example, strongly depend on the type of mem-
Oxygen permeation through perovskite-type oxides. brane used, its porosity, and pore size. As
Chem Lett 167:17431746
Zhu X, Sun S, He Y, Cong Y, Yang W (2008) New concept recommended by IUPAC, porous membranes are
on air separation. J Membr Sci 323:221224 classied according to their connected pore size
being microporous for pore diameters lower than
2 nm, mesoporous for pore diameters in the range
250 nm, and macroporous for pore sizes superior
Al2O3 Porous Membranes than 50 nm (Koros et al. 1996). Respectively,
porous membranes will be applied to separation
Sophie Cerneaux processes such as nanoltration, ultraltration,
UMR 5635 ENSCM, CNRS, UM, Institut and microltration.
Europen des Membranes, Montpellier, France The synthesis of macroporous and mesoporous
membranes is often made by consolidation of
particles followed by thermal removal of organic
Synonyms additives. Going to nanoltration application, the
microporous network is directly prepared from a
Aluminum (III) oxide porous membranes or alu- sol containing particles lower than 10 nm
mina porous membranes followed by an appropriate sintering step.

Characteristics References

Al2O3 is an amphoteric oxide that exhibits poly- Burggraaf AJ, Cot L (1996) Fundamentals of inorganic
membrane science and technology. Elsevier, Amsterdam
morphic crystalline forms upon temperature treat-
Koros WJ, Ma YH, Shimidzu T (1996) Terminology for
ment. A wide variety of alumina powders are membranes and membrane processes. Pure Appl Chem
commercially available with different particle 68(7):14791489
sizes. Lee BI, Pope EJA (1994) Chemical processing of
ceramics. Marcel Dekker, New York
Alumina porous membranes are commercially
available inorganic ceramic membranes widely
used in membrane processes related to water treat-
ment essentially. They are shaped in monolith, Alamine 336
honey comb, at, monochannel, and multichannel
congurations or as thin lms. Karel Friess
Alumina membranes may be prepared by Department of Physical Chemistry, University of
anodic oxidation of aluminum foil to design Chemistry and Technology Prague, Prague,
well-ordered and straight pore channels in the Czech Republic
membrane or by sol-gel route using colloids or
Al molecular precursors to yield porous supported
membranes. In addition, alumina macroporous Synonyms
supports are also used for multilayered structures
of other oxide or non-oxide materials. More Alamine 3365; Alamine 336S; Farmin 08;
recently, alumina porous membranes found a Octanamine; Tricaprylamine; Tridioctylamine;
new application as hard template for the fabrica- Tri-n-octylamine; Tri-n-caprylylamine;
tion of nanotubes and nanowires through Trioctylamine
42 Alamine 336

Alamine 336,
Fig. 1 Schematic structure
of Alamine 336
N

The IUPAC systematic name is N,N-dioctyl-1- Alamine 336, Table 1 Properties of Alamine 336 (Steele
octanamine (Fig. 1). Alamine 336 is colorless et al. 1996)
(C24H51N, CAS Reg. No. 1116-76-3) or light Molar mass 353.67 gmol1

yellow liquid (mixture of Tri C8-10 Alkyl Melting point 34.6 C

Amines, C27H57N CAS Reg. No. 57176-40-6, Boiling point 363.5 C
produced by Cognis Corp., now part of BASF). If Density 0.818 gcm3 at 25  C
released to air, estimated vapor pressure is about Viscosity 7.86102 Pas at 34.6  C
3.48102 Nm1 at 34.6  C
0.007 Pa at 25  C. It is moderately toxic by inges- Surface tension
Constant pressure 750.8 Jmol1K1 at
tion and intraperitoneal routes; when heated to
heat capacity of 25  C
decomposition, it emits toxic vapors of NOx liquid
(Zhu et al. 2012). Manufacturing of Alamine Solubility in 0.1 gcm3 at 25  C
336 is possible by catalytic amination of octanol chloroform
(Li et al. 2011) or by catalytic hydrogenation of Solubility in water 0.050 mgdm3 at 25  C
caprylonitrile (Lazier 1940). It is used as the
extractant for reactor fuel processing (Moyer and
References
McDowell 1981), for dye identication
(Puttemans et al. 1982), and for metal adsorption ChemSpider (CSID). http://www.chemspider.com/
(Tasker et al. 2003) and recovery from diluted Chemical-Structure.13591.html. Accessed 1 June 2012
aqueous solutions (Kislik 2012; Coca Coca J, Dez FV, Mors MA (1990) Solvent extraction of
molybdenum and tungsten by Alamine 336 and DEHP-
et al. 1990; Sun and Lee 2011). Mixtures of
A. Hydrometallurgy 25:125135
Alamine 336 with meta-xylene can be success- Dygiel P, Wieczorek PP (2010) Supported liquid membranes
fully applied for extraction metal ions from their and their modications: denition, classication, theory,
strong acidic aqueous chloride solutions (Sayar stability, application and perspectives. In: Kislik VS
(ed) Liquid membranes. Elsevier, Amsterdam, pp 73140
et al. 2007). Alamine 336 can be also used for
Kislik VS (2012) Examples of application of solvent
specic extractions in biotechnology, e.g., separa- extraction techniques in chemical, radiochemical, bio-
tion of carboxylic acids (Tamada et al. 1990; chemical, pharmaceutical, analytical separations, and
Yordanov and Boyadzhiev 2004), and in wastewater treatment. In: Kislik VS (ed) Solvent
extraction classical and novel approaches. Elsevier,
supported liquid membranes (San Romn
Amsterdam, pp 185314
et al. 2010; Dygiel and Wieczorek 2010) Lazier WA (1940) Process for catalytic hydrogenation of
(Table 1). higher aliphatic nitriles. US Patent 2225059
Albumin Purification with Affinity Membranes 43

Li Y, Li Q, Zhi L, Zhang M (2011) Catalytic amination of


octanol for synthesis of trioctylamine and catalyst char- Alamine 336S
acterization. Catal Lett 141:16351642
Moyer BA, McDowell WJ (1981) Factors inuencing A
phase disengagement rates in solvent extraction sys- Alamine 336
tems employing tertiary amine extractants. Sep Sci
Technol 16:12611289
National Institute of Standards and Technology (NIST)
database. http://webbook.nist.gov. Accessed 1 June
2012 Albumin Purification with Affinity
Puttemans ML, Dryon L, Massart DL (1982) Evaluation of Membranes
thin layer-, paper- and high performance liquid chro-
matography for the identication of dyes extracted as
ion-pairs with tri-n-octylamine. J Assoc Off Anal Chem Adil Denizli and Handan Yavuz
65:730736 Department of Chemistry, Biochemistry Division,
San Romn MF, Bringas E, Ibaez R, Ortiz I (2010) Hacettepe University, Ankara, Turkey
Liquid membrane technology: fundamentals and
review of its applications. J Chem Technol Biotechnol
85:210
Sayar NA, Filiz M, Sayar AA (2007) Extraction of Zn Nearly 175 years ago, a very accurate description
(II) from aqueous hydrochloric acid solutions into of the properties of human serum albumin (HSA)
Alamine 336m-xylene systems. Modeling consider- was available (Ancell 1839). HSA is one of the
ations to predict optimum operational conditions.
Hydrometallurgy 86:2736 most abundant proteins in plasma and, together
Steele WV, Chirico RD, Knipmeyer SE, Nguyen A, Smith with immunoglobulin, constitutes 80 % of all
NK, Tasker IR (1996) Thermodynamic properties and plasma proteins. In addition to plasma, HSA is
ideal-gas enthalpies of formation for cyclohexene, also found in tissues and bodily secretions
phthalan (2,5-dihydrobenzo-3,4-furan), isoxazole,
octylamine, dioctylamine, trioctylamine, phenyl throughout the body. It has several physiological
isocyanate, and 1,4,5,6-tetrahydropyrimidine. J Chem functions in vivo, which contribute signicantly
Eng Data 41:1269-1284 to colloid osmotic blood pressure and aid in the
Sun PP, Lee MS (2011) Separation of Pt(IV) and Pd transport, distribution, and metabolism of many
(II) from the loaded Alamine 336 by stripping. Hydro-
metallurgy 109:181184 endogenous and exogenous substances (He and
Tamada JA, Kertes AS, King CJ (1990) Extraction of Carter 1992). The ethyl alcohol fractionation is
carboxylic acids with amine extractants. Ind Eng the oldest process of industrial fractionation of
Chem Res 29:13191326 blood proteins but it cannot produce sufciently
Tasker PA, Plieger PG, West LC (2003) Metal
complexes for hydrometallurgy and extraction. In: pure albumin (Stotz et al. 1990). Of all purica-
McCleverty JA, Meyer TJ (eds) Comprehensive coor- tion methods, chromatography may be the best
dination chemistry II, vol 9. Elsevier: Oxford, UK,. candidate for minimizing process-generated albu-
pp 759808 min heterogeneity. Afnity chromatography is a
Yordanov B, Boyadzhiev L (2004) Pertraction of citric acid
by means of emulsion liquid membranes. J Membr Sci well-established method for the purication of
238:191197 proteins, and it is based on highly specic molec-
Zhu Y, Cao M, Ma X, Xu C, Wang X, Ren L, Hu C (2012) ular recognition. Conventional packed-bed col-
Dalton Trans 41(10):293540 umn chromatography is often limited by long
processing times due to low ow-rates, which
result from the high pressure drop (Denizli
et al. 1999). In order to overcome these opera-
tional limitations, microporous membrane
adsorbers have been developed (Ghosh 2002).
Alamine 3365 Microporous membranes as a support for chroma-
tography have several potential advantages.
Alamine 336 A conguration in which the feed solution ows
44 Alcohol and Water Separation

Albumin Purification with Affinity Membranes, Table 1 Albumin adsorption capacities for various membrane
affinity adsorbents
Adsorbent Ligand Ligand loading Qmax References
Polyethylene hollow ber CB F3GA 52 mmol/mL 6.5 mg/mL (Wolman et al. 2000)
PTFE membrane CB F3GA 89.8 mmol/g 85.3 mg/g (Gu et al. 2007)
P(GMA-DMAA) hollow ber CB F3GA 117 mmol/g 15.3 mg/mL (Wolman et al. 2005)
Polyamide hollow ber R. Green HE4BD 39.4 mmol/g 86.7 mg/g (Yavuz and Denizli 2004)
PTFE membrane CB F3GA/Zn2+ not reported 198.5 mg/g (Gu et al. 2007)
Polyamide hollow ber Cu2+ 150 mmol/g 226.0 mg/g (Uzun and Denizli 2002)
Ni2+ 250 mmol/g 289.0 mg/g (Uzun and Denizli 2002)
Co2+ 250 mmol/g 195.0 mg/g (Uzun and Denizli 2002)

through the membrane provides a very short, wide (EGDMA-HEMA) microbeads. J Appl Polym Sci
bed; thus, high velocities and very short residence 74:28032810
Ghosh J (2002) Protein separation using membrane chroma-
times are attainable with modest transmembrane tography: opportunities and challenges. J Chromatogr
pressure drops. Elimination of diffusional resis- A 952:327
tance usually leaves a system controlled by much Gu J, Lei Z, Qizhi Y (2007) Novel method for human
faster binding kinetics, thereby enabling adsorp- serum albumin adsorption/separation from aqueous
solutions and human plasma with Cibacron Blue
tive separation of proteins, typically, one-tenth the F3GA-Zn(II) attached microporous afnity membra-
time common for packed columns. Adsorptive nous capillaries. J Membr Sci 287:271279
membranes exhibit high binding capacities simi- He XM, Carter DC (1992) Atomic structure and chemistry
lar in magnitude to packed columns and using of human serum albumin. Nature 358:209215
Stotz JF, Rivat C, Geschier C, Colosett P, Streiff F (1990)
stepwise elution, proteins can rapidly be concen- Chromatography purication of a high purity human
trated tenfold or more with 85100 % recovery. plasmatic albumin for clinical or biological uses. Swiss
Analytical separations equivalent to those of col- Biotechnol 8:710
umn chromatography are reached by using suf- Uzun L, Denizli A (2002) Metal-chelated polyamide hol-
low bres for human serum albumin separation. J Appl
cient numbers of membrane stacks and gradient Polym Sci 86:33463354
elution methods. The linear scalability of the Wolman FJ, Graselli M, Smolko EE, Cascone O (2000)
membrane systems further adds to the attractive- Preparation and characterisation of cibacron blue
ness of the technology. When dealing with vis- F3GA poly(ethylene) hollow-bre membranes.
Biotechnol Lett 22:14071411
cous mediums such as blood, mass transfer in a Wolman FJ, Smolko EE, Cascone O, Grasselli M (2005)
diffusive-transport mode is more efcient, where Improved hollow-bre membranes for dye-afnity
the liquid is made to ow tangentially past the chromatography. J Sep Sci 28:4551
membrane surface while the adsorbate diffuses Yavuz H, Denizli A (2004) Dye afnity hollow bers for
albumin purication. Macromol Biosci 4:8491
into the microporous membrane to meet the selec-
tive ligand immobilized there. Several ligands can
be used for the afnity separation of albumin as
summarized in Table 1. Alcohol and Water Separation

Tadashi Uragami
Organization for Research and Development of
References Innovative Science and Technology (ORDIST),
Kansai University, Suita, Osaka, Japan
Ancell H (1839) Course of lectures on the physiology and
pathology of the blood and other animal uids. Lancet
1:222230
Cross-linked poly(vinyl alcohol) (PVA) composite
Denizli A, Kkturk G, Yavuz H, Pikin E (1999) Dye
ligand column chromatography: albumin adsorption membranes have been used in commercial PV
from aqueous media and human plasma with poly plants for dehydration of ethanol beyond the
Alcohol and Water Separation 45

azeotrope. However aqueous ethanol solutions that permeate through a poly(dimethylsiloxane)


can be produced by bio-fermentation are dilute (PDMS) membrane during PV and that sorbed
(about 10 wt.%). Therefore, if ethanol/water- into a PDMS membrane. These results support A
selective membranes with high efciency can be the hypothesis that the difference in the solubility
prepared, the distillation process in the rst stage to of the permeants contributes to the ethanol/water
obtain an azeotrope can be replaced ethanol-/ selectivity. PDMS membranes show high ethanol/
water-selective membrane which is very advanta- water selectivity, but their mechanical strength is
geous for reduction of energy cost. There are fewer weak, and it is difcult to prepare thin membranes
reports on ethanol-/water-selective membranes from PDMS. In order to obtain both ethanol/water
compared with those of water-/ethanol-selective selectivity and mechanical strength, graft copoly-
membranes. One reason why the development mers composed of PDMS macromonomer and
of efcient high-performance ethanol-/water- vinyl monomers were synthesized.
selective membranes is difcult can be attributed Graft copolymer membranes, which were
to the fact that ethanol has a larger molecular size either ethanol or water selective, were prepared
than water and must be preferentially permeated by copolymerization of a dimethylsiloxane
through the membrane. In fact, permeation and (DMS) macromonomer with methyl methacrylate
separation in a pervaporation (PV) process through (MMA) (Miyata et al. 1995, 1996). Two glass
dense membranes are based on the solution- transition temperatures (Tg) were observed at
diffusion mechanism (Binding et al. 1961; Aptel about 120  C and 127  C in the graft copolymer
et al. 1974). Therefore, when it is required that membranes. Transmission electron micrograph
ethanol molecules with larger molecular size pref- (TEM) demonstrated that the PMMA-g-PDMS
erentially permeate from an aqueous ethanol solu- membranes showed microphase-separated struc-
tion, it cannot be expected to be separated by the tures. When an aqueous solution of 10 wt.% eth-
diffusion process. Consequently, only a difference anol was permeated through the PMMA-g-PDMS
of solubility selectivity in the solution process in membranes by PV, the ethanol concentration in
which both ethanol and water components are the permeate and the permeation rate increased
dissolved can contribute to the separation. drastically with the DMS content in the copoly-
Figure 1 shows the ethanol concentration in the mer. In particular, at a DMS content of less than

100 100

ve
cur
EtOH in membrane (wt%)

80 80
EtOH in permeate (wt%)

ibrium
equl
id
or-liqu
vap
60 60

40 40

20 20

0
0 20 40 60 80 100
EtOH in feed solution (wt%) Alcohol and Water Separation, Fig. 2 Effects of the
DMS content on the normalized permeation rate () and
Alcohol and Water Separation, Fig. 1 Permeation and separation factor () through the PMMA-g-PDMS mem-
separation characteristics of aqueous ethanol solutions brane during PV. Feed: aqueous solution of 10 wt.% etha-
through a PDMS membrane during PV nol. Dashed line is the feed composition
46 Alcohol and Water Separation

Alcohol and Water Separation, Table 1 Performance of ethanol-/water-selective membranes


Feed Applied NPRa
(wt temperature aEtOH/ (kgmm
Membrane %) Method ( C) H2O (m2h)1) References
PDMS 7 PV 25 11.8 2.1 Eustache and Histi (1981)
PTMSP 7 PV 25 11.2 1.1 Ishihara et al. (1986)
PTMSP 10 PV 30 12 4.5 Masuda et al. (1986)
PEA-g-PDMS/ 10 PV 40 20 24.1 Uragami et al. (2000);
PTMSPb Uragami and Shinomiya
(1991)
PPP-g-PDMS 7.28 PV 30 22.5 5.5 Nagase et al. (1989)
PSt-g-PhdFDA (7.6/ 8 PV 30 45.9 0.6 Ishihara and Matsui (1987)
12.4)
TFE/i-OcVE/C18VE 15 PV 50 7.13 5 Kashiwagi et al. (1988)
terpolymer (50/25/25)
Modied silicone 10 PV 40 3.65 11 Uragami and Shinomiya
(1991)
Modied silicone 10 TDEV 30/40 19.3 16.6 Miyata et al. (1996)
PDMS 10 PV 40 7.44 6.4 Miyata et al. (1995, 1996)
PDMS 10 TDEV 30/40 85.7 0.9 Uragami and
Shinomiya (1992)
PMMA-g-PDMS 10 PV 40 7.1 4.8 Miyata et al. (1996)
(34/66)
PMMA-g-PDMS 10 PV 40 8 5.1 Miyata et al. (1999a)
(27/73)
PMMA-g-PDMS 10 PV 40 6.8 3.5 Miyata et al. (1999b)
(38/62)c
PTMST 10 TDEV 0/40 77.5 38 Uragami (2010)
Porous PDMS 10 TDEV 0.5 23.1 1,250 Uragami (2008)
a
Normalized permeation rate
b
PFA-g-PDMS is 0.2 wt.%
c
Annealing is 120  C, 2 h

40 mol%, water permeates preferentially from an In Table 1, the performance of the ethanol-/
aqueous solution of 10 wt.% ethanol, whereas water-selective polymer membranes is compared.
membranes with more than about 40 mol% of As can be seen in this Table, the addition of
DMS are ethanol/water selective, as shown in PFA-g-PDMS to the PTMSP membrane in PV
Fig. 2. The change in the ethanol/water selectivity was very effective, the application of TDEV
of the PMMA-g-PDMS membranes can be method to the membrane separation technique
explained by a microphase-separated polymer was also very interesting for the enhancement of
structure using Maxwells model and a combined the ethanol/water selectivity for the ethanol/water
model consisting of both parallel and series expres- mixtures, and in particular the application of
sions. Furthermore, image processing of TEMs porous PDMS membrane to temperature-
allowed the determination of the percolation tran- difference controlled evapomeation (TDEV)
sition of the PDMS phase at a DMS content of (Uragami 1998, 2005, 2006a, b, 2008, 2010,
about 40 mol%. These results suggest that the con- 2011; Uragami and Shinomiya 1991, 1992;
tinuity of the PDMS phases in the microphase- Uragami and Tanaka 1991, 1993, 1994; Uragami
separated PMMA-g-PDMS membranes directly et al. 2002; Uragami and Morikawa 1989) was a
affects their ethanol/water selectivity for aqueous very excellent performance for the ethanol/water
ethanol solutions (Miyata et al. 1995, 1996). mixtures.
Alcohol and Water Separation 47

References Uragami T (1998) Structures and properties of membranes


from polysaccharide derivatives. In: Dumitriu S (ed)
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Liquid transport through membranes prepared by satility. Marcer Dekker, New York/Basel/Hong Kong, A
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Eustache H, Histi G (1981) Separation of aqueous organic tin and chitosan. In: Uragami T, Tokura S (eds) Material
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Miyata T, Takagi T, Uragami T (1996) Microphase sepa- World Filtration Congress & Exhibition, p 313
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oligodimethylsiloxanes and their permselectivity for through polydimethyl siloxane membranes using
aqueous ethanol solutions. Macromolecules 29:7787 temperature-difference in membrane process of the
Miyata T, Obata S, Uragami T (1999a) Morphological evapomeation method. Makromol Chem Rapid
effects of microphase separation on the permselectivity Commun 10:287
for aqueous ethanol solutions of block and graft copol- Uragami T, Morikawa T (1992) Permeation and separation
ymer membranes containing poly(dimethylsiloxane). characteristics of alcohol-water mixtures through
Macromolecules 32:3712 dimethylsiloxane membrane by pervaporation and
Miyata T, Obata S, Uragami T (1999b) Annealing effect of evapomeation. J Appl Polym Sci 44:2009
microphase-separated membranes containing poly Uragami T, Shinomiya H (1991) Concentration of aqueous
(dimethylsiloxane) on their permselectivity for aqueous alcoholic solutions through a modied silicone rubber
ethanol solutions. Macromolecules 32:8465 membrane by pervaporation and evapomeation.
Nagase Y, Mori S, Matsui K (1989) Chemical modication Makromol Chem 192:2293
of poly(substituted-acetylene). 4. Pervaporation of Uragami T, Tanaka Y (1991) Method of separating liquid
organic liquid water mixture through poly(1-phenyl- component from a solution containing two or more
1-propylene) polydimethylsiloxane graft copolymer liquid component. European Patent 0,346,739
membrane. J Appl Polym Sci 37:1259 Uragami T, Shinomiya H (1992) Concentration of aqueous
Uragami T (1993) Separation of aqueous organic liquid dimethyl sulfoxide solutions through a chitosan mem-
solutions through polymer membranes. Desalination brane by permeation with a temperature difference.
90:325 J Membr Sci J Membr Sci 7:183
48 Alcohol Removal by Membrane Operations

Uragami T, Tanaka Y (1993) Method of separating liquid of dilute alcohol solutions (excluding methanol).
component from a solution containing two or more Especially the use of selective membranes
liquid component. U.S. Patent 5,271,846
Uragami T, Tanaka Y (1994) Separation method for mixed for ethanol or n-butanol removal from dilute fer-
solutions. Japanese Patent 1,906,854 mentation broths has gained a lot of interest
Uragami T, Doi T, Miyata T (1999) Control of recently.
permselectivity with surface modications of poly
[1-(trimethylsilyl)-1-propyne] membranes. Inter
J Adhes Adhes 19:405
Uragami T, Doi T, Miyata T (2000) Pervaporation property Membrane Operations
of surface modied poly[1-(trimethylsilyl)-1propyne]
membranes. In: Pinnau I, Freeman BD (eds) Membrane The most used membrane operations for alcohol
formation and modication, ACS Symposium Series
744. American Chemical Society, Washington, DC, removal include separation techniques like ltra-
pp 263279 tion, membrane distillation (also known as mem-
Uragami T, Tanaka Y, Nishida S (2002) Permeation and brane evaporation), pertraction, pervaporation
separation under high temperature and high pressure (PV), and vapor permeation (VP). Micro-, nano-,
for ethanol/water vapors through cross-linked
quaternized chitosan composite membranes. Desalina- and ultraltration are used in solid-liquid separa-
tion 147:449 tions mainly as a pretreatment step prior to the
alcohol removal. In pertraction, the membrane is
placed between fermentation broth and extractant.
The membrane passes through the alcohol
enabling its extraction, while other components
Alcohol Removal by Membrane such as nutrients and intermediate products remain
Operations in the feed side. In pervaporation and vapor per-
meation, desired minor compounds from a feed
Johanna Niemist solution are diffused through the hydrophobic
Helsinki Region Chamber of Commerce, membrane and desorbed in the permeate side of
Enterprise Europe Network, Helsinki, Finland the membrane as a vapor which can then be con-
densed back to the liquid state by, e.g., a condenser
(Schfer and Crespo 2005). Feed solution is in a
Synonyms liquid phase in PV applications and in a vapor
phase in VP processes. The driving force, a chem-
Alcohol separation by Membrane Distillation ical potential difference of the compounds, is
(MD); Alcohol separation by Pertraction; Alcohol obtained by applying different partial vapor pres-
separation by Pervaporation (PV); Alcohol sepa- sures of compound(s) on the opposite sides of the
ration by Vapor permeation membrane: The feed side is under atmospheric
pressure, whereas vacuum or very low pressure
Biochemical, i.e., fermentative, production of is applied in the permeate side. Because only per-
alcohols and other solvents has been increasing meated compounds are evaporated in
signicantly in the last years. Recovery and puri- pervaporation, lower energy, capital, and
cation of alcohols from dilute aqueous solutions processing costs can be obtained as compared to
obtained after fermentative solvent production is other separation techniques.
energy intensive and expensive. For example,
conventional distillation is stated to be an efcient
alcohol separation technique for the ethanol in Membranes
concentration range from 10 to 85 wt.% (Huang
et al. 2008). The use of membrane operations is Membranes used in alcohol removal are hydro-
however seen as a more cost- and energy-efcient phobic, i.e., organophilic, having preferential per-
method over conventional distillation in the case meation for organic compounds instead of water.
Alcohol Separation by Membrane Distillation (MD) 49

Nonporous membranes are used in PV and VP concentration of around 92.4 wt% (below the
applications, while membrane distillation opera- azeotropic point), and further dehydration is
tions are performed with semipermeable porous done by other separation techniques including, A
membranes. The semipermeable polymeric mem- e.g., adsorption by molecular sieves. Especially,
branes used mostly are made of polydimethyl- pervaporation and vapor permeation are more
siloxane (PDMS). Other used materials include, energy-efcient and promising techniques, but
e.g., polyether block amide (PEBA), only a few number of pilot- or industrial-scale
polyoctylmethyl siloxane (POMS), polypropyl- facilities for alcohol separation are in use, despite
ene (PP), polytetrauoroethylene (PTFE), the active research going on in laboratory scale.
polytrimethylsilylpropyne (PTMSP), Hence, there is still need for research and devel-
polyvinylidene uoride (PVDF), and liquid mem- opment activities to obtain feasible industrial-
branes. Ceramic and zeolite membranes are also scale applications.
available. Composite membranes having a porous
support layer and a thin separation layer are
widely used due to better separation efciency Cross-References
and membrane stability. Besides a good chemical,
mechanical, and thermal stability, membranes Alcohol and Water Separation
should also have high ux and selectivity toward Butanol-Water Mixtures: Separation by
alcohols. Membrane modules can be in the form Pervaporation
of at sheets or plates, spiral wounds, envelopes, Ceramic Membranes
or (hollow) tubular modules (Bruschke 2001). Fouling in Membranes
Pervaporation (PV)
Polarization in Membrane Operations
Advantages and Disadvantages
References
Advantages of membrane operations include the
possibility to be used also in the case of azeotropic Br
uschke HEA (2001) State-of-the-art of pervaporation
mixtures and for the separation of volatile organic processes in the chemical industry. In: Nunes SP,
compounds. In addition, combining the mem- Peinemann K-V (eds) Membrane technology in the
brane operation with a fermentor as a hybrid pro- chemical industry, 1st edn. Wiley VCH Verlag GmbH
& Co, Weinheim, pp 127172
cess as in situ product removal (ISPR) enables Huang H-J, Ramaswamy S, Tschirner UW, Ramarao BV
obtaining an increased yield in fermentation and (2008) A review of separation technologies in current
more efcient separation efciency. Other hybrid and future bioreneries. Sep Purif Technol 62:121
processes are typically a membrane operation Schfer T, Crespo JG (2005) Vapor permeation and
pervaporation. In: Afonso CAM, Crespo JPG (eds)
combined with distillation or with other mem- Green separation processes: fundamentals and applica-
brane technique. The main disadvantage in the tions. Wiley VCH Verlag GmbH & Co, Weinheim,
operation is the fouling tendency of the membrane pp 271289
surface or of the pores inside the membrane, in Vane LM (2005) A review of pervaporation for product
recovery from biomass fermentation processes. J Chem
addition to concentration polarization. Fouling Technol Biotechnol 80:603629
can be reduced by improved membrane module
design or operating procedures (Vane 2005).

Industrial Applications Alcohol Separation by Membrane


Distillation (MD)
In commercial scale, ethanol is usually rst
dehydrated by distillation up to the ethanol Alcohol Removal by Membrane Operations
50 Alginate

necessary to have an aqueous solvent free of


Alginate cross-linking ions to enable dissolution. The sol-
ubility of alginates in organic media requires for-
Emma Piacentini mation of a tetrabutylammonium (TBA) salt. The
Institute on Membrane Technology, National solubility of alginates depends strongly on the
Research Council of Italy, ITM-CNR, Rende, state of the backbone carboxylic acid groups.
Italy Alginic acid with its carboxylic acid groups in
their protonated form was not fully soluble in
any solvent system examined, including water.
Alginates are unbranched anionic polysaccharides
Chemical modication or derivatization of
consisting of 1!4 linked b-D-mannuronic acid
alginates is used as a tool to attain one of two
(M) and its C-5 epimer a-L-guluronic acid
ends, i.e., (a) enhance existing properties (such
(G) (Fig. 1).
as improvement of ionic gel strength by additional
The natural copolymer is an important compo-
covalent cross-linking, increase hydrophobicity
nent of algae such as kelp and is also an
of the backbone, improve biodegradation, or
exopolysaccharide of bacteria including Pseudo-
achieve greater HAP nucleation and growth) or
monas aeruginosa. The copolymer composition,
(b) introduce completely new properties other-
sequence, and molecular weights vary with the
wise not existing in unmodied alginates (such
source and species that produce the copolymer.
as afford anticoagulant properties, provide chem-
The molecular weights of commercially available
ical/biochemical anchors to interact with cell sur-
sodium alginates range between 32,000 and
faces, or bestow temperature-dependent
400,000 g/mol. The viscosity of alginate solutions
characteristics such as lower critical solution tem-
increases as pH decreases and reaches a maximum
perature). Alginate derivatization (Pawar and
around pH 33.5, as carboxylate groups in the
Edgar 2012) includes acetylation, phosphoryla-
alginate backbone become protonated and form
tion, sulfation, hydrophobic modication, attach-
hydrogen bonds. The solubility of alginates in
ment of cell signaling molecules, covalent cross-
water is governed by three parameters, i.e.,
linking, and graft copolymerization. In particular,
(a) pH of the solvent, (b) ionic strength of the
amphiphilic alginate derivatives have been syn-
medium, and (c) the presence of gelling ions in
thesized by introducing hydrophobic moieties
the solvent. To make alginates soluble, it is essen-
(e.g., alkyl chains, hydrophobic polymers) to the
tial that the pH be above a certain critical value
alginate backbone. These derivatives can form
and the carboxylic acid groups be deprotonated.
self-assembled structures such as particles and
Changing the ionic strength of the medium affects
gels in aqueous media and have potential in
solution properties such as polymer conformation,
many drug delivery applications. Alginate deriv-
chain extension, viscosity, and therefore solubil-
atives containing cell-adhesive peptides have
ity. Alginates gel in the presence of divalent cat-
been gaining signicant attraction recently.
ions such as Ca2+, Sr2+, and Ba2+. It is therefore
These derivatives are typically prepared by chem-
ically introducing peptides as side chains, using
O
carbodiimide chemistry to couple via the carbox-
ylic groups of the sugar residues. Since alginate
HO C
inherently lacks mammalian cell adhesivity,
-D-mannuronic acid (M)
O OH appropriate ligands are crucial to promote and
HO O regulate cellular interactions, especially for cell
O O
O culture and tissue engineering applications. Pep-
HO C OH
OH tides including the sequence arginine-glycine-
O
-L-guluronic acid (G)
aspartic acid (RGD) have been extensively used
as model adhesion ligands, due to the widespread
Alginate, Fig. 1 Components of alginates presence of integrin receptors for this ligand on
Alginate 51

various cell types. RGD-containing peptides can produces more uniform structures and greater
be chemically coupled to the alginate backbone mechanical integrity. One critical drawback of
using water-soluble carbodiimide chemistry. ionically cross-linked alginate gels is the limited A
Alginate is typically used in the form of a long-term stability in physiological conditions,
hydrogel. Hydrogels are three-dimensionally because these gels can be dissolved due to release
cross-linked networks composed of hydrophilic of divalent ions into the surrounding media due to
polymers with high water content. Hydrogels are exchange reactions with monovalent cations and
often biocompatible, as they are structurally sim- the hemostasis promoted by the calcium ions
ilar to the macromolecular-based components in released from the gel that serves as a matrix for
the body, and can often be delivered into the body aggregation of platelets and erythrocytes. Cova-
via minimally invasive administration. Alginate lent cross-linking has been widely investigated in
chelates with divalent cations to form hydrogels. an effort to improve the physical properties of gels
Gel formation is driven by the interactions for many applications, including tissue engineer-
between G blocks which associate to form tightly ing. However, covalent cross-linking reagents
held junctions in the presence of divalent cations. may be toxic, and the unreacted chemicals may
In addition to G blocks, MG blocks also partici- need to be removed thoroughly from gels. The
pate, forming weak junctions. Thus, alginates inability to dissociate and reform bonds leads to
with high G contents yield stronger gels. signicant elastic deformation. Thermosensitive
Chemical and/or physical cross-linking of hydrogels have been widely investigated to date
hydrophilic polymers are typical approaches to in many drug delivery applications, due to their
form hydrogels, and their physicochemical prop- adjustable swelling properties in response to tem-
erties are highly dependent on the cross-linking perature changes, leading to on-demand modula-
type and cross-linking density, in addition to the tion of drug release from the gels. When alginate
molecular weight and chemical composition of is modied with cell adhesion ligands, the ability
the polymers. The most common method to of cells to bind multiple polymer chains can lead
prepare hydrogels from an aqueous alginate to long-distance, reversible network formation
solution is to combine the solution with ionic even in the absence of chemical cross-linking
cross-linking agents, such as divalent cations. agents. Cells added to an RGD-modied alginate
The afnity of alginates toward divalent solution form a uniform dispersion within the
ions decreases in the following order: solution, and this system subsequently generates
Pb > Cu > Cd > Ba > Sr > Ca >Co, Ni, the cross-linked network structure via specic
Zn > Mn. Ca2++; however, it is the most com- receptor-ligand interactions without using any
monly used cation to induce alginate gel forma- additional cross-linking molecules. In contrast,
tion. Calcium cross-linking of alginates can be cells added to non-modied alginate solutions
performed by two methods. The rst is a diffu- aggregate and form a nonuniform structure, due
sion method, wherein cross-linking ions diffuse to the dominance of cell-cell interactions in that
into the alginate solution from an outside reser- system. This gelation behavior is shear reversible
voir. The second is the internal setting method, and can be repeated multiple times. Once the gel
where the ion source is located within the alginate structure is broken down by applying shear forces,
solution and a controlled trigger (typically pH or cross-linked structures are recovered within a few
solubility of the ion source) sets off the release of minute. This behavior is governed by the weak
cross-linking ions into solution. Diffusion set gels and reversible ligand-receptor interactions in the
are typically made by dropping a Na-alginate system. This system might be ideal for cell deliv-
solution into a CaCl2 bath. Internal set gels typi- ery in tissue engineering because a gel can ow
cally use insoluble calcium salts such as CaCO3 as like a liquid during injection into the body but
a calcium source. The gelation rate is a critical solidify once it is placed in the body.
factor in controlling gel uniformity and strength Large pellets (greater than 1.0 mm in diameter)
when using divalent cations, and slower gelation are conventionally prepared using a simple
52 Aligned Carbon Nanotube

syringe or pipette. Droplets of sodium alginate The chemical and physical properties of algi-
solution are extruded into a divalent cross-linking nates resulted in many commercial applications
solution, and pellets formed are then allowed to (Goh et al. 2012; Lee and Mooney 2012):
cure in the cross-linking solution (varying from a
few minutes to hours), rinsed with water, and (i) Food and beverage industry (stabilizers,
air-dried. Micropellets (less than 0.2 mm in diam- thickeners in the preparation of drinks, ice
eter) can be prepared using atomization, emulsi- cream, and jelly; encapsulation material of
cation, and coacervation methods. yeast cells in ethanol production)
Polysaccharides undergo hydrolytic cleavage (ii) Pharmaceutical industry (encapsulation
under acidic conditions. The mechanism of acid material in cell culture and transplantation,
hydrolysis of the glycosidic bond involves three mold in dental impression material,
steps: (1) protonation of the glycosidic oxygen to adhesive agent and sustained release in tab-
give the conjugate acid; (2) heterolysis of the lets, hemostatic and absorbent in wound
conjugate acid forming a nonreducing end group dressing
and a carbonium-oxonium ion; and (3) rapid addi- (iii) Other industries (adhesive agent and ller in
tion of water to the carbonium-oxonium ion, paper industry, stabilizer and suspending
forming a reducing end group. The enzymatic agent in paint industry)
degradation of alginates by lyase occurs by a
b-elimination mechanism resulting in unsaturated
compounds. The mechanism of b-elimination References
involves abstraction of the proton at the C-5 posi-
tion, which is enhanced by the electron- Goh CH, Heng PWS, Chan LW (2012) Alginates as a
useful natural polymer for microencapsulation and
withdrawing effect of the carbonyl group at C-6
therapeutic applications. Carbohydr Polym 88:112
position. Alginates chain degradation can occur Lee KY, Mooney DJ (2012) Alginate: properties
also at neutral pH values in the presence of reduc- and biomedical applications. Prog Polym Sci
ing compounds such as hydroquinone, sodium 37:106126
Pawar SN, Edgar KJ (2012) Alginate derivatization: a
sulte, sodium hydrogen sulde, cysteine,
review of chemistry, properties and applications. Bio-
ascorbic acid, hydrazine sulfate, and leuco- materials 33:32793305
methylene blue that also caused degradation in
alginates. The mechanism of degradation involves
the formation of a peroxide leading to free radical
creation, which eventually causes breakdown of
the alginate chain. Aligned Carbon Nanotube
Alginate is inherently nondegradable in mam-
mals, as they lack the enzyme (i.e., alginase) Cameron Shearer
which can cleave the polymer chains, but School of Chemical and Physical Sciences,
ionically cross-linked alginate gels can be Flinders University, Adelaide, South Australia,
dissolved by release of the divalent ions cross- Australia
linking the gel into the surrounding media due to Institute of Physical Chemistry, University of
exchange reactions with monovalent cations such Muenster, Muenster, North RhineWestphalia,
as sodium ions. An attractive approach to make Germany
alginate degradable in physiological conditions
includes partial oxidation of alginate chains.
Slightly oxidized alginate can degrade in aqueous
media, and these materials have demonstrated Synonyms
potential as a delivery vehicle of drugs and cells
for various applications. Alginate is typically oxi- A-CNT; Horizontally aligned carbon nanotube;
dized with sodium periodate. Vertically aligned carbon nanotube
Aligned Carbon Nanotube 53

Main Text et al. 2008). Horizontal CNTs can form a dense,


exible, stable mat (called a bucky paper) which
Carbon nanotubes (CNTs) are allotropes of car- can potentially be used as a membrane as the space A
bon in which the carbon atoms form a hexagonal between the CNTs is generally quite small
sheet of sp2 bonds (analogous to graphite) which (<50 nm) (Dume et al. 2010; Sears et al. 2010).
is seamlessly rolled up into a cylinder that can be Vertically aligned CNTs can be prepared via
microns long but is only nanometers in diameter the CVD growth of CNTs on pre-patterned sub-
(Yamamoto et al. 2008). Following typical syn- strate supported catalyst nanoparticles. Verti-
thesis procedures, CNTs exist as a tangled web of cally aligned CNTs produced via this method
randomly oriented bers. For many applications, have been grown greater than 1 mm in length
the CNTs are required to be aligned with either (Joselevich et al. 2008). Alignment is enhanced
horizontal or vertical alignment (Fig. 1). via the use of a strong electric eld such as in
Horizontally aligned CNTs are of particular plasma-enhanced CVD. Vertical alignment is of
importance in the generation of eld effect transis- importance in the elds of eld emission, chem-
tors and conductive wires based upon CNTs. CNTs ical sensing, and CNT nanoltration mem-
can be horizontally aligned via a range of processes branes (Endo et al. 2008; Shearer et al. 2012).
including spin coating, ltering, magnetic eld CNT nanoltration membranes are of particular
alignment, and drying-induced and chemical interest as molecular dynamics simulations have
vapor deposition (CVD) (Dai 2001; Joselevich shown that water can ow through CNTs at a

Aligned Carbon Nanotube, Fig. 1 SEM image CNTs produced via CVD showing (a) randomly entangled, (b)
horizontally aligned, and (c) vertically aligned
54 Alkaline Fuel Cells (AFCs)

remarkable rate (Hummer et al. 2001), while the


ow of contaminates is restricted by the nano- Alkaline Fuel Cells (AFCs)
size of the CNT inner pore ( 1 nm). The fabri-
cation of such a membrane required vertically Tanja Vidakovic-Koch
aligned CNTs, encased within an impermeable Max Planck Institute for Dynamics of Complex
matrix such that ow can only occur through the Technical Systems, Magdeburg, Germany
CNT inner pore. This is experimentally quite
difcult, but a few reports with promising
results have been published (Majumder Alkaline fuel cell (AFC) is a fuel cell type which
et al. 2005; Holt et al. 2006; Wu et al. 2010). utilizes alkaline electrolyte, usually potassium
hydroxide. It consumes hydrogen and oxygen
producing only water, heat, and electricity.
Depending on a concentration of potassium
References hydroxide, AFC can operate at temperatures
between 60  C and 250  C. The fuel cell reactions
Dai H (2001) Nanotube growth and characterization. In: are as follows:
Dresselhaus MS, Dresselhaus G, Avouris P (eds) Car-
bon nanotubes, topics in applied physics. Springer-
Verlag, Berlin, pp 2953 Anode : H2 2OH 2H2 O 2e
Dume LF, Sears K, Sch utz J et al (2010) Characterization
and evaluation of carbon nanotube bucky-paper mem-
branes for direct contact membrane distillation.
Cathode : 12 O2 2e 2H2 O 2OH
J Membr Sci 351(12):3643
Endo M, Strano M, Ajayan P (2008) Potential applications Overall reaction : H2 12 O2 H2 O
of carbon nanotubes. In: Jorio A, Dresselhaus G,
Dresselhaus MS (eds) Topics in applied physics: car-
bon nanotubes. Springer, Berlin, pp 1361 The main ionic charge carriers are OH ions
Holt J, Park H, Wang Y et al (2006) Fast mass transport which mitigate from the cathode to the anode.
through sub-2-nanometer carbon nanotubes. Science
312:1034 Water is formed at the anode side and has to be
Hummer G, Rasaiah JC, Noworyta JP (2001) Water con- removed from the system in order to prevent KOH
duction through the hydrophobic channel of a carbon dilution. The AFC has improved cathode perfor-
nanotube. Nature 414(6860):188190 mance compared to acidic fuel cells due to more
Joselevich E, Dai H, Liu J et al (2008) Carbon nanotube
synthesis and organization. In: Jorio A, Dresselhaus G, favorable oxygen reduction reaction kinetics. For
Dresselhaus MS (eds) Carbon nanotubes, topics in this reason, AFC can achieve higher efciency,
applied physics. Springer-Verlag, Berlin, pp 101164 i.e., higher voltage at comparable current densities
Majumder M, Chopra N, Andrews R, Hinds BJ than other fuel cell types. It has very long operat-
(2005) Enhanced ow in carbon nanotubes. Nature
438:44 ing life time, e.g., 15,000 h have been demon-
Sears K, Dume L, Sch utz J et al (2010) Recent develop- strated (Cifrain and Kordesch 2003).
ments in carbon nanotube membranes for water puri- Furthermore, alkaline conditions allow applica-
cation and gas separation. Mater Lett 3(1):127149 tion of nonprecious metal catalysts which could
Shearer C, Fahy A, Barr M et al (2012) Improved eld
emission stability from single-walled carbon nanotubes reduce signicantly the material costs of this fuel
chemically attached to silicon. Nanoscale Res Lett cell. One of major disadvantages of AFC is its low
7(1):432 CO2 tolerance due to formation of carbonates
Wu J, Paudel KS, Strasinger C et al (2010) Programmable according to:
transdermal drug delivery of nicotine using carbon
nanotube membranes. Proc Natl Acad Sci
107(26):1169811702
Yamamoto T, Watanabe K, Hernndez E (2008) Mechan- CO2 2OH CO3 2 H2 O
ical properties, thermal stability and heat transport in
carbon nanotubes. In: Jorio A, Dresselhaus G,
Dresselhaus MS (eds) Carbon nanotubes. Springer, The carbonates have low solubility in strong alka-
Berlin, pp 165194 line environments forming crystals, capable of
Alkane and Alkene Separation by Membrane Operations 55

blocking of electrolyte pathways. The low CO2


tolerance and the application of liquid electrolyte Alkane and Alkene Separation by
are two main hurdles for the broader commercial- Membrane Operations A
ization of these systems. However, due to its high
efciency and high power density, AFC found Chen Zhang
applications in aerospace industry, e.g., they School of Chemical and Biomolecular
were employed on the Apollo missions as well Engineering, Atlanta, GA, USA
as on the Space Shuttle orbitals. For other
examples of developed AFC systems, please
see Cifrain and Kordesch (2003) and Alkenes (e.g., ethene, propene, butadiene, and
Gulzow (2012). butenes isomers) are extremely important building
Hydrogen and oxygen gases in the AFC are blocks in petrochemical industries with many
separated by a membrane. Usually permeable derived chemicals and polymers. Traditionally,
membranes also called diaphragms have been alkenes are recovered from alkene/alkane
used (G ulzow 2012). A common diaphragm mixtures produced by cracking hydrocarbon feed-
material up to 1980s was asbestos which due to stocks (e.g., ethane, LPGs, and naphtha). Alkene/
health and environmental concerns is nowadays alkane separations (e.g., separation of ethene/eth-
abandoned. Alternative materials are different ane, propene/propane, and butadiene/crude C4) are
polymer materials like porous polyethylene traditionally performed on a massive scale by dis-
plates, nonwoven polypropylene, and similar. tillation, which are extremely energy intensive due
Potassium hydroxide electrolyte wets the dia- to these components close volatilities. For exam-
phragm pores in order to ensure its ionic conduc- ple, propene/propane separation was credited to be
tivity. For a good fuel cell performance, the the most energy intensive commercially practiced
electrolyte resistance induced by diaphragm has distillation (Jarvelin and Fair 1993).
to be minimized. This resistance is inuenced by Membrane gas separations, among other com-
the thickness of the diaphragm material, its pore peting alternatives (i.e., adsorptive separation and
size and tortuosity, and the KOH concentration. chemical absorption), can be used to either retrot
Since liquid electrolyte causes some practical or replace existing distillation columns to make
problems in AFC usage, new developments go commercial alkene/alkane separations more
into direction of alkaline polymer electrolyte energy efcient. Compared with well-developed
membranes which, in addition to separation, membrane gas separations such as air separation,
possesses ionic conductivity in the absence of membrane-based alkene/alkane separation is
liquid electrolyte. Currently there is no long-term more challenging. The feeds are highly condens-
stable membrane functioning without a liquid able and usually under high pressure (or in liquid
electrolyte phase. state), requiring that membrane materials must be
sufciently robust without being plasticized.
Among alkene/alkane separations, ethene/ethane
and propene/propane are most extensively studied
References with membranes. Conversely, membranes are less
commonly considered for separations of C4 and
Cifrain M, Kordesch K (2003) Hydrogen/oxygen (Air) fuel heavier alkene/alkane mixtures due to their much
cells with alkaline electrolytes. In: Vielstich W,
Gasteiger HA, Lamm A (eds) Handbook of fuel cells-
lower diffusivities and correspondingly unattrac-
fundamentals, technology and applications, tive productivities. Membrane separations are
vol 1, Fundamentals and survey of systems. Wiley, based on differences in how fast the penetrants
Chichester, pp 267280 diffuse through the membrane (i.e., diffusion
Gulzow E (2012) Alkaline fuel cells. In: Stolten D, Emonts
selectivity) and/or how much they sorb in the
B (eds) Fuel cell science and engineering: materials,
processes, systems and technology, vol 1. Wiley-VCH, membrane (i.e., sorption selectivity). For exam-
Weinheim, pp 97129 ple, propene molecule is slimmer than propane
56 Alkane Oxidative Dehydrogenation by Membrane Reactor

molecule. Remarkable propene/propane diffusion separations (Faiz and Li 2012). Alkene transport
selectivity is possible for materials with rigid in such membranes is assisted by carriers
structures and properly tailored ultramicropores. (e.g., Ag+ ions) that reversibly react with alkenes
Additionally, propene is slightly polar and a lim- through p-complexation. Amazing alkene perme-
ited (<10) propene/propane sorption selectivity ability and alkene/alkane selectivity can be
may be achieved with polar materials (e.g., cat- achieved in facilitated transport membranes at
ionic zeolites with high Al/Si ratio). the same time. Nevertheless, the carriers may be
Membranes for alkene/alkane separations can irreversibly deactivated by certain impurities
be categorized into two classes: membrane sepa- (e.g., hydrogen, hydrogen sulde, and acetylenes)
rations based on sorption-diffusion and others in the feed, resulting in permanent loss in both
based on facilitated transport. The majority of alkene permeability and alkene/alkane selectivity.
membranes in the rst category achieve the sepa- While in some cases membrane performance may
ration relying on diffusion selectivity. Polymer be partially recovered by periodically recharging
membranes, despite their excellent scalability, the carrier, such approach may not be practical for
are incapable of offering attractive alkene/alkane large-scale applications.
selectivity without signicantly compromising
their permeability due to the permeability-
selectivity trade-off (Burns and Koros 2003). References
Additionally, uncrosslinked polymer membranes
may be plasticized with high-pressure alkene/ Adams R, Johnson JR, Zhang C, Lively RP, Dai Y,
Esekhile O, Liu J, Koros WJ (2013) Preparation of
alkane feeds, resulting in signicant selectivity
mixed matrix membranes. In: Hoek EMV, Tarabara
loss. On the other hand, membranes derived VV (eds) Encyclopedia of membrane science and tech-
from more rigid molecular sieving materials nology. Wiley, New York, pp 398430
(e.g., zeolites, metal-organic frameworks Burns RL, Koros WJ (2003) Dening the challenges for
C3H6/C3H8 separation using polymeric membranes.
[MOFs], zeolitic imidazolate frameworks [ZIFs],
J Membr Sci 211:299309
and carbon molecular sieves [CMS]) can offer Faiz R, Li K (2012) Olen/parafn separation using mem-
simultaneously high permeability and selectivity. brane based facilitated transport/chemical absorption
However, fabrication of molecular sieve mem- techniques. Chem Eng Sci 72:261284
Jarvelin H, Fair JR (1993) Adsorptive separation of propylene-
branes is usually difcult and many technical
propane mixtures. Ind Eng Chem Res 32:22012207
challenges must be solved to deliver such perfor- Zhang C, Zhang K, Xu L, Labreche Y, Kraftschik B, Koros
mance economically on a large scale. Among WJ (2014) Highly scalable ZIF-based mixed-matrix
molecular sieve membranes, CMS membrane is hollow ber membranes for advanced hydrocarbon
separations. AIChE J 60:26252635
the most promising as it can be conveniently
realized in the scalable hollow ber geometry by
pyrolyzing polymer precursor hollow bers.
A compromise to address the limitations of both
polymer membrane and molecular sieve mem- Alkane Oxidative Dehydrogenation
brane is mixed-matrix membrane (Adams by Membrane Reactor
et al. 2013), which are formed by dispersing
molecular sieve particles/platelets in polymer Miguel Menendez
matrices. Selectivity and/or permeability of Department of Chemical and Environmental
mixed-matrix membranes may be substantially Engineering, University of Zaragoza, Zaragoza,
enhanced over the polymer matrices and in the Spain
meantime, the membrane can still be inexpen-
sively processed into hollow bers (Zhang
et al. 2014). Alkanes are converted to olens in the chemical
Facilitated transport membrane is another class industry because of the high demand of polyole-
of membrane studied for alkene/alkane ns, such as polypropylene or polybutadiene, and
Alkane Oxidative Dehydrogenation by Membrane Reactor 57

Alkane Oxidative
Dehydrogenation by
Membrane Reactor,
Fig. 1 Scheme of a A
membrane reactor for the
selective oxidation of
hydrocarbons with a
distributed feed of oxygen

also because olens are the starting materials for distributes oxygen along a packed bed of catalyst.
many other chemicals. These reactions can be This improvement is based on the favorable effect
represented as of low oxygen partial pressure on the selectivity.
In fact, for many catalysts the observed
Cn H2n2 ! Cn H2n H2 reaction order respect to oxygen for the above
reaction is lower than for the formation of CO
A common characteristic of these reactions is the and CO2. This observation implies that low partial
achievable conversion being limited by thermo- pressure of oxygen increases the selectivity to
dynamic equilibrium. Two options to increase the olens.
conversion are This general principle has been applied for the
oxidative dehydrogenation of ethane, propane,
Using a membrane reactor where H2 is and butane, with successful results in all cases
removed from the reactor. This will increase (Coronas and Santamara 1999). Details of the
the achievable conversion according to the results obtained with membrane reactors with pro-
Le Chaterliers principle. Any material which pane and butane (oxidative dehydrogenation and
can remove hydrogen selectively can be used, oxidation to maleic anhydride) are described in
but Pd and Pd alloys are the most employed. specic chapters.
The preparation of this kind of membranes A general scheme of a membrane reactor for
has been widely described (Basile and Gallucci this kind of reactions is shown in Fig. 1.
2011). The oxygen containing feed is usually intro-
Adding an oxidizing agent (e.g., oxygen) to the duced through the shell side. A porous membrane
reaction, in order to form water instead of distributes this oxygen along the catalyst bed,
hydrogen, the resulting reaction would be: keeping a low partial pressure of oxygen in all
the beds. A feed containing the hydrocarbon is fed
Cn H2n2 1=2 O2 ! Cn H2n H2 O to the tube side, i.e., to the catalyst bed. The
reaction products are removed at the exit of the
This approach has the advantage of being ther- catalyst bed.
modynamically favored but has the problem that As an alternative to porous membranes, dense
simultaneous formation of carbon oxides reduces ceramic membranes can provide an additional
the selectivity. advantage: the separation of oxygen-nitrogen
A way to improve the selectivity is to use a mixtures (Hashim et al. 2011). This would
membrane reactor, where the membrane decrease the cost of oxygen separation.
58 Alumina Membranes

References membrane cost, making it about one order of


magnitude higher than its polymeric counterparts.
Basile A, Gallucci F (eds) (2011) Membranes for mem- However, because of much longer lifetimes and
brane reactors. Preparation, optimization and selection.
higher uxes of alumina membranes, the long-
Wiley, Chichester
Coronas J, Santamara J (1999) Catalytic reactors based on term operating cost of alumina membrane plants
porous ceramic membranes. Catal Today 51:377389 is comparable with polymeric membrane plants,
Hashim SS, Mohamed AR, Bhatia S (2011) Oxygen sep- no mention there are many scenarios in which
aration from air using ceramic-based membrane tech-
only alumina/ceramic membranes can be used.
nology for sustainable fuel production and power
generation. Renew Sustain Energy Rev 15:12841293

Membrane Designs and Fabrication

Alumina Membranes Most alumina membranes use asymmetric mem-


brane architectures. Coarse alumina particles are
Bo Wang used for the supporting layer to provide mechan-
Department of Chemical Engineering, Imperial ical strength, and the transport resistance in this
College London, London, UK layer is usually low due to its big pore size; ne
alumina particles are coated on top of the support
to form a thin separating layer to reach desired
Alumina membranes are membranes made of pore sizes and high uxes; and depending on the
high-purity (mostly >97 %) aluminum oxides pore size difference between the top and the
(alumina). They belong to the categories of supporting layer, one or few transition layers
ceramic membranes and in most cases, might be used between the top and supporting
microltration and ultraltration membranes. layers to avoid coating defects and to increase
Pure alumina membranes are predominant in all adhesion between layers.
kinds of commercial ceramic membranes, and Alumina membranes may adopt a tubular
most other commercial ceramic membranes, if shape, plate shape, or monolithic multichannel
using other materials as the separation coating, design. The latest is the most commonly used
are based on alumina membrane support. design in industry because it provides higher
membrane area per unit volume, therefore reduces
the size of the separation plant and operating
Advantages and Disadvantages costs. Some commercial products can achieve an
area to volume ratio of 800 m2/m3 with the mono-
Alumina membranes are chemically inert and lithic design, which is comparable with spiral
mechanically strong, and also thermally stable, wound polymeric membrane modules.
therefore they can be used under very harsh con- Fabrication of alumina membranes usually
ditions such as aggressive chemical environments involves several forming and sintering steps due
and elevated temperatures, making them versatile to their multilayer asymmetric membrane archi-
in various industrial processes. Their strong tectures, and the total production process is often
mechanical properties allow them to be operated longer than 1 week. The supporting layer can be
under high pressures and high feed ow rates to formed by extrusion (for tubular or monolith
achieve high productivity and to tolerate high designs) or by pressing (for plate or disk designs),
solid contents in the feed. followed by partial sintering at a high temperature
The high fabrication cost is a major obstacle for (up to 1600  C) to achieve a high strength and
alumina membranes to expand its market share. porous structures. Transition layers and the top
Although alumina is widely available, the com- layer then can be coated on the support, also
plicated fabrication process and high energy con- followed by sintering after each coating.
sumption for sintering lift signicantly the total Depending on the pore size, two types of alumina
Americium Separation by Membrane Operation 59

could be used for the top layer coating: for Ebrahimi M, Willershausen D, Ashaghi KS, Engel L,
microltration membranes whose pore size is Placido L, Mund P, Bolduan P, Czermak P (2010)
Investigations on the use of different ceramic mem-
larger than 100 nm, a-alumina is used; for ultra- branes for efcient oil-eld produced water treatment. A
ltration membranes whose pore size is smaller Desalination 250(3):991996
than 100 nm, g-alumina or a mixture of a and g
types are often used.
There are also other fabrication techniques that
can produce unique alumina membranes, for
example, the anodic alumina membranes that Aluminum (III) Oxide Porous
have straight cylindrical pores and asymmetric Membranes or Alumina Porous
alumina membranes made by single-step phase Membranes
inversion/sintering methods. These membranes
have shown good potential in ltration but have Al2O3 Porous Membranes
not been widely accepted as a feasible replace-
ment of conventional alumina membranes yet.

Americium Separation by Membrane


Applications Operation

Alumina membranes are widely used in water and P. K. Mohapatra


wastewater treatment, pharmaceuticals, food Radiochemistry Division, Bhabha Atomic
processing, chemical processing, and others. Pro- Research Centre, Mumbai, Maharashtra, India
duction of drinking water and wastewater treat-
ment are the most important applications, which
occupy about half of the market share of alumina Americium (Am) is the rst among the trans-
membranes. The stable pore structure of alumina plutonium elements, produced in nuclear reactors
membranes even under high pressures and abra- in large quantities. Due to long half-lives of its
sive conditions guarantees constant quality of the isotopes (t1/2 of 241Am, 432 y; 243Am, 7370 y),
permeate and makes it preferable in the scenarios this element can have long-term hazards to the
where quality control is crucial, such as in drink- environment if not separated from the radioactive
ing water production and food industry. And the wastes before their disposal. Separation of Am
natural hydrophilic surface of alumina offers bet- mostly involves solvent extraction-based methods
ter anti-fouling property than polymeric mem- involving specially designed ligands for Am
branes; therefore its usage in wastewater uptake. Membrane-based separation has been
treatment is expanding rapidly; and in some used for Am separation using pressure-driven
other heavy-duty ltration processes such as techniques such as nanoltration, facilitated by
treating produced water from oil elds, alumina complexation (Favre-Rguillon et al. 2007).
membranes have been dominant. However, selectivity factors in such separation
systems are not encouraging. Liquid membrane-
based separation systems, with Am-specic car-
rier extractants, are reported to give better
Further Reading
decontaminations.
Benfer S, rki P, Tomandl G (2004) Ceramic membranes Some of the rst studies on Am transport
for ltration applications preparation and characteri- using supported liquid membranes include
zation. Adv Eng Mater 6(7):495500 the work of Danesi, who used CMPO
Lehman SG, Adham S, Liu L (2008) Performance of
new generation ceramic membranes using hybrid coag-
(carbamoylmethylphosphine oxide) as the carrier
ulation pretreatment. J Environ Eng Manage extractant (Danesi et al. 1983). Feed solutions
18(4):25760 containing LiNO3 resulted in highly encouraging
60 Americium Separation by Membrane Operation

Am transport rates which were signicantly TODGA-based hollow-ber supported liquid


affected in the presence of nitric acid in the feed, membrane system has been successfully used in a
attributed to the cotransport of nitric acid. The Am mini pilot-scale processing of synthetic high-level
transport rates could be improved by using a sec- waste (Ansari et al. 2011). A series of studies have
ond membrane in parallel containing Primene indicated that the diluents play a signicant role in
JM-T as the carrier extractant for selective trans- Am transport rates which are mainly due to two
port of nitric acid (Chiarizia and Danesi 1987). In factors: (i) nature of the extracted species and
another study, triphosphine trioxide extractants (ii) diffusivity of the extractable complex which
have been employed for Am(III) transport from is based on the viscosity of the medium (Panja
NaNO3 solutions with encouraging results et al. 2012).
(Cristau et al. 1999). Other extractants such as Am(III) separation of trivalent lanthanides has
tetra-alkyl malonamides and diglycolamides have also been studied using various Am(III) selective
shown comparable or even better transport ef- extractants such as Cyanex 301 (Hoshi et al. 2000),
ciency for Am as compared to CMPO. BTP (Geist et al. 2005), etc. In one of the early
Malonamides such as DMDBTDMA (N,N0 - reports on Am(III)Eu(III) separations using liquid
dimethyl-N,N0 -dibutyltetradecyl malonamide) membranes (Novikov and Myasoedov 1987),
0
and DMDOHEMA (N,N -dimethyl-N, almost no transport of Am(III) was observed
N0 -dioctylhexylethoxymalonamide) are reported while effecting complete quantitative Eu(III) trans-
to be quite efcient for Am(III) transport (Sriram port using a feed composition of 0.01 M DTPA,
et al. 2000; Patil et al. 2013). TODGA (N,N,N0 , 0.5 M citric acid, 0.5 M NaNO3 at pH 2.9, and 1 M
N0 -tetraalkyldiglycolamide) has been found to be HDEHP as the carrier extractant. Cyanex 301 has
one of the best carriers for Am(III) transport due to been used for highly selective Am(III) transport of
signicantly lower acid cotransport as compared to a feed also containing several trivalent lanthanide
CMPO or malonamides (Ansari et al. 2009). ions (Fig. 1; Bhattacharyya et al. 2006). Oxidation

Americium Separation 3000 166


Ho
by Membrane 2500
Operation,
Counts/900 s

2000
Fig. 1 Gamma ray 241
Am Feed (initial)
spectrum of the feed and 1500
152,154
receiver solutions measured 1000 Eu160 140 160
using HPGe detector Yb La Tb
500
(Bhattacharyya et al. 2006)
0
3000 166
Ho
2500
Count/900 s

2000 Feed after 4 hrs


1500 152,
154 140
1000 Eu 160 La 160
Yb Tb
500
0
3000
2500
Counts/900 s

2000 Strip after 4 hrs


1500
1000 241
Am
500
0
0 1000
Energy (keV)
Americium Separation by Membrane Operation 61

to the +4 and +6 states reportedly enhanced Am Bhattacharyya A, Mohapatra PK, Manchanda VK


transport rates due to higher extraction efciencies (2006) Separation of trivalent actinides and lanthanides
using a at sheet supported liquid membrane
of these ions. Tri-n-octylamine containing liquid containing Cyanex-301 as the carrier. Sep Purif A
emulsion membrane (LEM) systems has been Technol 50:278281
used for the transport of Am(IV) which was done Chiarizia R, Danesi PR (1987) A double liquid membrane
using phosphotungstate (Myasoedov et al. 1990). system for the removal of actinides and lanthanides
from acidic nuclear wastes. Sep Sci Technol
In another report (Mikheeva et al. 1994), the trans- 22:641659
port of hexavalent Am by electrochemical oxida- Cristau HJ, Virieux D, Dozol JF, Rouquette H (1999)
tion followed by simultaneous transport using Selective extraction of actinides by polyphosphine
HDEHP as the carrier. polyoxides through supported liquid membrane.
J Radioanal Nucl Chem 241:543547
There are several reports on the Am(III) recov- Danesi PR, Horwitz EP, Rickert PG (1983) Rate and mech-
ery from acidic feeds using liquid emulsion mem- anism of facilitated americium(III) transport through a
branes (LEM) using extractants such as HDEHP, supported liquid membrane containing a bifunctional
PC-88A, and TODGA as well. Usually, the LEM organophosphorus mobile carrier. J Phys Chem
87:47084715
methods are much faster as compared to the Favre-Rguillon A, Sorin A, Pellet-Rostaing S, Bernier G,
SLM-based separation methods which are due to Lemaire M (2007) Nanoltration assisted by complex-
highly dispersed globules containing the internal ation: a promising process for the separation of trivalent
phase as the strippants present in the emulsion long-lived minor actinides from lanthanides. C R Chim
10:9941000
which effect rapid mass transfer. In a recent Geist A, Weigl M, Gompper K (2005) Small-scale actinide
study, multifunctional ligands such as the (III) partitioning processes in miniature hollow bre
calixarenes anchoring diglycolamide functional modules. Radiochim Acta 93:197202
groups have shown improved transport behavior Hoshi H, Tsuyoshi A, Akiba K (2000) Separation of amer-
icium from europium using liquid membrane impreg-
as compared to the simple extractants (Ansari nated with organodithiophosphinic acid. J Radioanal
et al. 2013). The liquid membrane methods with Nucl Chem 243:641644
lower ux as compared to the solvent extraction Mikheeva MN, Novikov AP, Myasoedov BF, Tikhomirov
methods can be used for pre-concentration SV (1994) Kinetics of americium(VI) mass transfer
through solid supported liquid membrane with HDEH-
and separation of Am from dilute solutions P. J Radioanal Nucl Chem Art 185:265271
including environmental samples and radioactive Myasoedov BF, Novikov AP, Milyukova MS, Mikheeva
wastes. MN, Bunina TV (1990) Emulsion membrane extrac-
tion of Am(III) and Am(IV) in systems with tertiary and
secondary amines. J Radioanal Nucl Chem
142:481487
References Novikov AP, Myasoedov BF (1987) Separation of trivalent
europium, terbium, americium and curium by a
Ansari SA, Mohapatra PK, Raut DR, Kumar M, supported liquid membrane impregnated with
Rajeswari B, Manchanda VK (2009) Performance of di-(2-ethylhexyl)phosphoric acid. Solvent Extr Ion
some extractants used for actinide partitioning in a Exch 5:117127
comparative hollow bre supported liquid membrane Panja S, Mohapatra PK, Tripathi SC, Gandhi PM, Janardan
transport study using simulated high level nuclear P (2012) Role of organic diluents on Am(III)
waste. J Membr Sci 337:304309 pertraction across N, N, N0 N0 -tetraoctyl-3-
Ansari SA, Gujar RB, Mohapatra PK, Kandwal P, oxapentanediamide (TODGA) supported liquid mem-
Sengupta A, Thulasidas SK, Manchanda VK branes. J Membr Sci 403404:7177
(2011) A cold actinide partitioning run at 20 L scale Patil AB, Shinde V, Pathak PN, Mohapatra PK (2013)
with hollow ber supported liquid membranes Evaluation of DMDOHEMA based supported
containing diglycolamide extractants. Radiochim Acta liquid membrane system for high level waste remedia-
99:815821 tion under simulated conditions. J Membr Sci
Ansari SA, Mohapatra PK, Iqbal M, Kandwal P, 442:4856
Huskens J, Verboom W (2013) Novel diglycolamide- Sriram S, Mohapatra PK, Pandey AK, Manchanda VK,
functionalized calix[4]arenes for actinide extraction Badheka LP (2000) Facilitated transport of americium
and supported liquid membrane studies: part II. Role (III) across a PTFE membrane containing dimethyl
of substituents in the pendent arms and mass transfer dibutyl tetradecyl-1,3-malonamide as carrier. J Membr
modeling. J Membr Sci 430:304311 Sci 177:163175
62 Ammonia Decomposition in Catalytic Membrane Reactors

SRM reaction : CH4 2H2 O $ CO2 4H2


Ammonia Decomposition in Catalytic DH 164:5 kJ=mol
Membrane Reactors MTH cycle : C7 H14 $ C7 H8 3H2
DH 204:6 kJ=mol
Toshinori Tsuru NH3 system : NH3 ! 0:5N2 1:5H2
Department of Chemical Engineering, Hiroshima DH 46 kJ=mol
University, Higashi-Hiroshima, Japan
Membrane reactors can be categorized based on
conguration of catalysts as packed type membrane
reactor, uidized membrane reactor, and catalytic
Recently, NH3 has been proposed as a H2 car- membrane reactor. As shown in Fig. 1, packed bed
rier in a promising solution that would bypass membrane reactors consist of catalysts for reaction as
the intractable issues related to H2 storage and well as membranes for separation. Both catalyst
delivery, since NH3 has a high hydrogen stor- particles and membranes are packed into one unit,
age capacity of 17.6 wt.% and can be easily but reaction and separation occur separately. On the
stored and transported in liquid form under other hand, catalytic membranes have catalytic activ-
mild conditions. NH3 decomposes to H2, ity as well as separation ability in one membrane.
which produces only H2O after combustion, Zeolite membranes such as ZSM-5 and TS-1 are
and N2, which is not a greenhouse gas; in inherently catalytically active, while another type
other words, NH3 is a COx-free H2 carrier. of catalytic membrane is a silica hydrogen separation
Another class of a hydrogen carrier is an membrane on catalytically active support which can
organic hydride such as cyclohexane (CH) and be prepared using catalytically active powders such
methylcyclohexane (MCH). In dehydrogenation as nickel oxides or impregnation of Ni-catalyst inside
reaction, CH and MCH reversibly produce ben- porous a-alumina supports (Tsuru et al. 2004).
zene (BEN) and toluene (TOL), based on the Membrane reactors combining a catalytic reac-
equilibrium reaction, respectively, while BEN tion with the separation process into a single unit
and TOL are re-hydrogenated into CH and offer an ideal device to produce H2 from NH3
MCH, respectively. Methylcyclohexane- efciently, where enhanced NH3 conversion and
toluene-hydrogen (MTH cycle) and high-purity COx-free H2 can be simultaneously
cyclohexane-benzene-hydrogen (CBH cycle) obtained by applying a hydrogen separation mem-
need reversible and highly selective conversion brane. Ru is reported the most active catalyst for
to sustainable use. Therefore, the advantages of ammonia decomposition and is supported on
NH3 mentioned above make the NH3-mediated porous carbon such as carbon nanotubes (CNT)
hydrogen economy extremely attractive and with supporting catalysts such as potassium (K).
promising. Other H2 carriers, such as methanol, To date, only a few studies have reported mem-
dimethyl ether, etc., inevitably cause end-user brane reactors for NH3 decomposition in a packed
CO2 emissions, since they are carbonaceous bed Pd membrane reactor, and improved NH3
compounds and on-board CO2 capture is not conversion was obtained after H2 extraction.
feasible. Another class of membrane reactor is a cata-
As shown in the following equations, lytic membrane reactor. Figure 2 shows a sche-
another advantage of NH3-energy systems is matic bimodal catalytic membrane reactor
the low heat of reaction. Approximately 30 kJ (BCMR) (Li et al. 2013). This new type of mem-
is required for one mole of produced H2 in NH3 brane reactor had a conguration that consisted of
system, which is lower than in MTH cycle a silica separation layer and a bimodal catalytic
(70 kJ) and steam reforming of methane support (Ru/g-Al2O3/a-Al2O3). The impregnation
(SRM) (40 kJ). of g-Al2O3 into an a-Al2O3 membrane support to
Ammonia Decomposition in Catalytic Membrane Reactors 63

Reactants retentate
Reactants retentate

A
packed catalyst catalytic
permeate membrane permeate
membrane

Packed Bed Membrane Reactor (PBMR) Catalytic Membrane Reactor (CMR)

Ammonia Decomposition in Catalytic Membrane Reactors, Fig. 1 Conguration of membrane reactors

COx-free H2

Silica membrane
Intermediate layer

Ru catalyst
-Al2O3
Bimodal catalytic support layer
-Al2O3


NH3 1.5H2 0.5N2
NH3 N2

Ammonia Decomposition in Catalytic Membrane Reactors, Fig. 2 Schematic diagram of the proposed bimodal
catalytic membrane reactor for COx-free H2 production via NH3 decomposition (Li et al. 2013)

Ammonia
Decomposition
in Catalytic Membrane
Reactors, Fig. 3 Bimodal
catalytic membrane reactor
performance for NH3
decomposition at 450  C
(Li et al. 2013)

form a bimodal support is expected to effectively improved catalytic activities by mesopores and
improve catalytic membrane reactor performance, high gas diffusivity by macropores.
since the bimodal structure contains both Figure 3 shows an example of enhancement of
mesopores and macropores, which results in conversion for the BCMR performance for NH3
64 Amorphous Fluoropolymers

decomposition at 450  C. During the initial of the polymeric sequences and increase the
250 min without sweep gas, a NH3 conversion intermolecular distances. The complete suppres-
was 45 %. When N2 sweep gas was applied to sion of the crystallinity is, instead, more easily
the permeate stream of the membrane reactor, achieved by introduction of elevated percentage
NH3 conversion was signicantly enhanced from of cyclic monomeric units; by following this strat-
45 to 95 % after the selective H2 extraction. NH3 egy, new families of amorphous glassy peruor-
decomposition rate is strongly inhibited by the opolymers (Teon AF, Cytop , and Hyon
presence of H2, particularly at a high pressure. AD whose structures are reported in Fig. 1) were
Therefore, the highly enhanced NH3 conversion developed and commercialized starting from the
can be ascribed to the improved kinetics from H2 late of 1980s (Merkel et al. 2006).
extraction in the BCMR. The cyclic groups, present in each of these
three structures, hinder efcient chain packing,
thus preventing crystal formation and yielding
References completely amorphous polymers with a glass
transition (Tg)tunable but always sensibly above
Li G, Kanezashi M, Tsuru T (2013) Highly enhanced room temperature (from 95  C of Hyon AD40
ammonia decomposition in bimodal catalytic silica
to 240  C of Teon AF2400).
membrane reactors for COx-free hydrogen production.
AIChE J 59:168179 Teon AF, Cytop , and Hyon AD com-
Tsuru T, Yamaguchi K, Yoshioka T, Asaeda M (2004) bine the properties typical of peruorinated semi-
Methane steam reforming by microporous catalytic crystalline materials (high thermal and chemical
membrane reactors. AIChE J 50:2794
resistance, low dielectric constant, low surface
energy) with new peculiar properties imparted
by the amorphous structure such as the high sol-
ubility in uorinated solvents and excellent trans-
Amorphous Fluoropolymers parency across a broad wavelength range (from
UV to near IR). Furthermore, the high chain stiff-
Marco Avataneo ness imparted by the cyclic units leads to a dif-
RD&T, Solvay Specialty Polymers, Bollate (MI), cult packing of the chain segments with the
Italy consequent formation of nano-voids which are
responsible for the high gas diffusion of these
polymers. Gas separation membranes, pellicles
Synonyms for microlithography, protective coatings, dielec-
tric layers for organic and electronic and plastic
Fluorinated polymers; Fluoroplastics; optical bers are the most important applications
Noncrystalline of these glassy peruoropolymers.
Other two important families of amorphous
Amorphous uoropolymers are noncrystalline uoropolymers, in this case displaying a Tg
synthetic polymers where the hydrogen atoms of value below room temperature, are peruoropo-
the backbone have been partially or completely lyethers (PFPEs) and uorinated elastomers. The
replaced by uorine atoms. While common former (Fig. 2), obtained by means of different
uoroplastics are semicrystalline, the number of manufacturing technologies (Rizvi Syed 2009;
commercial amorphous peruoropolymers is rel- Marchionni et al. 1996), are low molecular weight
atively limited (Scheirs 2001). polymers containing etheric oxygen atoms in the
In uorinated polymers the crystallinity, char- backbone which make the chains extremely ex-
acteristic of peruorocarbon CF2CF2- units, can ible so preventing the formation of crystallite
be reduced by incorporation of monomers with phases.
pendant side groups, like hexauoropropene or These synthetic uids display extremely low
peruorovinyl ethers, which disrupt the regularity Tg, even below 100  C. They nd applications
Amorphous Fluoropolymers 65

Amorphous a b c
Fluoropolymers, OCF3
Fig. 1 Structure of three CF CF CF2 CF2 CF2 CF CF CF2
commercial amorphous CF C CF2 CF2 m A
glassy peruropolymers m O O O CF2
O O
C CF2
CF2 n
n CF3 CF3
n
Hyflon AD Teflon AF Cytop

Amorphous CF3CF2CF2O- (CFCF2O)nCF2CF3 Krytox, Du Pont


Fluoropolymers,
Fig. 2 Structure of the four CF3
most important commercial CF3CF2CF2O- (CF2CF2CF2O)nCF2CF3 Demnum, Daikin
peruoropolyethers
CF3O- (CF2CFO)m(CFO)n(CF2O)p-CF3 Fomblin Y, Solvay

CF3 CF3

CF3O- (CF2O)m(CF2CF2O)n-CF3 Fomblin Z, Solvay

as lubricants for extreme conditions (high temper- Cross-References


atures, high pressure, presence of aggressive
chemicals), as testing and heat transfer uids in Gas Separation
electronic, and as inert solvents. PFPEs Glass Transition Temperature (Tg)
containing functional-end groups can be used as Hyon AD
building blocks for the synthesis of two-phase
materials (partially uorinated, partially hydroge-
References
nated), surface treatment agents, and surfactants.
Few applications in the eld of membranes are Chaouk H, Wilkie JS, Meijs GF, Cheng HY (2001) New
known for PFPEs (Chaouk et al. 2001). porous peruoropolyether membranes. J Appl Polym
Fluorinated elastomers (Moore 2006) are Sci 80:17561763
cross-linked amorphous polymers with Tg Marchionni G, Ajroldi G, Pezzin G (1996)
Structureproperty relationships in peruoropo-
below room temperature. They are generally lyethers: a family of polymeric oils. In: Allen SG,
obtained by copolymerization of at least two of Aggarwal SL, Russo S (eds) Comprehensive polymer
the following monomers: tetrauoroethylene, science, 2nd suppl. Pergamon Press, Oxford, UK,
vinylidene uoride, hexauoropropene, and pp 347388
Merkel TC, Pinnau I, Prabhakar R, Freeman BD
peruorovinyl ethers. Fluorosilicone elastomers, (2006) Gas and vapour properties of peruoro-
i.e., uorochemically modied polysiloxanes, are polymers. In: Yampolskii Y, Pinnau I, Freeman BD
another important class of uorinated elastomers. (eds) Materials science of membranes for gas and
Fluoroelastomers show extreme resistance to vapour separation. Wiley, New York, pp 251270
Moore AL (2006) Fluoroelastomers Handbook, Schroeder
high temperatures and to a variety of aggressive H. In: Rubber Technology (Morton, M., Ed.), 3rd ed.
uids. They exhibit excellent resistance to oils, William Andrew Publishing, Norwich: NY, p. 105
solvents, acids, alkalis, and ozone over a wide Rizvi Syed QA (2009) A Comprehensive Review of Lubri-
temperature range (30  C to 250  C) and, there- cant Chemistry, Technology, Selection and Design,
ASTM International, West Conshohocken, PA, pp
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industrial applications in the eld of membranes trends a Rapra industry analysis report, Rapra Tech-
are known. nology Limited, Shawbury
66 Amorphous Perfluoropolymers

Cross-References
Amorphous Perfluoropolymers
Glass Transition Temperature (Tg)
Marco Avataneo Hyon AD
RD&T, Solvay Specialty Polymers, Bollate (MI),
Italy
References

Marchionni G, Ajroldi G, Pezzin G (1996)


Synonyms Structureproperty relationships in peruoropolyethers:
a family of polymeric oils. In: Allen SG, Aggarwal SL,
Fully uorinated polymers; Noncrystalline Russo S (eds) Comprehensive polymer science, 2nd
suppl. Pergamon Press, Oxford, pp 347388
Marshall JB (1997) In: Scheirs J (ed) Modern
Amorphous peruoropolymers are noncrystalline uoroplastics. Wiley, Chichester
fully uorinated synthetic polymers composed Merkel TC, Pinnau I, Prabhakar R, Freeman BD
exclusively by carbon, uorine, and oxygen (2006) Gas and vapour properties of peruoro-
polymers. In: Yampolskii Y, Pinnau I, Freeman BD
atoms. The most relevant product family for mem- (eds) Materials science of membranes for gas and
brane applications is represented by the glassy vapour separation. Wiley, New York, pp 251270
amorphous peruoropolymers containing dioxole Moore AL (2006) Fluoroelastomers handbook the den-
groups (Teon AF, Hyon AD, and Cytop) itive users guide and databook. William Andrew Pub-
lishing/Plastics Design Library, Norwich, NY
which display a glass transition above room tem- Sanguineti A, Guarda PA, Marchionni G, Ajrolidi G (1995)
perature (Merckel et al. 2006). Peruoropolyethers Solution properties of peruoropolyether polymers.
and peruorinated elastomers are, instead, the two Polymers 36:36973703
most important families of amorphous peruoro-
polymers with a glass transition below room tem-
peratures. Peruoropolyethers (Marchionni
et al. 2006; Sanguineti et al. 1995) are a class of
synthetic lubricants characterized by extremely low Amorphous Polymers
Tg, also below 100  C. They nd applications as and the Amorphous Region
lubricants for extreme conditions (high tempera-
tures, high pressure, presence of aggressive Petr Sysel
chemicals), as heat transfer uids and as inert sol- Department of Polymers, Institute of Chemical
vent (they are good solvent for the glassy amor- Technology, Prague, Czech Republic
phous peruoropolymers). The commercially
available PFPEs include Krytox, Fomblin, and
Demnum. Peruoroelastomers (Moore 2006), Polymers consist of the large molecules (polymer
also referred to as FFKM elastomers, are amor- chains). An arrangement of these chains in
phous cross-linked polymers obtained by copoly- the bulk polymer is given by their chemical com-
merization of tetrauoroethylene with position, spatial orientation (e.g., an isotactic vs
hexauoropropene and/or peruorovinyl ethers atactic polypropylene), molecular weight, and
which effectively disrupts the crystallinity imparted processing conditions (e.g., a cooling rate).
by the TFE segments (Marshall 1997). Peruoroe- Based on these factors, bulk polymers show an
lastomers are characterized by improved thermo- amorphous or partially crystalline
oxidative stability and oil resistance (compared (semicrystalline) phase state. In the amorphous
with VDF-based elastomers) for extreme industrial state, an ordering of the (entangled) polymer
and military applications. Unlike the glassy amor- chains is random. The amorphous polymer does
phous peruoropolymers, no relevant industrial not include a long-range order, but it is character-
membrane applications for peruoropolyethers ized by the existence of some regularity on a
and for peruoroelastomers are known. short-range order. As a consequence of it, an
Amorphous Polymers and the Amorphous Region 67

deformation
A
glassy state rubbery state plastic state

glass transition flow temperature


temperature
temperature

Amorphous Polymers and the Amorphous Region, Fig. 1 Thermomechanical curve of an amorphous polymer

X-ray diffraction provides a diffuse ring only An extent of this (segmental) chain motion and
(a set of discrete rings is typical for well-ordered free volume inuences a lot of the polymer prop-
structures). If the amorphous polymer is exposed erties, e.g., a transport of the different
to a gradually increased temperature, it passes low-molecular-weight media through the mem-
from a glass (hard and rigid) to a rubber (soft branes made of these polymers (Strathmann
and exible) and nally to a molten consistency. 2011). For example, a nonporous (dense)
Boundaries between the glass/rubber and rubber/ membrane made of a rubbery polysiloxane [(Si
molten consistency are given by a glass transition (R)2-O-)n, where R is often CH3] shows a much
temperature (Tg) and ow temperature, respec- higher gas permeation (and also diffusivity) in
tively (see a thermomechanical curve of an amor- comparison with those made of common glassy
phous polymer, Fig. 1). polymers at room temperature (Pandey 2001;
The glass transition temperature of the polymer Bernardo et al. 2009). But their selectivity is tra-
is also an important indicator of its application ditionally low (Robeson 2008).
temperature region (e.g., polydimethylsiloxane Some polymers (e.g., polyethylene, polyam-
(Tg = ca 120  C) is rubbery and polystyrene ides) include both amorphous and crystalline frac-
(Tg = ca +100  C) is a glassy polymer at room tions, and they are called semicrystalline ones.
temperature). A character of the main backbone Chains of such polymers may be organized in
(exible/rigid), its substitution (small vs bulk sub- spherulites having a well-ordered lamellar struc-
stituents), and a level of molecular (chain) inter- ture (i.e., a folded chain) with an incorporated
actions (e.g., van der Waals forces vs hydrogen disordered amorphous fraction (Fig. 3).
bonds) are important factors inuencing the posi- Amorphous polymers are usually transparent;
tion (value) of this transition. A exibility of the semicrystalline ones are opaque. A segmental
chains (or segments) of an amorphous polymer is mobility of the amorphous regions in semicrystal-
restricted at temperatures below its Tg. Under line polymers varies from that of the amorphous
heating, molecular interactions (secondary forces) polymer. These regions are affected by the pres-
are disrupted, and a free volume among more ence of crystalline phase, and this phenomenon
exible chains increases (Fig. 2). inuences also transport characteristics of the
68 Amphipathic Molecules

Amorphous Polymers
and the Amorphous
Region,
Fig. 2 Temperature specific
dependence of the specic volume
volume of an amorphous
polymer

glass transition
temperature

temperature

Amorphous Polymers
and the Amorphous
Region, Fig. 3 Schematic
amorphous region
arrangement of the
spherulite

lamellar structure

penetrating media. Traditionally, the more Colomines G, Ducruet V, Courgneau C, Guinault A,


dense crystalline phase decreases a chain mobil- Domenek S (2010) Barrier properties of poly(lactic
acid) and its morphological changes induced by
ity and prolongs a transport trajectory of penetrat- aroma compound sorption. Polym Int 59:818826
ing media, and as a consequence of this their Pandey P, Chauhan RS (2001) Membranes for gas separa-
permeability decreases (Pandey 2001). Neverthe- tion. Prog Polym Sci 26:853893
less, some exceptions were also found, e.g., an Robeson LM (2008) The upper bound revisited. J Membr
Sci 320:390400
increase of gas permeability in a polylactide mem- Strathmann H (2011) Introduction to membrane science
brane with its increasing crystallinity (Colomines and technology. Wiley-VCH, Weinheim
et al. 2010).

References
Amphipathic Molecules
Bernardo P, Drioli E, Golemme G (2009) Membrane gas
separation. Ind Eng Chem Res 48:46384663 Amphiphilic Molecules
Amphiphilic Membrane 69

Amphiphilic Membrane from


Amphiphiles Amphiphilic Molecules
A
Amphiphilic Molecules Amphiphilic membrane is a kind of planar arrays
of one or two monomolecular layers, which are
derived from self-assembly of amphiphilic mole-
cules, such as lipids, surfactants, or block copoly-
Amphiphilic Block Copolymers mer amphiphiles, through noncovalent interactions
in aqueous solution or in oilwater mixtures
Amphiphilic Molecules (Lipowsky et al. 1992; Lipowsky 1991). Amphi-
philic molecules, such as lipids or surfactants, pos-
sess a hydrophilic (lipophobic) head and a
hydrophobic (lipophilic) tail consisted of one or
Amphiphilic Conetwork Membrane two hydrocarbon chains. The hydrophilic head pre-
fers to be in contact with water in aqueous solution,
Amphiphilic Membrane
whereas the hydrophobic tail tends to minimize
contact with water. In aqueous solution or in
oilwater mixtures, such molecules can form a
Amphiphilic Film variety of structures (assemblies) due to the hydro-
phobic effect. In many cases, the molecules form
Amphiphilic Membrane amphiphilic membranes consisted of a monomo-
lecular monolayer of amphiphiles. For example,
the phospholipid molecules self-assemble verti-
cally as a monolayer lm at the interface between
Amphiphilic Lamellar Structure water and air, with their hydrophilic head groups
immersed in the water and their hydrophobic tails
Amphiphilic Membrane pointed to the air, as shown in Fig. 1a (Costa
et al. 2012). The two-dimensional membrane also
can be observed in the lamellar aggregates of sur-
factant molecules at the oilwater interface in a
Amphiphilic Membrane microemulsion. These two-dimensional monomo-
lecular insoluble membranes formed by spreading
Jianhua Zhang amphiphilic molecules on the surface of a liquid are
Department of Polymer Science and Engineering, also referred to as Langmuir monolayers (Kaganer
School of Chemical Engineering and Technology, et al. 1999; Duchs and Schmid 2001). These
Tianjin University, Tianjin, China one-molecule-thick lms display many advantages
Tianjin Key Laboratory of Membrane Science and compared to the other model membranes, which
Desalination Technology, Tianjin University, are excellent model systems for studying chemical
Tianjin, China and biological reactions in two dimensions,
dynamic adsorptions and interfacial behaviors, as
well as membrane hydrolysis processes
Synonyms (Dynarowicz-atka et al. 2001). These monolayers
also provide a way to manipulate molecules and
Amphiphilic conetwork membrane; Amphiphilic construct articial materials for optical, electronic,
lm; Amphiphilic lamellar structure; Amphiphilic or sensor applications (Kaganer et al. 1999).
monolayer/bilayer; Hydrophilic-hydrophobic Amphiphilic molecules dissolved in water at
membrane; Lipid monolayer/bilayer; Two- appropriate concentrations can also self-assemble
dimensional amphiphilic aggregates into bilayer structures with a thickness of only a
70 Amphiphilic Membrane

a Curved bilayer
Monolayer membrane Planar bilayer membrane Solid-supported membrane membrane
air

water
asymmetric symmetric asymmetric symmetric Liposome
b Block copolymeric membrane c Polymeric vesicles(Polymersomes)
Hydrophilic brush
Hydrophobic
membrane

100nm
Polymeric Bilayer Interdigitated layer
Vesicle Wall
Bilayer membrane

Amphiphilic Membrane, Fig. 1 Typical amphiphilic schematic illustrations were made according to the refer-
membranes based on the self-assembly of amphiphiles. ences (Gutsmann and Seydel 2010; Battaglia and Ryan
(a) Phospholipid molecules. (b) Amphiphilic diblock 2005; Du and OReilly 2009 with permission from
copolymers. (c) Amphiphilic diblock copolymers. The Elsevier and The Royal Society of Chemistry)

few nanometers, as shown in Fig. 1a. Such bilayer have universal application in biology and nanotech-
membranes consist of two opposing layers of nology, such as ion channel activity, lipid phase
amphiphiles. The hydrophilic heads are oriented separation, charged lipids manipulation, cell signal-
towards the surrounding water, while the hydropho- ing, cell-cell interaction, membrane base biosensor,
bic tails overlapped and packed the middle of the and protein binding (Han et al. 2013).
membrane (Lipowsky et al. 1992; Lipowsky 1991). Amphiphilic membranes prepared from the
The bilayer membranes are usually found either in self-assembly of lipids have a certain amount of
the form of closed vesicles or as part of a multilayer uidity, depending crucially on the temperature as
stack of lamellae (Chowdhury and Stauffer 1991; well as chain structures and physicochemical
Leibler and Andelman 1987). Particularly, lipid properties of amphiphiles. Therefore, their perme-
bilayers are one of most important amphiphilic ability, stability, and mechanical characteristics
membranes due to their properties and their impor- are not particularly well controlled (Illya
tance in biological systems. The lipid bilayers are a et al. 2005; Discher et al. 1999; Discher and
general structure of cell membrane of almost all Eisenberg 2002). Like natural phospholipids,
living organisms, forming the barrier between cyto- amphiphilic block copolymers in water can also
sol and extracellular environment. Many biological self-assemble into various ordered lamellar struc-
functions and cellular processes for cell-surface tures. The morphology of the resultant
recognition, signaling, and transport are performed nanostructures was controlled by many factors.
at such biological interfaces (Shillcock and The volume ratio of the hydrophilic to hydropho-
Lipowsky 2002; Han et al. 2013). The importance bic block of membrane-forming amphiphiles was
of the lipid bilayers have aroused great interest in proposed to be one of the most important param-
fabricating articial bilayer membranes, including eters in the self-assembly process. Bilayer mem-
both freestanding lipid membranes and solid- branes, as shown in Fig. 1b, can be formed if the
supported membranes. These bilayer membranes hydrophilic/hydrophobic length ratio is suf-
are popular models of cell membranes, which ciently small (i.e., the critical aggregation
Amphiphilic Membrane 71

Amphiphilic Membrane, Fig. 2 Amphiphilic mem- response to hydrophobic and hydrophilic solvents. The
branes based on amphiphilic polymer conetworks. (a) schematic illustrations were made according to the refer-
Typical structures of segmented amphiphilic polymer ences (Patrickios and Georgiou 2003; Erdodi and Kennedy
conetworks. (b) A typical synthesis method of amphiphilic 2006 with permission from Elsevier)
polymer conetworks. (c) Amphiphilic membranes

concentrations approach zero) (Battaglia and make amphiphilic conetworks exhibit amphi-
Ryan 2005; Du and OReilly 2009). Moreover, philic characters (Isayeva and Kennedy 2004;
the lamellar structures of amphiphilic diblock Bruns et al. 2005; Erdodi and Kennedy 2006).
copolymers are often thermodynamically unstable, They commonly can be synthesized by a
which tend to close to form a hollow structure, i.e., multistep condensation (Fig. 2b) or a free-radical
polymer vesicles or polymersomes (Fig. 1c). Com- copolymerization with simultaneous cross-
pared to lipid-based vesicles, the stiffness and sta- linking (Erdodi and Kennedy 2006; Patrickios
bility of polymersomes are higher because of the and Georgiou 2003). As shown in Fig. 2c, such
length and conformational freedom of polymer networks can swell in both aqueous and organic
chains, which made polymersomes have potential media without losing their dimensional stability
for more applications in materials science, biology, and without encountering macroscopic phase sep-
and biomedical science (Battaglia and Ryan 2005; aration or polymer leaching, which have a great
Du and OReilly 2009). potential for applications such as contact lenses,
pervaporation membranes, and drug delivery sys-
tems (Erdodi and Kennedy 2006; Patrickios and
Amphiphilic Membrane Based Georgiou 2003; Isayeva and Kennedy 2004).
on Amphiphilic Conetworks

The term amphiphilic membrane also refers to a Cross-References


polymeric membrane based on amphiphilic
conetworks (Fig. 2a), which consist of hydro- Amphiphilic Molecules
philic and hydrophobic chain segments covalently Cell Membrane
bonded to each other. The cocontinuous Langmuir and LangmuirBlodgett (LB) Films
interconnected hydrophilic/hydrophobic phases Plasma Membrane
72 Amphiphilic Molecules

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polymer networks. Curr Opin Colloid Interface Sci
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Mulhaupt R, Tiller JC (2005) Nanophase separated Phys 117:50485061
amphiphilic conetwork coatings and membranes. Mac-
romolecules 38:24312438
Chowdhury D, Stauffer D (1991) Lifetime of unstable
bilayers: a lattice model for amphiphilic membranes.
Phys Rev A 44:22472250 Amphiphilic Molecules
Costa AP, Xu X, Burgess DJ (2012) Langmuir balance
investigation of superoxide dismutase interactions with Jianhua Zhang
mixed-lipid monolayers. Langmuir 28:1005010056 Department of Polymer Science and Engineering,
Discher DE, Eisenberg A (2002) Polymer vesicles. Science
297:967973 School of Chemical Engineering and Technology,
Discher BM, Won YY, Ege DS, Lee JCM, Bates FS, Tianjin University, Tianjin, China
Discher DE, Hammer DA (1999) Polymersomes: Tianjin Key Laboratory of Membrane Science and
tough vesicles made from diblock copolymers. Science Desalination Technology, Tianjin University,
284:11431146
Du J, OReilly RK (2009) Advances and challenges in Tianjin, China
smart and functional polymer vesicles. Soft Matter
5:35443561
Duchs D, Schmid F (2001) Phase behaviour of amphiphilic Synonyms
monolayers: theory and simulation. J Phys Condens
Matter 13:48534862
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(2001) Modern physicochemical research on Langmuir philic block copolymers; Amphiphilic polymers;
monolayers. Adv Colloid Interface Sci 91:221293 Amphipols; Detergents; Emulsiers;
Erdodi G, Kennedy JP (2006) Amphiphilic conetworks:
denition, synthesis, applications. Prog Polym Sci Hydrotropes; Lipids/phospholipids; Soaps;
31:118 Surfactants
Gutsmann T, Seydel U (2010) Impact of the glycostructure
of amphiphilic membrane components on the function Amphiphilic molecules is a general term that
of the outer membrane of Gram-negative bacteria as a
matrix for incorporated channels and a target for anti- describes any compound that contains two distinct
microbial peptides or proteins. Eur J Cell Biol covalently bonded components with different
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Han X, Qi G, Xu X, Wang L (2013) Lipid bilayer mem- which one part possesses a high afnity for polar
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Isayeva IS, Kennedy JP (2004) Amphiphilic membranes
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Kaganer VM, Mhwald H, Dutta P (1999) Structure and molecules.
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Phys 71:799819
Leibler S, Andelman D (1987) Ordered and curved meso-
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Nature 349:475481
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Amphiphilic Molecules 73

Amphiphilic Molecules, Fig. 1 Schematic illustrations segment. When p < 1/3, spheres are formed; when 1/3 <
of surfactants and corresponding assemblies. (a) Structures p < 1/2, cylinders will be favored; when 1/2 < p <
of surfactants, (b) Surfactant assemblies and the effect of 1, exible lamellae or vesicles are produced; nally,
the packing parameter (p). p = n/(a0lc), determining the when p = 1, planar lamellae are obtained. If p > 1, reversed
assemblies morphologies, where n is the volume of the structures can be observed (The schematic illustrations
hydrophobic segment, a0 is the contact area of the polar were made according to the Zhang et al. (2012) with
head group, and lc is the length of the hydrophobic permission from Elsevier)

such as cleaning products, food, cosmetics, phar- attracted much attention because of greater sur-
maceuticals, and oileld chemicals as well as face activity (Chevalier 2002; Fuhrhop and Wang
biological processes (Holmberg et al. 2002; 2004). Owing to their special structures and
Schramm et al. 2003; Chevalier 2002). Generally amphiphilic properties, surfactants can reduce
speaking, surfactants possess a hydrophilic head the surface tension when adsorbing at airwater
which might be either charged or uncharged and a or oilwater interface at very low concentration,
hydrophobic tail composed of one or more hydro- which can offer a number of surface chemistry
carbon, uorocarbon, or dimethylsiloxane chains functions, such as solubilizing, wetting, emulsify-
(Fig. 1a). According to the nature of their polar ing, foaming, and surface conditioning
head group, these molecules can be typically clas- (Holmberg et al. 2002; Schramm et al. 2003).
sied into four categories (Fig. 1a): (1) cationic More importantly, these amphiphilic molecules
surfactants containing a positively charged head can spontaneously segregate and self-assemble
group (e.g., fatty amine salts and quaternary into a wide variety of nanostructures through
ammoniums); (2) anionic surfactants with a neg- solvophobic interactions, when the concentration
atively charged head group such as carboxylate, of amphiphiles is above a certain critical concen-
sulfate, sulfonate, or phosphate; (3) nonionic sur- tration (i.e., the critical micelle concentration,
factants with an oligo(ethylene glycol) chain as CMC, dened as the concentration of surfactants
hydrophile; and (4) Zwitterionic surfactants com- above which micelles are spontaneously formed)
prised of a long hydrocarbon chain and a (Holmberg et al. 2002). The morphologies,
hydrophile containing both positive and negative including spherical micelles, cylindrical micelles,
charges. Some new surfactants such as lamellae, vesicles, etc. (Fig. 1b), are governed by
bolaamphiphiles and Gemini surfactants have the molecular structure of the surfactants as well
74 Amphiphilic Molecules

Amphiphilic Molecules, Fig. 2 Schematic illustrations schematic illustrations were made according to the Wang and
of typical chain structures (a) and morphologies of Grayson (2012), Mai and Eisenberg (2012) with permission
amphiphilic polymers in solution (b) and in bulk (c) (The from Elsevier and The Royal Society of Chemistry)

as by physical parameters such as concentration, (Holmberg et al. 2002; Nagarajan 2011). Due to
temperature, and ionic strength. The size and the coexistence of both hydrophobic and hydro-
shape of the aggregates were often predicted by philic moieties on the same molecule, they are
using the packing parameter (p), which is the ratio also able to self-assemble into a number of
of area occupied by the hydrophilic head and nanostructures in solution (Fig. 2b) and in bulk
hydrophobic groups of amphiphiles (Fig. 2c), which are analogous to those aggregates
(Israelachvili et al. 1976). The properties and per- of the small-molecule amphiphiles. Moreover,
formances of surfactants are closely related to their self-assembly behaviors follow the same
their self-assembly behaviors, and thus it still principle as that of surfactants (Mai and Eisenberg
requires much deeper understanding on the rela- 2012), and thus at least to some degree, the mor-
tionship among the molecular structures, aggrega- phologies of polymer assemblies can also be
tion behaviors, and application properties of these predicted by the dimensionless p, as shown in
amphiphiles. Fig. 2b. In addition, the hydrophilic/hydrophobic
ratio, copolymer concentration, solvent proper-
ties, etc. can signicantly affect the morphologies
Macromolecular Amphiphiles of the nal nanostructures (Mai and Eisenberg
2012). Due to the great versatility of polymers in
Amphiphilic polymers are another kind of typical terms of their molecular weight, chain architec-
amphiphilic molecules of high molecular weight ture, polydispersity, and reactivity as well as
Amphipols 75

synthetic diversity, amphiphilic polymers can pro- Israelachvili JN, Mitchell J, Ninham BW (1976) Theory of
vide greater opportunities for exibility, diversity, self-assembly of hydrocarbons amphiphiles into
micelles and bilayers. J Chem Soc Faraday Trans
and functionality. This is especially true in the 72:15251568 A
light of recent advances in controlled/living radi- Mai Y, Eisenberg A (2012) Self-assembly of block copol-
cal polymerization chemistry, such as ATRP and ymers. Chem Soc Rev 41:59695985
RAFT polymerization, for the preparation of Nagarajan R (2011) Amphiphilic surfactants and amphi-
philic polymers: principles of molecular assembly.
polymers of various architectures, including lin- ACS Symp Ser 1070(1):122
ear block copolymers, graft copolymers, dendritic Schacher FH, Rupar PA, Manners I (2012) Functional
polymers, star-like polymers, and cyclic poly- block copolymers: nanostructured materials
mers, as shown in Fig. 2a. Under certain condi- with emerging applications. Angew Chem Int Ed
51:225
tions, all of these types of amphiphilic polymers Schramm LL, Stasiuk EN, Marangoni DG (2003) Surfac-
can also self-organize into aggregates of diverse tants and their applications. Annu Rep Prog Chem Sect
morphologies (Mai and Eisenberg 2012; Wang C Phys Chem 99:348
and Grayson 2012). In addition, the size, mor- Wang Y, Grayson SM (2012) Approaches for the prepara-
tion of non-linear amphiphilic polymers and their appli-
phology, and function of the resulting polymeric cations to drug delivery. Adv Drug Deliv Rev
assemblies can be easily controlled by adjusting 64:852865
the structure of the amphiphilic copolymers. Zhang J, Li X, Li X (2012) Stimuli-triggered structural
Compared to small-molecule aggregates, polymer engineering of synthetic and biological polymeric
assemblies. Prog Polym Sci 37:11301176
aggregates exhibit higher stability and durability
(Mai and Eisenberg 2012). Particularly, stimuli-
sensitive polymer assemblies that can respond to
subtle changes in surrounding environment such
as pH, temperature, and solvent quality can be
feasibly realized via the self-assembly of polymer Amphiphilic Monolayer/Bilayer
amphiphiles with responsive groups (Schacher
et al. 2012; Zhang et al. 2012). Therefore, it is Amphiphilic Membrane
no wonder that amphiphilic polymers and their
assemblies have attracted considerable attention
and achieved signicant success in many elds,
such as biomedicine, biomaterials, pharmaceuti-
cals, microelectronics, and photoelectric Amphiphilic Polymers
materials.
Amphiphilic Molecules

Cross-References

Lipid Monolayer/Bilayer
Surface Tension Amphiphilic Substances:
Amphiphiles
References Encapsulation
Chevalier Y (2002) New surfactants: new chemical func-
tions and molecular architectures. Curr Opin Colloid
Interface Sci 7:311
Fuhrhop JH, Wang T (2004) Bolaamphiphiles. Chem Rev
104:29012937
Holmberg K, Jonsson B, Kronberg B, Lindman B (2002)
Amphipols
Surfactants and polymers in aqueous solution, 2nd edn.
Wiley, Chichester Amphiphilic Molecules
76 Amphoteric Ion Exchange Membrane

Amphoteric Ion Exchange Membrane

Tongwen Xu
Collaborative Innovation Centre of Chemistry for
Energy Materials, School of Chemistry and
Material Science, University of Science and
Technology of China, Hefei, China

Amphoteric ion exchange membrane is a kind


of membrane containing random arrangements of
both cation and anion exchange groups. When
rstly proposed by Sllner in 1932 (Sllner
1932), amphoteric ion exchange membranes Amphoteric Ion Exchange Membrane, Fig. 1 Transport
mainly refer to membranes having a combination number of hydrogen ions relative to sodium ions (PNaH)
and current efciency of cations to the composition of
of weak acidic (cation exchange) and weak basic
amphoteric ion exchange membranes. (,): quaternized
(anion exchange) groups. Nowadays, they are membranes (N-methyl pyridinium and sulfonic acid
expanded to include membranes containing a groups); (D, ~): tertiary amino groups membrane;
combination of weak acidic (or weak basic) with (pyridinium hydrochloride and sulfonic acid groups); (,
~): PNaH; (, D): current efciency (%). Electrodialysis
strong basic (or acidic) functionalities or a com-
was carried out at a current density of 20mAcm2 using a
bination of strong acidic and basic groups. Basi- mixed solution of 0.25 N sodium chloride and 0.25 N
cally, there are four types (Sata 2004): hydrochloric acid for 60 min at 25.0  C (Yamane
(1) membranes in which both anion and cation et al. 1965)
exchange groups are distributed at random during
the preparation procedures, such as copolymeri-
zation, (2) snake cage-type amphoteric mem- Meanwhile, some of the membranes have com-
branes, (3) polysalt membranes, and positions that show hydrogen ion
(4) membranes prepared by a layer-by-layer permselectivity relative to sodium ions in elec-
method. The amphoteric ion exchange mem- trodialysis (Yamane et al. 1965) (Fig. 1).
branes can show superior antifouling properties,
peculiar selectivity, and permeability and hence
are useful in the biomedical and industrial elds,
such as medical devices (e.g., hemodialysis References
membrane), separation of ionic drugs and pro-
teins, and depletion of electrolytes by Eguchi T, Mori S, Shimokawa M (1981) Process for pre-
nanoltration or piezodialysis as well as high paring a composite amphoteric ion exchange mem-
brane. US patent US874,687
performance gel actuator. Membrane having Sata T (2004) Ion exchange membranes: preparation, char-
properly combined anion and cation exchange acterization, modication and application. Royal soci-
groups shows selective permeability for inor- ety of Chemistry, Cambridge
ganic salts and, therefore, is able to separate a Sllner K (1932) Uber mosaikmembranen. Biochem
Z 244:390
low molecular organic substance from an inor- Yamane R, Izuo R, Mizutani Y (1965) Permselectivity
ganic salt, acid, or alkali as well as salt from acid of the amphoteric ion-exchange membranes(2).
or salt from alkali (Eguchi et al. 1981). Denki Kagaku (J Electrochem Soc Jpn) 33:589593
Analytical Pervaporation 77

Analytical Pervaporation
A
Wanqin Jin
State Key Laboratory of Materials-Oriented
Chemical Engineering, Nanjing University of
Technology, Nanjing, China

The relatively new developed pervaporation in


analytical chemistry is in principle a separation Analytical Pervaporation, Fig. 1 Conventional
technique for the removal of volatile analytes or pervaporation module. DC donor chamber, AC acceptor
their volatile derivatives from the sample matrix. chamber, MS membrane support, m membrane, AG air gap,
AS aluminum supports, DI, DO inlet/outlet of donor
Also, it can be used for sample pretreatment, e.g.,
stream, respectively, AL, AO inlet/outlet of acceptor
for solid samples where leaching and derivatiza- stream, respectively
tion of the analytes are done simultaneously. Ana-
lytical pervaporation can be dened as the
integration of evaporation and gas diffusion in a order to increase the volume of the corresponding
single module. Through a porous membrane, the chamber. The different parts of the module are
volatile substances present in a heated donor aligned by inserting metallic rods into four ori-
phase evaporate. And on the other side of the ces and a closer contact is achieved by screwing
membrane, the vapor condenses on the surface them between two aluminum supports (AS). The
of a cool acceptor stream. The driving force for whole module is normally made of methacrylate,
the separation is due to the temperature difference, which permits continuous monitoring of the sam-
which leads to a vapor pressure difference across ple level in the lower chamber during the experi-
the membrane. For analytical pervaporation, an ments Luque de Castro and Papaefstathiou
important feature is that the existence of a (1998).
constant-volume air gap between the sample in Constantly being hydrophobic, the membranes
the donor chamber and the membrane, which for analytical pervaporation are usually employed
hinders any contact between them. As a result, in ultraltration and gas-diffusion processes.
the clogging and/or deterioration of the membrane Practically, polytetrauoroethylene (PTFE) is the
can be avoided (Luque de Castro 1998). most frequently used membrane material,
The conventional version of the analytical followed by hydrophobic polyvinylidene uoride
pervaporation module is shown in Fig. 1 and (PVDF) Luque de Castro and Gdmiz-Gracia
consists of the following parts: (i) a lower donor (2000). In combination with the large surface
chamber (DC) in which the sample containing the area of both the donor and acceptor chambers,
analyte is introduced, either by injection or by the ultraltration membranes, which are very
continuous aspiration for liquid samples and by thin, lead to their easy bending. In result, the ux
direct weighing for solid samples, (ii) an upper of the permeating component changes through an
acceptor chamber (AC) in which an appropriate altered membrane area, and therefore, it leads to a
uid is circulated for receiving the pervaporated change in the efciency of the process in addition
analytes, (iii) a membrane support (MS) approxi- to reproducibility problems; consequently, the
mately 1 mm thick, and (iv) spacers of varying membranes must be changed quite often. Due to
thickness (between 2 and 10 mm) which can be their thickness, gas-diffusion membranes are not
placed above or below the membrane support in so easily bent, so the same membrane can be used
78 Anion-Exchange Membrane (AEM)

over longer periods. The efciency of the process Anion-exchange groups are positively charged
is inuenced by the pore size of the membrane groups: primary, secondary, and tertiary amino
(or its directly proportional thickness) and hence groups, quaternary ammonium groups, tertiary
the sensitivity of the method; it affords application sulfonium groups, quaternary phosphonium
to samples with variable analyte concentrations, groups, cobalticinum groups, and other groups
as a result. that provide a positive xed charge in aqueous
Analytical pervaporation can be used for the or mixed water and organic solvent solutions.
determination of a single analyte or a number of Based on the materials constituting membranes,
analytes, being of inorganic, organic, or organo- AEMs can be classied as (i) organic membranes,
metallic nature. Application of analytical (ii) inorganic membranes, and (iii) composite
pervaporation in the environmental eld has membranes of inorganic ion exchangers and
been reported especially for food analysis organic polymers. AEMs are also classied into
Amador and Luque de Castro (2000). which is two types by their microstructure: heterogeneous
the analytical eld in which pervaporation has and homogeneous. Heterogeneous AEMs consist
been most widely applied. Other elds of appli- of nely powdered anion exchanger and an inert
cation of pervaporation have been pharmaceutical binder polymer. Various methods have been reported
and clinical analyses. for preparing homogeneous AEMs. A typical exam-
ple of a hydrocarbon AEMs is a copolymer mem-
brane composed of styrene and divinylbenzene with
References benzyltrimethylammonium groups. These mem-
branes will be prepared, for example, by the reaction
Amador HJ, Luque de Castro MD (2000) Pervaporation: a of trimethylamine with a copolymer membrane pre-
useful tool in food analysis. Food Chem 68:387394
pared from chloromethylstyrene and divinylbenzene
Luque de Castro MD, Gdmiz-Gracia L (2000) Analytical
pervaporation: an advantageous alternative to head- or by alkylation with alkyl halide of a copolymer
space and purge-and-trap techniques. Chromatographia membrane prepared from vinylpyridine and
52:265272 divinylbenzene.
Luque de Castro MD, Papaefstathiou I (1998) Analytical
Though AEMs have been used in many elds,
pervaporation: a new separation technique. Trends
Anal Chem 17:4149 most are used in electrodialysis, separation of
electrolysis, and solid polymer electrolytes for
fuel cells. The properties required depend on the
intended application of AEMs. Generally required
properties are (1) low electrical resistance,
Anion-Exchange Membrane (AEM) (2) high transport number of anions, (3) low dif-
fusion coefcient of electrolytes, (4) low osmotic
Mitsuru Higa water and low electroosmotic water, (5) antifoul-
Graduate School of Science and Engineering, ing properties, (6) mechanical strength, (7) dimen-
Yamaguchi University, Ube, Yamaguchi, Japan sional stability, (8) high chemical stability and
durability, and (9) low cost (Sata 2004).
AEMs with low sulfate ion permeability have
The anion-exchange membrane (AEM) is a thin been industrially used to prevent precipitation of
lm with anion-exchange groups (positively calcium sulfate in the AEMs and electrodialyzer.
charged groups) and permeates anions selectively. A nitrate ion permselective AEM has been devel-
AEMs are classied according to the species oped and has contributed to human health because
of the ion-exchange groups and materials the concentrations of nitrate ions are greatly
constituting the membrane and microstructure. increased in groundwater. To prepare these
Anion-Exchange Resin 79

functionalized AEMs, ordinary AEMs are modi-


ed by suitable chemical or physical methods. For Anion-Exchange Resin
example, most commercially available homoge- A
neous AEMs are mainly cross-linked with Tongwen Xu
divinylbenzene. When the contents of Collaborative Innovation Centre of Chemistry for
divinylbenzene increase or compact layers are Energy Materials, School of Chemistry and
formed on the AEMs, the pore size of the mem- Material Science, University of Science and
brane decreases and the transport number of sul- Technology of China, Hefei, China
fate ions, which are bulky relative to chloride ions,
decreases.
Fouling of separation membranes is a common Anion-exchange resin contains positively
problem. AEMs are fouled by ionic materials of charged groups, such as NH3+, NRH2+,
medium molecular weight such as ionic surfac- NR2H+, NR3+, PR3+, SR2+, etc., which
tants having the charge opposite to the xed are xed to the membrane backbone and allow the
charged of the membrane. Almost all of organic exchange of anions but repulse cations. As shown
foulants in many efuent streams have negative in Fig. 1, the active groups existed in the body of
charges; hence, fouling of AEMs due to deposi- resin determine its chemical behavior. It has a
tion and/or adsorption of the foulants on/in the highly developed structure of pores on the surface,
AEM is one of the serious problems in their appli- which could easily trap and release ions.
cations. The pore size of the AEM is generally There are two main types of anion-exchange
recognized to be about 1 nm; therefore, ions of resins differing in their active groups: strongly
medium molecular weight permeate with dif- basic and weakly basic. (1) Strongly basic resins
culty through the membrane. Consequently, the are highly ionized, and their chemical behavior is
fouling can lead to an unacceptably high stack similar to that of a strong base which can be used over
resistance and replacement of membranes in an the entire pH range. They can react with anions in
electrodialysis system due to clogging of the solution and convert an acid solution to pure water.
membrane pores with the medium molecular The exhausted resin can be regenerated with concen-
weight ions. To alleviate the problem of organic trated sodium hydroxide (NaOH) and converted to
fouling, there are basically two methods on the the hydroxide form. (2) The degree of ionization of
membrane side: rst, to increase the pore size of weakly basic resin is strongly inuenced by pH
the membrane to allow easy permeation of large because it is like a weak base. The weak base resin
ionic materials and, second, to prevent penetration does not have a hydroxide ion form as does the
of the materials into the membrane at the mem- strong base resin. Consequently, its regeneration
brane surfaces. There are two methods to prevent needs only to neutralize the absorbed acid and does
penetration of large organic materials into the not need to provide hydroxide ions. Less expensive
membrane matrix: forming a thin charged layer weakly basic reagents such as ammonia (NH3) or
opposite in sign to the ion-exchange groups of the sodium carbonate can be employed.
membrane or forming a very thin and dense layer The selectivity of a resin for a given ion is
on the membrane surfaces. measured by the selectivity coefcient (K), as for
the reaction

Reference R  A B R  B A

Sata T (2004) Ion exchange membrane. The Royal Society The K can be expressed as K = (concentration
of Chemistry, Cambridge of B in resin/concentration of A in resin) 
80 Annealing of Polymer Membranes

Anion-Exchange Resin,
Fig. 1 Diagram of anion-
backbone
exchange resin

+ +

+ + active group


+ active group (fixed group)

+
free ion
+

(concentration of A in solution/concentration of then cooled to room temperature in order to alter


B in solution). the material properties. The annealing process is
In general, introducing ionic groups could start time and temperature dependent.
with a monomer containing a moiety, a polymer Annealing of polymers is a heating of a poly-
lm, or start with polymers or polymer meric part to below its glass transition temperature
blends (Helfferich 1962; Strathmann 2004). As in order to relieve the internal stresses introduced
summarized in our recent book chapter, the during its fabrication (molding, cooling after
specic implementation methods include molding, machining, welding, etc.).
(1) amidoalkylation of cross-linking polystyrene, Annealing of conjugated polymers and poly-
(2) copolymerization of (chloromethyl) styrene, mer blend lms is a widely used process that
(3) chloroacetylation of polymers, (4) acetylation achieves optimal lm morphology and therefore
of cross-linked polystyrene, and (5) grafting improves material properties, such as electrical
vinylbenzyl ammonium chloride onto inert poly- mobility for photovoltaic devices and other appli-
mers (Xu 2009). cations. Annealing of ion-conducting polymers
reduces the excessive swelling observed in pres-
ence of water.
References
In particular, annealing is used (Young and
Helfferich FG (1962) Ion exchange. Dover Publications Lovell 1991):
Strathmann H (2004) Ion-exchange membrane separation
processes. Elsevier Science (a) To increase the melting point of some poly-
Xu T (2009) Advances in membrane science and technol-
ogy. Nova Science mers because it facilitates the melting of small
and irregular crystals in favor of larger and
better formed ones
(b) To reduce or cancel deformations previously
Annealing of Polymer Membranes provoked at higher temperature which remain
as frozen (permanent) deformations when the
Maria Luisa Di Vona material is cooled to room temperature
Dip. Di Scienze Technologie Chimiche, (c) To increase crystallization
University of Rome Tor Vergata, Rome, Italy (d) To decrease the free volume between poly-
meric chains thus inducing a mechanical sta-
bilization of polymeric materials
Annealing can be dened as a process where a
material undergoes a heat treatment to a certain Annealing of liquid crystalline polymers
temperature, is kept there for a denite time, and is between the glass transition temperature and the
Antibiological Fouling Surface 81

melting temperature leads to an increased level of the crystallization temperature (Tc) and it became
crystallinity and increased crystalline perfection clear that the annealing temperature cannot be
analogous to the behavior of conventional semi- higher than the melting temperature (Tm) of the A
crystalline polymers. Annealing at or above the semicrystalline phase.
melting point also leads to enhanced crystallinity
and crystalline perfection.
The annealing of semicrystalline polymers References
may change the crystal structure, the degree of
crystallinity, the perfection of the crystals, the Alberti G, Narducci R, Di Vona ML, Giancola S (2013)
Annealing of Naon 1100 in the presence of an
orientation of both crystalline and amorphous
annealing agent: a powerful method for increasing
phases, their contiguous structural morphology, ionomer working temperature in PEMFCs. Fuel Cells
and the number of tie chains between the crystal- 13:4247
lites. Morphological changes are also observed on Young RJ, Lovell PA (1991) Introduction to polymers,
2nd edn. CRC Press, Boca Raton
annealing bulk-crystallized samples. Polymor-
phism may result due to annealing crystalline
polymers as its one crystalline form transforms
into another. The concept that mechanical stabili-
zation was due to a generic decrease of the free Antibiological Fouling Surface
volume between ionomer chains when thermally
treated was abandoned and replaced by the con- Franois Perreault
sideration that the mechanical stabilization was School of Sustainable Engineering and the Built
induced by an increased crystallization of a Environment, Arizona State University, Tempe,
preexisting semicrystalline phase (Alberti AZ, USA
et al. 2013).
Thermal annealing is a simple route for stabi-
lizing glassy polymers via the densication of Antibiological fouling surface is a surface hav-
their polymer chains and is accomplished through ing the property to resist the attachment or prolif-
thermal treatment of the glassy thermoplastics. eration of living organisms. In membrane
For amorphous polymers, the thermal treatment systems, the main organisms of concern for
can play a very important role in changing the biological fouling are microorganisms. Anti-
morphology. If the temperature is lower than the biological fouling membranes may resist biologi-
glass transition temperature Tg, the polymer cal fouling, or biofouling, by three main
chains are mainly immobile, thereby maintaining mechanisms: reducing the attachment of microor-
the existing morphology; however, if the ganisms to the surface, killing the microorganisms
annealing temperature is greater than the Tg, the to prevent their multiplication, or inhibiting
polymer chains will relax. It has been found that their proliferation on the membrane surface
the morphology can be modied upon annealing (De Kwaadsteniet et al. 2011).
at a temperature higher than the Tg, thus changing Biological fouling can be reduced by reducing
the physical properties of the polymers. the adhesion of microorganisms and biological
A certain amount of molecular rearrangement foulants to the membrane. Adhesion of foulants
must take place during crystallization but this on a membrane depends on the physicochemical
rearrangement cannot arise through large-scale properties of the surface and is increased with
molecular diffusion as the process is occurring in higher surface roughness, hydrophobicity, and
the solid state. Thermal treatments were believed electrostatic charge. Surface roughness increases
to be more and more efcient as the temperature fouling by increasing the contact area between the
increases and therefore empirical short treatments cell and the surface (Vrijenhoek et al. 2001). Strat-
were performed at high temperatures. Thus, the egies to reduce the surface roughness include
annealing temperature (Tann) was connected with changes in the fabrication procedure or lling
82 Antibiotic Production by Membrane Operations

the valleys of the surface with polymers or Such compounds can be directly attached to the
nanomaterials (Rana and Matsuura 2010). Hydro- membrane or included in a slow-release platform
phobic surfaces increase fouling due to the hydro- such as polymeric particle (Glinel et al. 2012).
phobic nature of most biological foulants.
Increase in the hydrophilicity of a surface gener-
ates a hydrated layer that reduces the adhesion of References
hydrophobic proteins and microorganisms. To
achieve a more hydrophilic surface, the mem- Banerjee I, Pangule RC, Kane RS (2011) Antifouling coat-
ings: recent developments in the design of surfaces that
brane may be coated or functionalized with hydro-
prevent fouling by proteins, bacteria, and marine organ-
philic polymers and nanomaterials or chemically isms. Adv Mater 23:690718
modied by treating the membrane with plasma, De Kwaadsteniet M, Botes M, Cloete TE (2011) Applica-
UV light, different acids or bases, and oxidizing tion of nanotechnology in antimicrobial coatings in the
water industry. Nano 6:395407
agents (Rana and Matsuura 2010). Electrostatic
Glinel K, Thebault P, Humblot V, Pradier CM, Jouenne
interactions may increase the adhesion of micro- T (2012) Antibacterial surfaces developed from
organisms on the membrane. Proteins and micro- bio-inspired approaches. Acta Biomater 8:16701684
bial cells are generally negatively charged in Rana D, Matsuura T (2010) Surface modications for
antifouling membranes. Chem Rev 110:24482471
natural pH. Therefore, lowering the surface
Vrijenhoek EM, Hong S, Elimelech M (2001) Inuence of
charge may decrease foulant adhesion by increas- membrane surface properties on initial rate of colloidal
ing the electrostatic repulsion. The surface charge fouling of reverse osmosis and nanoltration mem-
of a membrane can be modied by changing the branes. J Membr Sci 188:115128
nature of the functional groups present on the
membrane surface (Rana and Matsuura 2010).
Finally, adhesion of biological foulants and
microorganisms may be decreased by surface Antibiotic Production by Membrane
modication with polymer brushes. The use of Operations
long-chain molecules such as polyethylene glycol
increases steric repulsion between foulants and Cristiana Boi
the membrane surface (Banerjee et al. 2011). Dipartimento di Ingegneria Civile, Chimica,
The antifouling effectiveness of the polymer Ambientale e dei Materiali, Universit di
brushes depends on the length and density of the Bologna, Bologna, Italy
polymer layer.
Biological fouling can be reduced by
inactivating microorganisms in order to prevent Synonyms
their development on the membrane surface. Anti-
microbial compounds can be integrated in a mem- Membranes in antibiotic production
brane by including them in the polymer solution
during membrane fabrication or by post- Antibiotics are medicines produced by fermenta-
fabrication membrane functionalization. These tion that ght bacterial infections; they can either
antimicrobial compounds may be biocide- kill other microorganisms or inhibit their growth.
releasing materials, contact-action antimicrobial The development of antibiotics started with the
agents, or photocatalytic materials (Banerjee discovery of penicillin by Fleming in 1928 that
et al. 2011). gave rise to many other discoveries in the subse-
Biological fouling may be reduced by quent 40 years. The number of new antibiotics on
preventing the development of microbial commu- the market had a steady increase until the 1980s,
nities without directly killing the microorganisms. but the unrestrained use of antibiotics led to the
This is accomplished by using bacteriostatic or emergence of antibiotic-resistant pathogens and
quorum-sensing inhibitors that prevent the assem- the number of approved antibiotics decreased
bly of deposited microorganisms into a biolm. constantly in the last 30 years (Coates
Antifouling Membrane Surface 83

et al. 2011). The research for therapeutics may also be used. The introduction of an ultral-
endowed with a broaden antimicrobial range tration step greatly improves the extraction pro-
brought to the development of semisynthetic anti- cess (Koltuniewicz 2010). A
biotics which are produced by chemical or enzy- Other membrane technologies like membrane
matic transformation of penicillin and contactors, liquid membranes, and membrane bio-
cephalosporins (Srirangan et al. 2013). Penicillin reactors are less established; however, they have
is still one of the antibiotics with the largest annual great potential for industrial applications in anti-
bulk production; it is part of the b-lactam antibi- biotic production.
otic class, with about 15 billion US$ annual sales
and a market share of about 65 % of the total
world antibiotic market (Elander 2003). References
The production of antibiotics typically
involves a series of process steps consisting of Coates ARM, Halls G, Hu Y (2011) Novel classes of
antibiotics or more of the same? Br J Pharmacol
fermentation, removal of biomass, purication,
163:184194
and crystallization (Koltuniewicz 2010). Mem- Elander RP (2003) Industrial production of ?-lactam anti-
brane operations can be integrated within this biotics. Appl Microbiol Biotechnol 61:385392
process sequence, both in the upstream and in Koltuniewicz A (2010) Integrated membrane operations in
various industrial sectors. In: Drioli E, Giorno L (eds)
the downstream processing, for production of
Comprehensive membrane science and engineering,
either natural or semisynthetic antibiotics. vol 4. Elsevier, Oxford, pp 109164
In upstream processing, membranes are uti- Lipnizki F (2010) Basic aspects and applications of mem-
lized for ancillary operations and, in particular, brane processes. In: Drioli E, Giorno L (eds) Compre-
hensive membrane science and engineering,
for sterile ltration of culture media and air
vol 4. Elsevier, Oxford, pp 165194
which is supplied as a source of oxygen for aero- Srirangan K, Orr V, Akawi L, Wesrbrook A,
bic fermentation, whereas in the downstream part Moo-Young M, Perry Chou C (2013) Biotechnological
of the process, they can be utilized as alternative advances on penicillin G acylase: pharmaceutical
implications, unique expression mechanism and pro-
unit operations. In the dowstream section,
duction strategies. Biotecnol Adv 31:13191332
membranes can be applied for cell harvest,
clarication, and concentration. Among the mem-
brane technologies used for recovery and puri-
cation, crossow microltration and ultraltration
can be employed for biomass separation, often in
combination with dialtration to improve product Antifouling Membrane Surface
yield and purity (Lipnizki 2010).
Antibiotic recovery from fermentation broths Zhongyi Jiang1, Jinming Peng2, Xueting Zhao1,
can be done directly if the product is extracellular, Yanlei Su1 and Hong Wu1
1
as in penicillin production, or following cell dis- School of Chemical Engineering and
ruption if the product is intracellular, as for some Technology, Tianjin University, Nankai, Tianjin,
tetracyclines. Since antibiotics are relatively small China
2
molecules, with molecular weights of less than Key Laboratory for Green Chemical Technology
2,000 amu, the MF/UF membrane retains the bio- of Ministry of Education, School of Chemical
mass or the cell debris when the antibiotic is an Engineering and Technology, Tianjin University,
intracellular products, while the antibiotics are Tianjin, China
found in the permeate side. The claried antibiotic
stream can then be concentrated with
nanoltration and/or reverse osmosis (Lipnizki The term fouling generally refers to an undesir-
2010). Purication of antibiotics is generally car- able process in which a surface becomes
ried out with solvent extraction, but depending on encrusted due to the undesirable accumulation
the target molecule, absorption or precipitation of foulants, such as biomacromolecules,
84 Antifouling Membrane Surface

microorganisms, hydrocarbons, particles, and col- (Callow and Callow 2011). The hydrophilic mem-
loids from the surrounding environment. Anti- brane surface can resist the fouling caused by
fouling surface, also referred to as a stealth biomacromolecules and natural organic matter.
surface, can minimize the intermolecular forces The hydrophobic surface is based on nonpolar,
of interactions between the foulants and the syn- low surface energy hydrophobic polymers, such
thetic surface so that the foulants can be easily as poly(dimethylsiloxane) (PDMS) elastomers
released under low shear stresses. Antifouling and uoropolymers. The mechanism of this
surfaces lie at the heart of several contemporary hydrophobic surface is that polar molecules
and advanced technologies, ranging from coat- (including adhesive protein) barely adhere to
ings for ship hulls, biomedical implants, biosen- membrane surface because of reduced opportuni-
sors, drug delivery, and membrane separations. ties for forming the hydrogen-bonding and polar
Antifouling membrane surface is one kind of anti- interactions. This hydrophobic surface aims to
fouling surfaces. The antifouling surface is often weaken the interfacial bonds so that the attached
relevant to membranes utilized in microltration, foulants are more readily removed by hydraulic
ultraltration, nanoltration, and reverse osmosis. shear forces, not prevent foulants from attaching,
The major foulants are different for different which is known as fouling release. The hydro-
membrane processes. The main foulants are phobic membrane surface is suitable for mitigat-
microorganisms and emulsied oils for ing the microorganism and hydrocarbon fouling.
microltration, biomacromolecules and colloids The amphiphilic surface comprising hydrophilic
for ultraltration, natural organic matters for domains and hydrophobic domains on membrane
nanoltration, inorganic salts and bioorganic/ surface incorporates some of the benets of both
organic substances for reverse osmosis. hydrophobic and hydrophilic surfaces. The gen-
All the strategies for construction of antifoul- eral aim is to create a dynamic and compositional
ing membrane surface are based on manipulating surface complexity that deters settlement of
the physicochemical and/or topography structure foulants and reduces the interfacial bonding with
of membrane surface to weaken the interactions membrane surface. The general aim of amphi-
between foulants and membrane surface and thus philic surface is to combine the nonpolar, low
inhibiting foulants adsorption or settlement. There surface energy properties of hydrophobic
are four major types of antifouling membrane domains to reduce polar and hydrogen-bonding
surfaces, including hydrophilic surface, hydro- interactions with foulants, with the well-known
phobic surface, amphiphilic surface, and reactive protein repellency properties of the hydrophilic
surface. Whitesides (Ostuni et al. 2001) rst pro- domains. The resulting amphiphilic surface may
posed that antifouling surface showing resistance lower the entropic and enthalpic driving forces for
to protein should have the following four attri- the adsorption of the protein and organism. The
butes: hydrophilic, hydrogen-bond acceptors but amphiphilic membrane surface can defer the foul-
not hydrogen-bond donors, and overall electri- ing caused by microorganisms, biomacro-
cally neutral. Poly(ethylene glycol) (PEG)-based molecules, natural organic matter, and
polymers and zwitterionic polymers are the most hydrocarbons. Therefore, the amphiphilic mem-
widely used materials to fabricate antifouling brane surface is the most promising antifouling
membranes. The antifouling mechanism of the membrane surface for the practical separation sys-
PEG-based polymers can be mainly ascribed to tem containing a wide range of foulants. The
the large repulsive hydration forces of tightly reactive surface immobilizes the component
bound water layer around the polymer chains via which can degrade organic composition of
hydrogen bonds or electrostatic attraction. The foulants on membrane surface. The proteases
objective of hydrophilic surface is to prevent the and titania nanoparticles are often immobilized
foulants from attaching onto the membrane sur- on membrane surface, thus preventing biomacro-
face, which is known as fouling resistance molecules and microorganism fouling via
Antimicrobial Activity 85

enzymatic or photocatalytic degradation References


(Banerjee et al. 2011).
Several modication approaches are employed Banerjee I, Pangule RC, Kane RS (2011) Antifouling coat-
ings: recent developments in the design of surface that A
to create antifouling membrane surface including
prevent fouling by proteins, bacteria, and marine organ-
surface coating, surface grafting, and surface seg- isms. Adv Mater 23:690718
regation (Shannon et al. 2008; Rana and Matsuura Callow JA, Callow ME (2011) Trends in the development
2010; Wang et al. 2005). For surface coating, of environmentally friendly fouling-resistant marine
coatings. Nat Commun 2:244253
membranes are immersed in a polymer modier
Ostuni E, Chapman RG, Holmlin RE, Takayama S,
solution or inorganic particles suspension. The Whitesides GM (2001) A survey of structure-property
modier is settled on membrane surface to create relationships of surfaces that resist the adsorption of
antifouling coating through van der Waals force or protein. Langmuir 17:56055620
Rana D, Matsuura T (2010) Surface modication for anti-
electrostatic interactions. For surface grafting, the
fouling membranes. Chem Rev 110:24482474
modier is settled on membrane surface via graft Shannon MA, Bohn PW, Elimelech M, Georgiadis JG,
polymerization including graft-to and graft-from Marinas BJ, Mayes AM (2008) Science and technology
approach. The termed graft-to approaches consist for water purication in the coming decades. Science
452:301310
of the grafting of the pre-synthesized polymer
Wang YQ, Wang T, Su YL, Peng FB, Wu H, Jiang ZY
chains with a reactive terminal group. Alterna- (2005) Remarkable reduction of irreversible fouling
tively, graft-from approaches, in which a poly- and improvement of the permeation properties of poly
mer is grown in situ from the surface via a (ether sulfone) ultraltration membranes by blending
with Pluronic F127. Langmuir 21:185611862
surface-adsorbed initiation group, are generally
capable of producing denser polymer layers. The
surface coating and surface grafting belong to the
post-modication approach, whereas surface
segregation belongs to the in situ modication Antimicrobial Activity
approach. The polymer modiers comprising
hydrophobic backbones and hydrophilic side Franois Perreault
chains are added to casting solution, lining mem- School of Sustainable Engineering and the Built
brane surfaces, and internal pore during the con- Environment, Arizona State University, Tempe,
ventional phase inversion process. The AZ, USA
hydrophilic chains segregate to membrane sur-
face and endow membrane with surface hydro-
philicity and antifouling property, while Antimicrobial activity of a compound is dened
hydrophobic backbones anchor to membrane as its capacity to prevent the development of
matrix polymers to defer loss of modier during microorganisms. Antimicrobial compounds can
phase inversion process. be divided into two main categories according to
The fouling resistance property could be eval- their mechanisms of antimicrobial action: bacteri-
uated by ux recovery ratio (FRR), while the cidal and bacteriostatic. Bactericidal agents act by
fouling release property could be evaluated by killing bacterial cells. Common bactericidal
ux decline ratio (FDR). The ux recovery ratio mechanisms include inhibition of cell wall syn-
(FRR) is the ratio of the water ux after hydraulic thesis, disruption of the cytoplasmic membrane,
cleaning to initial water ux, while the ux and inhibition of nucleic acid synthesis. Bacterio-
decline ratio is the ratio of ux decline (the initial static agents are compounds that prevent micro-
water ux minus the ux for real feed) to initial bial development by inhibiting specic metabolic
water ux. The higher the value of FRR, the better pathways, thus preventing cell growth and multi-
the fouling resistance property of the membrane; plication. Bacteriostatic agents act by inhibiting
the lower the FDR, the better the fouling release protein synthesis, by acting on the 30S, 50S, or
property of the membranes. 70S ribosomal complexes, or by inhibiting other
86 Antimicrobial Membrane

essential metabolic pathways such as folic acid polycations, silver and metal oxide nanoparticles,
synthesis. Bacteriostatic effect is reversible and carbon nanomaterials, biocide-releasing poly-
bacteria can proliferate once the bacteriostatic meric structures, and photoactive materials
agent is removed (McCarter 2005). (Banerjee et al. 2011).
Methods to evaluate the antimicrobial activity
can be divided into two categories: diffusion
methods and dilution methods. Diffusion References
methods, also called agar diffusion methods,
depend on the diffusion of an antimicrobial com- Banerjee I, Pangule RC, Kane RS (2011) Antifouling coat-
ings: recent developments in the design of surfaces that
pound in an agar plate covered by a bacterial lawn.
prevent fouling by proteins, bacteria, and marine organ-
Antimicrobial activity is measured in terms of the isms. Adv Mater 23:690718
diameter of the zone of inhibition, where bacterial Matin A, Khan Z, Zaidi SMJ, Boyce MC (2011) Biofouling
growth is inhibited. The most common agar dif- in reverse osmosis membranes for seawater desalina-
tion: phenomena and prevention. Desalination
fusion assay is the Kirby-Bauer assay. Dilution
281:116
methods aim to determine the minimum inhibi- McCarter YS (2005) Antimicrobial modes of action. In:
tory concentration of a compound, dened as the Coyle MB (ed) Manual of antimicrobial susceptibility
minimal concentration that completely inhibits testing. American Society for Microbiology, Washing-
ton, DC
microbial growth, by incubating a dened quan-
tity of bacteria with different dilutions of an anti-
microbial compound. Dilution methods can be
performed in culture broth or in agar media.
In membrane processes, antimicrobial com- Antimicrobial Membrane
pounds are used to reduce microbial growth and
biological membrane fouling. Antimicrobial com- Jun Yin and Baolin Deng
pounds can be introduced in the feed efuent Department of Civil and Environmental
continuously or intermittently, during membrane Engineering, University of Missouri-Columbia,
cleaning stages, to kill microorganisms and Columbia, MO, USA
reduce biolm development (Matin et al. 2011).
Traditional approach using chlorine-based disin-
fectants is usually effective to control biolm Antimicrobial membrane (also called antibacterial
development; however, chlorine disinfection membrane or anti-biofouling membrane) is a
leads to the formation of undesirable and carcino- membrane capable of reducing or inhibiting
genic disinfection by-products. Additionally, microbial growth on its surface. The biocidal abil-
chlorine is not compatible with polyamide thin- ity of the antimicrobial membrane can generally
lm composite membranes due to the susceptibil- be exerted by (1) active amphiphilic polymers or
ity of the aromatic polyamide layer to chlorine synthetic mimics of naturally occurring
attack. Alternative strategies to disinfection of antibacterial peptides, (2) microbe-repelling anti-
the feed efuent include ozone, UV treatments, adhesive polymers, and (3) composite materials
or advanced oxidation processes, which produce containing various slow-releasing biocides
less disinfection by-products but are limited by (Sambhy et al. 2006; Yin and Deng 2015).
their higher cost compared to chlorine. Microbial
growth and biolm development may also be
reduced by imparting antimicrobial properties Why Antimicrobial Membrane Is
directly to the membrane by modication with Important?
antimicrobial compounds. Antimicrobial coating
of membranes can be achieved using different Membrane biofouling due to the microbial growth
types of antimicrobial compounds, such as anti- and biolm formation is one of the most challeng-
microbial polymers, antimicrobial peptides, ing issues in membrane separation for water and
Antimicrobial Membrane 87

wastewater treatment (Zhu et al. 2010). This Recently, Cu is explored as an alternative of Ag


undesirable phenomenon decreases membrane due to its relatively low cost and decent biocidal
permeability, reduces permeate quality, and property. The antimicrobial property of TiO2 is A
increases energy consumption of the separation driven by the photocatalytic reaction, where light
process. It is therefore critical to develop anti- irradiation is necessary.
microbial membranes that will most likely
increase membrane efciency and application
duration. In addition, use of antimicrobial
Fabrication and Modification Methods
membrane is important to provide pathogen-
free clean water.
The antimicrobial functionalization of mem-
branes could be implemented through procedures
including blending, surface coating, or grafting. In
Commonly Used Biocidal Agents
the blending approach, biocidal agents are mixed
for Membrane Modification
with polymer solution during the membrane fab-
rication. In the coating or grafting approach, bio-
Biocidal agents that could be used for water treat-
cidal agents are attached onto membrane surface
ment include quaternary ammonium compounds
through adsorption, deposition, electrostatic
(QACs), metal ions or nanoparticles (NPs) such as
attraction, or chemical bonding. For instance, Ag
silver (Ag) and copper (Cu), titanium dioxide
NPs or Cu NPs could be encapsulated in posi-
(TiO2), and so on.
tively charged polyethylenimine (PEI) and then
QACs possess good antibacterial properties,
attached onto a negatively charged membrane
low toxicity, environmentally friendly perfor-
surface (Mauter et al. 2011; Ben-Sasson
mance, and excellent cell membrane penetration
et al. 2014). In order to improve the durability of
properties (Song et al. 2011).
antimicrobial function, Ag NPs can also be
Silver ions/NPs and silver-based compounds
attached onto thin-lm composite (TFC) mem-
have excellent biocidal properties and are widely
branes through chemical bonding, resulting in
used to prepare antimicrobial plastics, coatings,
membranes with excellent antimicrobial proper-
and wound and burn dressing, etc. They could
ties and reduced membrane biofouling (Fig. 1, Yin
inhibit the growth of microbes through multiple
et al. 2013).
pathways. Firstly, released Ag+ ions could interact
with disulde or thiol groups of enzymes or DNA
and then disrupt microbial metabolic processes,
generate reactive oxygen species, or interrupt rep- Challenges
lication of DNA (Russell and Hugo 1994; Feng
et al. 2000; Matsumura et al. 2003), leading to the Antimicrobial membrane has attracted much
damage or even the death of bacterial cells. attention due to its demonstrated resistance to
Secondly, Ag NPs can attach to the surface of membrane biofouling. However, several chal-
the cell membrane and disturb its proper func- lenges need to be addressed in its practical appli-
tion including destabilizing the outer mem- cations. For long-term application, the loss of
brane, collapsing the plasma membrane antimicrobial activity due to the depletion of bio-
potential, and depleting the levels of intracellu- cidal agents or insufcient contact between bac-
lar ATP (Sondi and Salopek-Sondi 2004; Lok teria and biocide caused by other foulants
et al. 2006; Choi et al. 2008). Thirdly, Ag NPs necessitates frequent recharging and cleaning of
with smaller particle size (110 nm) are able to membranes. How to attach biocidal agents onto
penetrate inside the bacteria and cause further membrane and control their release in a most
damage by possibly interacting with sulfur- and effective way should be further explored. For
phosphorus-containing compounds such as commercial applications, there is a need to con-
DNA (Morones et al. 2005). sider cost-effectiveness of attaching biocidal
88 Antimicrobial Membrane

Antimicrobial Membrane, Fig. 1 SEM image of membrane surface (1) and TEM image of membrane cross section (2)
(Yin et al. 2013)

agents onto a membrane and recharging them as Matsumura Y, Yoshikata K, Kunisaki SI, Tsuchido
needed. T (2003) Mode of bactericidal action of silver zeolite
and its comparison with that of silver nitrate. Appl
Environ Microbiol 69:42784281
Mauter MS, Wang Y, Okemgbo KC, Osuji CO, Giannelis
Cross-References EP, Elimelech M (2011) Antifouling ultraltration mem-
branes via post-fabrication grafting of biocidal
Antifouling Membrane Surface nanomaterials. ACS Appl Mater Interfaces 3:28612868
Morones JR, Elechiguerra JL, Camacho A, Holt K, Kouri
Bacterial Biolm Formation JB, Ramrez JT, Yacaman MJ (2005) The bactericidal
Cross-Linked Aromatic Polyamide Membranes effect of silver nanoparticles. Nanotechnology
Inorganic Fillers 16:23462353
Mixed Matrix Membranes (MMMs) Russell AD, Hugo WB (1994) Antimicrobial activity and
action of silver. Prog Med Chem 31:351370
Nanocomposite Membranes Sambhy V, MacBride MM, Peterson BR, Sen A (2006)
Silver bromide nanoparticle/polymer composites: dual
action tunable antimicrobial materials. J Am Chem Soc
References 128(30):97989808
Sondi I, Salopek-Sondi B (2004) Silver nanoparticles as
Ben-Sasson M, Zodrow KR, Genggeng Q, Kang Y, antimicrobial agent: a case study on E. coli as a model
Giannelis EP, Elimelech M (2014) Surface functiona- for Gram-negative bacteria. J Colloid Interface Sci
lization of thin-lm composite membranes with copper 275:177182
nanoparticles for antimicrobial surface properties. Song J, Kong H, Jang J (2011) Bacterial adhesion inhibition
Environ Sci Tech 48:384393 of the quaternary ammonium functionalized silica
Choi O, Deng KK, Kim NJ, Ross L Jr, Surampalli RY, Hu nanoparticles. Colloids Surf B Biointerfaces 82:651656
Z (2008) The inhibitory effects of silver nanoparticles, Yin J, Deng B (2015) Polymer-matrix nanocomposite
silver ions, and silver chloride colloids on microbial membrane for water treatment. J Membr Sci 479:
growth. Water Res 42:30663074 256275
Feng QL, Wu J, Chen GQ, Cui FZ, Kim TN, Kim JO Yin J, Yang Y, Hu Z, Deng B (2013) Attachment of silver
(2000) A mechanistic study of the antibacterial effect nanoparticles (AgNPs) onto thin-lm composite (TFC)
of silver ions on Escherichia coli and Staphylococcus membranes through covalent bonding to reduce mem-
aureus. J Biomed Mater Res 52:662668 brane biofouling. J Membr Sci 441:7382
Lok CN, Ho CM, Chen R, He QY, Yu WY, Sun H, Tam Zhu X, Bai R, Wee KH, Liu C, Tang SL (2010) Membrane
PKH, Chiu JF, Che CM (2006) Proteomic analysis of surfaces immobilized with ionic or reduced silver and
the mode of antibacterial action of silver nanoparticles. their anti-biofouling performances. J Membr Sci
J Proteome Res 5:916924 363:278286
Antimicrobial Properties of Membranes 89

upon interaction with cell wall components or


Antimicrobial Properties penetration through the cytoplasmic membrane.
of Membranes This mechanism does not deplete over time and A
may be effective as long as a direct contact
Francois Perreault between the cell and the membrane surface is
School of Sustainable Engineering and the Built provided.
Environment, Arizona State University, Tempe, Photocatalytic materials generate reactive oxy-
AZ, USA gen species upon exposure to visible or ultraviolet
light. Their main applications in membrane pro-
cesses are contaminant degradation and disinfec-
Antimicrobial properties of membrane improve tion, where the membrane serves as a support to
the membrane resistance to biological fouling. immobilize photocatalysts. The generation of
Antimicrobial properties can be provided to mem- reactive oxygen species by these materials causes
branes by modication with different types of bacterial inactivation by inducing oxidative dam-
antimicrobial compounds, which can be divided age to cell membranes, proteins, and nucleic
into three categories based on their mechanisms of acids, leading to cell death. Integration of
bacterial inactivation: biocide-releasing com- photocatalytic materials into membranes therefore
pounds, contact-action antimicrobial agents, and improves the antimicrobial properties of the mem-
photocatalytic materials. brane (Kwak and Kim 2001). Several compounds
Biocide-releasing materials inactivate microor- may be light-activated to generate reactive oxygen
ganisms by the release of biocide in the vicinity of species. Among them are dyes likes rose bengal,
the membrane. Common examples of biocide- porphyrins, and toluidine blue and particles such
releasing compounds used for antimicrobial coat- as TiO2 and fullerene (Banerjee et al. 2011). The
ings are silver nanoparticles, metal oxide most common photocatalytic material used in
nanoparticles, and polymeric capsules (Banerjee membrane processes is TiO2 due to its low cost,
et al. 2011). Biocide-releasing materials may be durability, and self-cleaning properties.
included in the polymer solutions during fabrica-
tion or attached to the membrane via post-
fabrication membrane modication. Embedding
the biocide in the depth of the membrane may References
however limit its diffusion to the microorganisms
and therefore decrease the antimicrobial activity Banerjee I, Pangule RC, Kane RS (2011) Antifouling coat-
ings: recent developments in the design of surfaces that
of the modied membrane (Zodrow et al. 2009). prevent fouling by proteins, bacteria, and marine organ-
To maximize the effectiveness of biocide release, isms. Adv Mater 23:690718
surface attachment of biocide can be preferred Kwak S-Y, Kim S (2001) Hybrid organic/inorganic reverse
(Mauter et al. 2011). A limitation to biocide- osmosis (RO) membrane for bactericidal anti-fouling.
1. Preparation and characterization of TiO2 nanoparti-
release materials is the eventual depletion of the cle self-assembled aromatic polyamide thin-lm-
biocide and loss of antimicrobial activity. composite (TFC) membrane. Environ Sci Technol
Contact-action antimicrobials are compounds 35:23882394
that require direct contact with microorganisms Mauter MS, Wang Y, Okemgbo KC, Osuji CO, Giannelis
EP, Elimelech M (2011) Antifouling ultraltration
for cell inactivation. Examples of contact-action membranes via post-fabrication grafting of biocidal
antimicrobial materials are antimicrobial nanomaterials. ACS Appl Mater Interfaces
peptides, enzymes, polycationic polymers, and 3:28612868
nanomaterials such as carbon nanomaterials Zodrow K, Brunet L, Mahendra S, Li D, Zhang A, Li Q,
Alvarez PJJ (2009) Polysulfone ultraltration mem-
(Banerjee et al. 2011). A common mechanism of branes impregnated with silver nanoparticles show
cell inactivation by contact-action antimicrobial improved biofouling resistance and virus removal.
compounds is the disruption of cell integrity Water Res 43:715723
90 Antioxidant Recovery by Membranes

improve the efciency of antioxidant production


Antioxidant Recovery by Membranes (Table 1).

Laurent Bazinet Pressure-Driven Membrane Processes


Department of Food Sciences, Universit Laval, Pressure-driven membrane technologies are often
Quebec, QC, Canada used in the food industry to isolate antioxidant
molecules such as specic peptides or peptide
fractions (Bazinet and Firdaous 2012; Pouliot
Antioxidants and Membrane Processes et al. 2000; Tessier et al. 2006a, b; Vandanjon
et al. 2009) and phenolic compounds (Nawaz
Antioxidants are natural or synthesized sub- et al. 2006; Kalbasi and Cisneros-Zevallos 2007;
stances that inhibit or retard the oxidation of Mello et al. 2010; Tylkowski et al. 2010). Pressure
other molecules (fat, oil, food, petroleum is the main driving force for these processes. The
product. . .) (Focke et al. 2012; Rozoy pressure used depends on the pore size of the
et al. 2012; Roblet et al. 2012). However, for ltration membrane and has to be adjusted as a
natural antioxidants, which are present in complex function of the concentration rate desired.
matrices, their separation and purication are Pressure-driven membrane processes comprise
required. Indeed, they must be separated from microltration (MF), ultraltration (UF),
the feedstock in order to increase their purity and nanoltration (NF), and reverse osmosis (RO).
antioxidant capacity. The solution properties, charges of ionic species
Membrane processes are the main processes and the type of membrane used, affect the behav-
used for the separation of antioxidant molecules. ior and the efciency of the separation method
Membranes are selective barriers that allow for (Martin-Orue et al. 1998). Working at low con-
the transmission of certain feed components centration is preferable to avoid the formation of a
while retaining other components. Membrane polarization layer which could affect selectivity of
technology can be used to concentrate and/or the membrane (Shahidi 2004).
selectively fractionate bioactive compounds For the separation of tocopherols and
with antioxidant activity from aqueous and alco- tocotrienols, only MF (de Souza et al. 2008) and
holic processing streams of products, NF (Subramanian et al. 1998a, b, 2003) were
by-products, and wastes from agro-food indus- reported. For phenols recovery, MF was used on
try (Diaz-Reinoso et al. 2011). It is important to vegetation waters (VW) (Russo 2007) and pine-
note that, when compared with other concentra- apple juice (Laorko et al. (2010). The authors
tion methods (evaporation, spray drying. . .), showed that MF did not affect signicantly the
during membrane processes the product is not pH, reducing sugar and acidity of claried juice
subjected to high temperatures and there is no whereas the suspended solids and microorganism
change in the physical state of the solvent, were completely removed. UF was studied on
meaning that the functional properties of the different sources such as olive mill wastewater
compounds of interest are preserved and the (Russo 2007; El-Abbassi 2012), fruit juices
process as a whole is energy saving (Negrao (Borneman et al. 2001; Cassano et al. 2008;
Murakami et al. 2011). Laorko et al. 2010; Ciss et al. 2011; Conidi
et al. 2011), grape seeds (Nawaz et al. 2006),
and green tea (Li et al. 2005). NF was tested on
Membrane Processes and Applications roselle extract (Ciss et al. 2011), on mate (Negrao
to Antioxidant Recovery Murakami et al. 2011), on aqueous propolis
extract (Mello et al. 2010), and on bergamot
On a large production scale, pressure-driven juice (Conidi et al. 2011). Organic acids such as
membrane technologies and electrically driven Ascorbic, isoascorbic, folic, and citric acids can
membrane technologies have been developed to also be recovered by ltration process. Hence,
Antioxidant Recovery by Membranes 91

Antioxidant Recovery by Membranes, Table 1 Membrane processes for separation/concentration of different types
of antioxidants
Driving force Membrane process Antioxidants References
A
Pressure-driven Microltration Tocopherols (de Souza et al. 2008)
membrane and
processes tocotrienols
Phenols (Russo 2007; Laorko et al. 2010)
Organic (Laorko et al. 2010)
acids
Ultraltration Phenols (Russo 2007; Laorko et al. 2010; El-Abbassi 2012;
Borneman et al. 2001; Cassano et al. 2008; Ciss
et al. 2011; Conidi et al. 2011; Nawaz et al. 2006; Li
et al. 2005)
Organic (Cassano et al. 2006)
acids
Peptides (Bouhallab and Touz 1995; Lajoie et al. 2001;
Vandanjon et al. 2007)
Nanoltration Tocopherols (Subramanian et al. 1998a, b, 2003)
Phenols (Ciss et al. 2011; Negrao Murakami et al. 2011; Mello
et al. 2010; Conidi et al. 2011)
Peptides (Vandanjon et al. 2007; Fenton-May et al. 1971; Tessier
et al. 2006b)
Electrically Electrodialysis Phenols (Bazinet et al. 2005)
driven membrane Organic (Vera Calle et al. 2003)
processes acids
Electrodialysis Organic (Vera Calle et al. 2002)
with bipolar acids
membranes
Electrodialysis Phenols (Labb et al. 2005; Bazinet et al. 2009, 2012)
with ltration Organic (Bazinet et al. 2012)
membranes acids
Peptides (Langevin et al. 2012)

MF was used for the recovery of ascorbic acid of molecular weight (Vandanjon et al. 2007). The
(Laorko et al. 2010), while UF was tested on use of integrated membrane system (UF/MF/RO,
kiwifruit juice to recover folic, ascorbic, and citric MF/NF, . . .) is becoming another real alternative
acids (Cassano et al. 2006). Concerning antioxi- to recover, purify, or concentrate antioxidants as it
dant peptides, they are separated into fractions is established in some recent works (Paraskeva
using membranes in the range 110 kDa et al. 2007; Russo 2007; Garcia-Castello
(Je et al. 2005; Jeon et al. 1999; Rajapakse et al. 2010; Conidi et al. 2011; Diaz-Reinoso
et al. 2005). NF can be used to concentrate hydro- et al. 2011).
lysates (Vandanjon et al. 2007; Fenton-May
et al. 1971; Tessier et al. 2006b) whereas UF Electrically Driven Membrane Processes
membranes with high MWCO (20100 kDa) are Electrically driven processes, like electrodialysis
adapted to the separation of peptides and (ED) and hybrid processes (ED with bipolar mem-
nonhydrolyzed proteins or proteolytic enzymes branes (EDBM) and ED with ltration mem-
(Bouhallab and Touz 1995; Lajoie et al. 2001). branes (EDFM)), use ion-exchange membranes
On the other hand, UF membranes with interme- and/or ltration membrane to separate molecules
diate molecular weight cutoffs (about (Bazinet 2005). The electric eld is the main
40008000 Da) allow hydrolysates to be fraction- driving force involved in these processes. Molec-
ated with the result of enrichment in some ranges ular transfer is mainly due to the charge of the
92 Antioxidant Recovery by Membranes

molecule and the ux depends on the strength of EDFM recovered larger range of peptide molec-
the electric eld (Poulin et al. 2007; Doyen ular weights and amount of polar amino acids.
et al. 2012).
Conventional electrodialysis has been tested
as a mean of selectively extracting polyphenols
from aqueous tobacco extracts (Bazinet References
et al. 2005). High polyphenol migration rates
around 31.190.8 % were reported. EDFM a Bazinet L (2005) Electrodialytic phenomena and their
new electrically driven technology has been applications in the dairy industry: a review. Crit Rev
Food Sci Nutr 44:525544
recently tested for the recovery of polyphenols.
Bazinet L, Firdaous L (2013) Separation of bioactive pep-
EDFM was used on green tea to perform selective tides by membrane processes: technologies and
extraction of catechins (Labb et al. 2005) and on devices. Recent Pat Biotechnol 7 (1): 927
cranberry juice to enrich cranberry juice in its own Bazinet L, DeGrandpr Y, Porter A (2005)
Electromigration of tobacco polyphenols. Sep Purif
natural phenolic antioxidant compounds (Bazinet
Technol 41:101107
et al. 2009, 2012). For organic acids having anti- Bazinet L, Cossec C, Gaudreau H, Desjardins Y (2009)
oxidant properties,Vera Calle et al. (2003) were Production of a phenolic antioxidant enriched cran-
indirectly precursor in the use of ED for the berry juice by electrodialysis with ltration membrane.
J Agric Food Chem 57:1024510251
recovery of citric acid. In all the deacidied juices,
Bazinet L, Brianceau S, Dub P, Desjardins Y (2012) Evo-
a decrease in the citrate and malate concentrations lution of cranberry juice physico-chemical parameters
was obtained. Vera Calle et al. (2002) also tested during phenolic antioxidant enrichment by electrodial-
the deacidication of claried passion fruit juice, ysis with ltration membrane. Sep Purif Technol
87:3139
by electrodialysis with bipolar membrane
Borneman Z, Gkmen V, Nijhuis HH (2001) Selective
(EDBM). Citric acid was formed in the concen- removal of polyphenols and brown colour in apple
trate compartment by citrate ions extracted from juices using PES/PVP membranes in a single ultral-
juice and protons provided by the BM separating tration process. Sep Purif Technol 2223:5361
Bouhallab S, Touz C (1995) Continuous hydrolysis of
the concentrate and electrode compartments. This
caseinomacropeptide in a membrane reactor: kinetic
conguration allowed the production of citric acid study and gram-scale production of antithrombotic
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(2006) Integrated membrane process for the production
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Ciss M, Vaillant F, Pallet D, Dornier M (2011) Selecting
juice was not signicant due to the high ratio of ultraltration and nanoltration membranes to concen-
raw juice/enriched juice. Very recently, a combi- trate anthocyanins from roselle extract (Hibiscus
nation of UF membrane stacked in an electrodial- sabdariffa L.). Food Res Int 44:26072614
Conidi C, Cassano A, Drioli E (2011) A membrane-based
ysis cell was tested successfully for the selective
study for the recovery of polyphenols from bergamot
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Antioxidant Recovery by Membranes 93

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using ultraltration membranes. Eur Food Res Technol Rajapakse N, Mendis E, Jung W-K, Je J-Y, Kim S-K
221:157162 (2005) Purication of a radical scavenging peptide
Jeon Y-J, Byun H-G, Kim S-K (1999) Improvement of from fermented mussel sauce and its antioxidant prop-
functional properties of cod frame protein hydrolysates erties. Food Res Int 38:175182
using ultraltration membranes. Process Biochem Roblet C, Amiot J, Lavigne C, Marette A, Lessard M,
35:471478 Jean J, Ramassamy C, Moresoli C, Bazinet L (2012)
Kalbasi A, Cisneros-Zevallos L (2007) Fractionation of Screening of in vitro bioactivities of a soy protein
monomeric and polymeric anthocyanins from concord hydrolysate separated by hollow ber and spiral-
grape (Vitis labrusca L.) juice by membrane ultraltra- wound ultraltration membranes. Food Res Int
tion. J Agric Food Chem 55:70367042 46:237249
Labb D, Araya-Farias M, Tremblay A, Bazinet L (2005) Rozoy E, Simard S, Liu Y, Kitts D, Lessard J, Bazinet L
Electromigration feasibility of green tea catechins. (2012) The use of cyclic voltammetry to study the
J Membr Sci 254:101109 oxidation of l-5-methyltetrahydrofolate and its preser-
Lajoie N, Gauthier SF, Pouliot Y (2001) Improved storage vation by ascorbic acid. Food Chem 132:14291435
stability of model infant formula by whey peptides Russo C (2007) A new membrane process for the selective
fractions. J Agric Food Chem 49:19992007 fractionation and total recovery of polyphenols, water
Langevin M-E, Roblet C, Moresoli C, Ramassamy C, and organic substances from vegetation waters (VW).
Bazinet L (2012) Comparative application of pressure- J Membr Sci 288:239246
and electrically-driven membrane processes for isola- Shahidi F (2004) Functional foods: their role in health
tion of bioactive peptides from soy protein hydrolysate. promotion and disease prevention. J Food Sci
J Membr Sci 403404:1524 69:146149
Laorko A, Li Z, Tongchitpakdee S, Chantachum S, Subramanian R, Nakajima M, Kawakatsu T (1998a)
Youravong W (2010) Effect of membrane property Processing of vegetable oils using polymeric composite
and operating conditions on phytochemical properties membranes. J Food Eng 38:4156
and permeate ux during clarication of pineapple Subramanian R, Nakajima M, Kimura T, Maekawa T (1998b)
juice. J Food Eng 100:514521 Membrane process for premium quality expeller-pressed
Li P, Wang Y, Ma R, Zhang X (2005) Separation of tea vegetable oils. Food Res Int 31:587593
polyphenol from green tea leaves by a combined Subramanian R, Raghavarao KSMS, Nakajima M,
CATUFM-adsorption resin process. J Food Eng Nabetani H, Yamaguchi T, Kimura T (2003) Applica-
67:253260 tion of dense membrane theory for differential perme-
Martin-Orue C, Bouhallab S, Garem A (1998) ation of vegetable oil constituents. J Food Eng
Nanoltration of amino acid and peptide solutions: 60:249256
mechanisms of separation. J Membr Sci 142:225233 Tessier B, Harscoat-Schiavo C, Marc I (2006a) Contribu-
Mello BCBS, Petrus JCC, Hubinger MD (2010) Concen- tion of electrostatic interactions during fractionation of
tration of avonoids and phenolic compounds in aque- small peptides complex mixtures by UF/NF mem-
ous and ethanolic propolis extracts through branes. Desalination 200:333334
nanoltration. J Food Eng 96:533539 Tessier B, Harscoat-Schiavo C, Marc I (2006b) Selective
Nawaz H, Shi J, Mittal GS, Kakuda Y (2006) Extraction of separation of peptides contained in a rapeseed
polyphenols from grape seeds and concentration by (Brassica campestris L.) protein hydrolysate using
ultraltration. Sep Purif Technol 48:176181 UF/NF membranes. J Agric Food Chem 54:35783584
94 Antioxidants Recovery by Integrated Membrane Operations

Tylkowski B, Trusheva B, Bankova V, Giamberini M, which should be processed by selective tech-


Peev G, Nikolova A (2010) Extraction of biologically niques able to produce concentrated streams with
active compounds from propolis and concentration of
extract by nanoltration. J Membr Sci 348:124130 enhanced antioxidant activity.
Vandanjon L, Johannsson R, Derouiniot M, Bourseau P, The recovery of antioxidants from agricultural
Jaouen P (2007) Concentration and purication of blue by-products can be conducted according to the 5-
whiting peptide hydrolysates by membrane processes. Stages Universal Recovery Processing strategy
J Food Eng 83:581589
Vandanjon L, Grignon M, Courois E, Bourseau P, Jaouen P which includes (1) a macroscopic pretreatment,
(2009) Fractionating white sh llet hydrolysates by (2) a macro- and micro-molecule separation,
ultraltration and nanoltration. J Food Eng 95:3644 (3) an extraction step, (4) an isolation and puri-
Vera Calle E, Ruales J, Dornier M, Sandeaux J, cation step, and (5) a product formation
Sandeaux R, Pourcelly G (2002) Deacidication of
the claried passion fruit juice. Desalination (Galanakis 2012).
149:357361 Conventional extraction methodologies are
Vera Calle E, Ruales J, Dornier M, Sandeaux J, Persin F, based on the use of resins, organic solvents,
Pourcelly G, Vaillant F, Reynes M (2003) Comparison enzymes, g-irradiation, and heat treatment.
of different methods for deacidication of claried
passion fruit juice. J Food Eng 59:361367 These methodologies have drawbacks to some
degree. For example, the extraction with organic
solvents is characterized by safety problems
(some of them are believed to be toxic), low
efciency, and time consumption; heat treatment
Antioxidants Recovery by Integrated results in pyrolysis; enzymes can be denatured in
Membrane Operations enzyme-assisted extraction; and g-irradiation-
assisted extraction is still unknown in terms of
Alfredo Cassano and Rosalinda Mazzei safety.
Institute on Membrane Technology, National Membrane technologies are the main processes
Research Council of Italy, ITM-CNR, Rende, used at large scale for the separation of antioxidant
Italy compounds from different sources. They offer
several advantages over conventional methods,
in terms of high separation efciency, low energy
Natural antioxidants are synthesized by plants, requirements, mild operating conditions, no addi-
microorganisms, fungi, and animals. They include tives, absence of phase transition, simple equip-
phenolics, terpenes, proteins, peptides, and carbo- ment, and easy scale-up. Pressure-driven
hydrates. Waste streams from the processing of membrane operations include microltration
agricultural feedstocks (residues from grape and (MF), ultraltration (UF), nanoltration (NF),
wine, apple pomace, peels, woods, olives, seeds, and reverse osmosis (RO). These processes
leaves) are particularly attractive as sources of cover most of the 5-Stages Universal Recovery
antioxidants. Processing strategy since they can be used as
Antioxidant compounds play an essential role macroscopic pretreatment (MF), in macro- and
in the human body to reduce oxidative processes. micro-molecule separation (UF), in purication
Therefore they offer interesting perspectives and (NF), and in concentration (RO).
opportunities in the production of dietary supple- These processes lead to the partial separation
ments and functional foods and potential utiliza- of the targeted compounds through size
tion in pharmaceutical and cosmetic industries. exclusion.
However, since these compounds are generally In addition to pressure-driven membrane oper-
present in complex matrices, extraction, separa- ations, membrane distillation (MD), osmotic dis-
tion, and purication methods are required in tillation (OD), and electrodialysis (ED) have
order to improve their purity. Extraction methods emerged as new membrane technologies with
ideally should be nondestructive, time efcient, great potential in integrated systems for the recov-
and suitable for producing high quantity of extract ery of antioxidants from vegetable sources.
Antioxidants Recovery by Integrated Membrane Operations 95

Retentate

MICROMOLECULES SEPARATION
A
Pre-
FEED MF UF/ED
treatment

MACROSCOPIC PRE-TREATMENT

NF
RO

ISOLATION AND PURIFICATION

OD/MD

CONCENTRATION

Antioxidants Recovery by Integrated Membrane microltration, UF ultraltration, NF nanoltration, RO


Operations, Fig. 1 Schematic representation of antioxi- reverse osmosis, OD osmotic distillation, MD membrane
dants recovery by membrane operations (MF distillation, ED electrodialysis)

In addition to RO, the concentration of bioac- low-molecular weight (MW) molecules cross the
tive compounds can be also performed by mem- membrane, while higher-MW molecules remain
brane distillation (MD) or osmotic distillation in the feed.
(OD). In these processes the driving force for the Specic applications of pressure-driven and
removal of water vapor across the pores of a electrically driven membranes processes for the
hydrophobic membrane is given by a vapor pres- recovery of antioxidant molecules have been
sure difference between the two sides of the mem- recently reviewed by Bazinet and Doyen (2016).
brane generated by a concentration (OD) or A schematic of integrated membrane opera-
thermal (MD) gradient. Electrically driven pro- tions, such as those previously described, for the
cesses, such as electrodialysis (ED) or a combina- recovery, separation, purication, and concentra-
tion of ED with UF membranes (EDUF), have tion of antioxidants, is depicted in Fig. 1. Such
demonstrated very high selectivity for the separa- ow sheet is an example of exible approach to
tion of organic charged biomolecules. These pro- valorize different agro-food by-products, as alter-
cesses use ion-exchange membranes and/or native to their disposal, within the logic of process
ltration membranes (such as UF) to separate intensication strategy.
molecules. The electric eld is the main driving A further improvement of the proposed inte-
force involved in these processes. Molecular grated system has been recently investigated
transfer is mainly due to the charge of the mole- through the addition of a nal step of membrane
cules and the ux depends on the strength of the emulsication (EM) or biocatalytic membrane
electric eld. In EDUF, fractionation of molecules reactor (BMR) nalized to the formulation and
is a function of their charges and molecular valorization of antioxidant compounds in olive
weights: according to the molecular weight cutoff mill wastewaters (OMWWs) (Bazzarelli
of the UF membrane located in the cell, et al. 2015; Conidi et al. 2014).
96 Antiscalant

References membrane. The selective and precise dosing of


the antisolvent, controlled by the porous mem-
Bazinet L, Doyen A (2016) Antioxidants, mechanisms, brane, allows a more ne control of the crystal-
and recovery by membrane processes. Crit Rev Food
lizing solution composition during the process
Sci Nutr. doi:10.1080/10408398.2014.912609
Bazzarelli F, Poerio T, Mazzei R, DAgostino N, Giorno and at the nucleation point, with consequent
L (2015) Study of OMWWs suspended solids destabi- advantages for the nal crystal characteristics.
lization to improve membrane processes performance. In solvent/antisolvent demixing conguration,
Sep Purif Technol 149:183189
a certain solute is dissolved in an appropriate mix
Conidi C, Mazzei R, Cassano A, Giorno L (2014) Inte-
grated membrane system for the production of of a solvent and an antisolvent whose composition
phytotherapics from olive mill wastewaters. J Membr is chosen in such a way that the solute remains
Sci 454:322329 indenitely in the solution in the original condi-
Galanakis C (2012) Recovery of high added-value compo-
tions. When a gradient of chemical potential is
nents from food wastes: conventional, emerging tech-
nologies and commercialized applications. Trends generated between the two sides of the mem-
Food Sci Technol 26:6887 branes, e.g., by a temperature difference, the sol-
vent, which is supposed to have a higher vapor
pressure than the antisolvent at the same temper-
ature, evaporates at higher ow rate thus produc-
Antiscalant ing solvent/antisolvent demixing. As the amount
of solvent in the mixture decreases, the lower
Scale Inhibitor solubility of the solute generates supersaturation
and a phase separation occurs when the
antisolvent exceeds a certain volume fraction.
The requirements for this conguration are that:
Antisolvent Membrane (i) the antisolvent and the solvent are miscible;
Crystallization (ii) the initial solvent/antisolvent balance in the
mixture guarantees that the solute is under its
Gianluca Di Proo solubility limit; and (iii) the solvent evaporates at
Institute on Membrane Technology, National higher velocity than the antisolvent. Crystalliza-
Research Council of Italy, ITM-CNR, Rende, tion of a solute from an aqueous/organic extrac-
Italy tion mixture can be successfully carried out by
this system.
In antisolvent addition conguration, a sol-
This is an extension of the solvent evaporation ute is dissolved in a solvent and then an
membrane crystallization concept, where a antisolvent is gradually evaporated from the
porous membrane is used to dose the amount other side of the membrane by applying a gra-
of antisolvent in the crystallizing solution, dient of chemical potential. As the antisolvent
which has been proposed very recently mixes with the solvent the solute dilutes but, at
(Di Proo et al. 2009). In this system, two the same time, the composition of the mixture
operative congurations have been developed: changes. At a certain point, the excess of
solvent/antisolvent demixing and antisolvent antisolvent creates supersaturation and solute
addition membrane crystallization. In both crystallization. This conguration requires that
cases, solvent/antisolvent migration occurs in the antisolvent and the solvent are miscible. In
vapor phase, according with the general con- this case, the compound to be crystallized can
cept of membrane crystallization and not by be soluble in aqueous solutions and poorly sol-
forcing it in liquid phase through the uble in organic low boiling liquids.
Antoine Equation 97

References the liquid states of the component, which depends


on the cohesive forces linking the molecules. In a
Di Proo G, Stabile C, Caridi A, Curcio E, Drioli E (2009) closed cell, the vapor pressure of a pure compo-
Antisolvent membrane crystallization of pharmaceuti- A
nent is a nonlinear relation of the temperature: the
cal compounds. J Pharm Sci 98:4902
more the component is volatile, the more the
vapor pressure is high.

Antoine Equation Antoine Equation

Denis Roizard For a given pure component in a closed cell, it


Laboratoire Ractions et Gnie des Procds, calculates the saturated vapor pressure P (mmHg)
CNRS- Universit de Lorraine, Nancy, France with the temperature T ( C) as follows:

log10 P A  B=T C (1)


Synonyms
with A, B, and C being the Antoine coefcients, in
Vapor PressureTemperature Relationship mmHg and  C units, which are component-
specic constants; e.g., for water : A = 8.07131;
B = 1730.63 and C = 233.426 in the tempera-
History ture range 199  C.
Other forms of the Antoine equation can be
Until the mid-nineteenth century, the prediction of deduced:
the saturated vapor pressure of a liquid mixture or
even of a pure liquid in relation with the temper- P 10AB=TC (2)
ature was not accurate despite the phenomena
being studied long before the Middle ages. The T B=A  log10 P  C (3)
Antoine equation, which solves this problem for
pure components, is due to a French engineer These equations t very well for experimental
(Louis Charles Antoine, 18251897) and was vapor pressure data.
rst published in Annales de Physique et de It is worth noting that the Antoine equation can
Chimie in 1891 (Antoine 1891). Antoine intro- also be used at high pressure or near the critical
duced an equation able to predict the vapor pres- point. Indeed, for each component, two sets of
sure of pure liquids (vaporization) and solids parameters can be used according to the consid-
(sublimation). It is worth noting that this equation ered temperature range, i.e., either up to the nor-
is still widely used today because of its accuracy. mal boiling point or from normal boiling point to
Wisniak (2001) has recently reviewed the histor- the critical point; in this last range, the Clausius-
ical development of the vapor pressure equations Clapeyron relation (Reid 1990) does not apply
from Dalton to Antoine. properly. In the case of pure water, in the temper-
ature range 99374  C, the dedicated Antoine
coefcients are A = 8.140191, B = 1810.94,
Phenomenon and C = 244.485.
The extension (Wagner 1973) of the Antoine
The vapor pressure over a liquid is due to the equation has been worked out to cover with a
thermodynamic equilibrium between the gas and single set of parameters the whole temperature
98 Antoine Equation

Antoine Equation, 180000


Fig. 1 Curves of P(sat) H2O
versus temperature; range 160000
50150  C calculated with
the Antoine equation 600
140000
ZOOM
120000 400 0100C

P mmHg
100000 200

80000 00
100

60000

40000

20000

0
0 100 200 300 400
T C

range going from the critical point to the triple For C coefcient, subtract 273.15 to take into
point. This expression is required when computa- account the modication of the
tional techniques must be used. temperature unit.
On the other hand, a simplied equation using
only two parameters was known to evaluate the The Antoine coefcients have been tabulated
vapor pressure; it was the August equation in for most of pure compounds. They can be
which the parameter C is set to zero, thus assum- obtained from various sources, including web
ing a temperature-independent heat of access Data banks of Antoine Coefcients
vaporization. (visited June 2013).

Antoine Coefficients Example Calculation

Two systems of units can be used, either based This calculation has been done for water with the
on temperature and pressure, respectively, in coefcients: A = 8.07131, B = 1730.63, and

C and in mmHg or on K and Pa (SI system). C = 233.426. The temperature validity range is
Note that for historic reasons, the Antoine from 1 C to100 C.
coefcients are still normally given based on
the CGS system. Conversion from the histori- At T = 50  C: log10 (P) = 8.071311730.63/
cal system unit to the SI one can be made (50 + 233.426) = 1.9652
easily: Hence, P(sat) H2O = 92 mmHg

B coefcient is the same in both systems; The results shown in Fig. 1 and Table 1 corre-
To get A coefcient in SI, add 2.124903 to the spond to water vapor pressure calculated with the
historical A; this value corresponds the respective sets of parameters of each domain with
pressure unit modication, i.e., to log10 the Eq. 1. The discontinuity at 100  C can be seen
(101325/760). in the Table 1.
Apple Juice and Membrane Operations 99

Antoine Equation, Table 1 Example calculation of P(sat) H2O; range 50150  C


T C log10 (P) P mmHg T C log10 (P) P mmHg
50 1.9652012 92.30 100 2.8832575 764.29 A
60 2.1732982 149.04 110 3.0320002 1076.47
70 2.3676788 233.17 120 3.1745848 1494.81
80 2.5496558 354.53 130 3.3093227 2038.56
90 2.7203796 525.27 140 3.4368443 2734.29
100 2.8808629 760.09 150 3.5577142 3611.72
A = 8.07131 B = 1730.63 C = 233.426 A = 8.140191 B = 1810.94 C = 244.485

References phenolic compounds. Most part of the juice is


consumed as claried product.
Antoine C (1891) Annales de Physique et de Chimie 22: Traditional methods of processing apple juice
281; ibid, Annales de Physique et de Chimie (1892) 26:
are based on the use of several batch operations
426; Comptes Rendus Acad Sci (Paris) (1888) 107:
1143 that are labor and time-consuming. Typically,
Data banks of Antoine Coefcients (visited June 2013) after preliminary operations (sorting, washing,
http://webbook.nist.gov/ http://booksite.elsevier. and peeling steps), apple fruits are crushed and
com/9780080966595/content/Appendices/Appendix%
then pressed.
20C.pdf (free download) http://www.eqi.ethz.ch/fmi/
xsl/eqi/eqi_property_details_en.xsl?node_id=983 The juice is submitted to a heat treatment for
(directory for Physical Properties Sources) Vapor- 16 s at temperature of 72  C to inhibit yeast
Liquid Equilibrium Data Collection, DECHEMA growth and avoid fermentation. During the press-
Chemistry Data Series, Jurgen Gmehling
ing step, pectinase is added in order to hydrolyze
et al. (Frankfurt)
Reid CE (1990) Chemical thermodynamics. McGraw-Hill, the pectin, reducing juice viscosity and making
New York, p 73 the product easier to lter. This process is
Wagner W (1973) New vapour pressure measurements for performed at temperatures in the range of 40 to
argon and nitrogen and an new method for establishing
50  C for 1 h. After this step, ning agents such as
rational vapour pressure equations. Cryogenics
13(8):470482 bentonite, gelatine, or silica solution are added to
Wisniak J (2001) Historical development of the vapor the juice to improve the effect of settling.
pressure equation from Dalton to Antoine. J Phase After decanting, the juice is submitted to a
Equilib 226:622630. doi:10.1007/s11669-001-
precoat ltration, using lter aids, i.e., diatoma-
0026-x1143
ceous earths and perlite, to remove suspended
solids, colloidal particles, proteins, and
polyphenols.
Apple Juice and Membrane The nal product can be submitted to a con-
Operations centration process by evaporation. It is generally
performed in multiple effect evaporators at tem-
Carmela Conidi peratures between 45  C and 90  C. During this
Institute on Membrane Technology, National step, undesirable alterations of the original aroma
Research Council of Italy, ITM-CNR, Rende, prole of the juice due to high operating temper-
Italy atures are produced.
Membrane operations are competitive and
attractive alternatives to the conventional treat-
Apple juice is one of the most popular juices ments of apple juices. The advantages of using
worldwide. It approximately accounts for a 20 % membrane technology, over conventional
of the juice market share, with a production of 1.5 methods, are related to product costs, working
million tons per year. Besides vitamins and min- conditions, environmental aspects, and product
erals, apple juice is characterized by high levels of quality.
100 Apple Juice and Membrane Operations

Apple juice clarication, stabilization, recov- RO is a pressure-driven membrane process that


ery of aroma, and concentration are typical steps can be used as an alternative process for apple
where membrane operations as microltration juice concentration, as it does not involve phase
(MF), ultraltration (UF), enzymatic membrane change or the use of high temperatures. The main
reactors (EMR), pervaporation (PV), reverse advantages of RO concentration are the attain-
osmosis (RO), osmotic distillation (OD), and ment of high-quality products due to low operat-
membrane distillation (MD) are successfully ing temperatures, resulting in the retention of
utilized. nutritional compounds and lower energy
The clarication of apple juice by membrane consumption.
processes has been used commercially for over However, the performance of RO mem-
30 years. In particular, the use of MF and UF branes is limited by the osmotic pressures of
represents a valid alternative to traditional the juice when the concentration reaches
methods in apple juice clarication and stabiliza- values of 2530  Brix; therefore, RO can be
tion, resulting in increase juice yield, improved considered an advantageous technique as a
product quality, and avoidance of ning agents pre-concentration step.
(gelatin, bentonite, and silica sol) and lter aids Polyamide and cellulose acetate RO mem-
that are costly and present disposal problems. branes in both tubular and spiral wound congu-
MF or UF permits the removal of haze-forming rations have been extensively used during the
components, such as suspended solids, colloidal concentration of apple juice (Alvarez et al. 2002).
particles, and proteins resulting in the production In order to overcome the limitation of RO in
of superior juice quality. Turbidity values less apple juice concentration , more recently, osmotic
than 0.10.2 NTU are typically obtained if com- distillation (OD) and membrane distillation
pared to 25 NTU of conventional methods with (MD) have been proposed as attractive membrane
ning agents. processes for apple juice concentration allowing
Polymeric membranes made from very high concentrations (up to 65  Brix) to be
polyethersulfone (PES), polyvinylidene uoride reached under atmospheric pressure and at room
(PVDF), cellulose acetate (AC), and polysulfone temperature, thus avoiding thermal and mechani-
(PS) with pore size of 0.10.2 mm and molecular cal damage (Onsekizoglu et al. 2010).
weight cutoff (MWCO) of 10100 kDa are used These different membrane-based concentra-
for the clarication of apple juice. tion techniques resulted very efcient in the con-
Tubular, capillary, and plate-and-frame mem- centration of apple juice, since the concentrated
brane modules are the most important congura- juice presented nutritional and sensorial quality
tions used at industrial level. similar to that of the original juice, especially
The claried juice is usually concentrated in regarding the retention of the bright color and
order to reduce storage, package, and shipping pleasant aroma, which are lost during thermal
costs. In addition, concentrated apple juice is evaporation.
more stable, presenting higher resistance to Esters, aldehydes, and alcohols such as ethyl
microbial and chemical deterioration than the butanoate, ethyl-2-methylbutanoate, and hexanal
original juice as a result of water activity are the main compounds which contribute to the
reduction. aroma prole of apple juice.
Conventional methods of apple juice con- PV constitutes a promising alternative to tradi-
centration, such as vacuum evaporation, usu- tional techniques, such as distillation and partial
ally employ high temperature to remove water. condensation, for aroma recovery from apple
However, heat determines undesirable changes juices.
of juice quality such as color changes, Alvarez et al. (2000) proposed an integrated
off-avor formation, and reduction in the membrane process for producing apple juice and
nutritional value. apple juice aroma concentrates.
Application of FEEM to Monitoring Membrane Fouling 101

Apple
References

Alvarez S, Riera FA, lvarez R, Coca J, Cuperus FP, Th


Juice extraction PV Bouwer S, Boswinkel G, Van Gemert RW, Veldsink A
JW, Giorno L, Donato L, Todisco S, Drioli E, Olsson J,
Trgrdh G, Gaeta SN, Panyor L (2000) New inte-
apple juice aroma recovery grated membrane process for producing claried
apple juice and apple juice aroma concentrate. J Food
Eng 46:109125
Alvarez S, Riera FA, lvarez R, Coca J (2002) Concentra-
tion of apple juice by reverse osmosis at laboratory
depectinization EMR and pilot-plant scales. Ind Eng Chem Res 41:
61566164
Onsekizoglu P, Savas Bahceci K, Jale Acar M (2010)
MF UF Clarication and concentration of apple juice using
membrane processes: a comparative quality assess-
ment. J Membr Sci 352:160165
Clarified juice

RO OD MD
Application of FEEM to Monitoring
Membrane Fouling
Concentrated juice Raymond L. Legge
Department of Chemical Engineering, University
Apple Juice and Membrane Operations, of Waterloo, Waterloo, ON, Canada
Fig. 1 Membrane operations for the treatment of apple
juice

FEEM refers to a uorescence excitation-


The process involves the clarication of raw emission matrix that consists of a collection of
apple juice by using an enzymatic membrane reac- intensity values for a group of excitation-emission
tor, an RO unit to pre-concentrate the claried juice pairs over a range of emission and excitation
up to 25  Brix, a PV unit to recover and concentrate wavelengths. FEEM or uorescence excitation-
aroma compounds, and a nal evaporation step to emission matrix is important in the context of
concentrate the juice up to 72  Brix. monitoring membrane fouling because NOM, or
Rejection of aroma compounds in the PV step natural organic matter, is a signicant foulant in
exceeded 90 % for most compounds considered. some cases for drinking water production, and
Organoleptic evaluation of the claried and con- some components of NOM are uorescent.
centrated juice resulted excellent in terms of odor Fluorophores can be classied into two categories
and avor. The nal products were more clear and that can be described as intrinsic or extrinsic
brilliant than apple juice produced by conven- (Lakowicz 2006). Two of the three major fractions
tional methods. of NOM are intrinsic uorophores: protein and
An economic evaluation of the integrated humic substances. Other biological constituents
membrane system indicated a reduction of the that may end up in water may also be uorescent
total capital investment of 14 % and an increase and can contribute to the FEEM, but this will
in process yield of 5 % when compared with the depend on the water source. For the protein com-
conventional process. ponent, the amino acids that can contribute to the
A conceptual process design based on the inte- uorescent signal are tryptophan, tyrosine, and
gration of membrane operations in apple juice phenylalanine. The third component, the colloid/
processing is depicted in Fig. 1. particulate matter, may be captured in the
102 Aptamer Membrane Functionalization

Rayleigh scattering portion of the FEEM and is Peiris RH, Hall C, Budman H, Moresoli C, Peldszus S,
not necessarily uorescent (Peiris et al. 2010a). Huck PM, Legge RL (2010b) Identifying fouling
events in a membrane-based drinking water treatment
This approach has the advantage that little or no process using principal component analysis of uores-
sample preparation is required so analysis is rapid cence excitation-emission matrices. Water Res
and can possibly be conducted online. Analysis of 44:185194
the FEEM data is required because it is rich in
information, but various approaches are required
to identify or correlate which components are
contributing to fouling. Among the various
approaches for analysis of the data is principle Aptamer Membrane
component analysis or PCA (Peiris et al. 2010b). Functionalization
The advantage of FEEM-based analysis is that
this approach can provide potentially online infor- Thomas Schfer
mation. Possible options that would allow data Institute for Polymer Materials (Polymat),
acquisition online would include ow through University of the Basque Country (UPV/EHU),
systems or ber optic approaches. The data Donostia-San Sebastin, Spain
acquired can then be used in concert with instan-
taneous membrane ux or transmembrane pres-
sure (TMP) measurements to garner more
information related to the important foulants. Aptamer Membrane Functionalization. Aptamers
Advantages of this approach are that water can be incorporated into adequate porous mem-
pretreatment strategies can be tuned or tailored brane structures in order to obtain stimulus-
to minimize the components that are contributing responsive membranes whose permeability is
to the NOM-based fouling or to take appropriate modulated via a molecular recognition event.
action before membrane fouling becomes signi- The concept relies on the fact that aptamers can
cant. Similarly, it may provide a useful technique recognize very specically a molecular target,
for monitoring the membrane permeate for NOM upon which a signicant conformational change
constituents that may contribute to disinfection can occur if the aptamer is designed accordingly.
by-products (DBPs) which can serve as possible In this sense, aptamer-modied membranes fol-
carcinogens. low the concept structure determines separa-
tion. The stimulus-responsive membranes so
obtained therefore do not require a bulk stimulus,
such as a change in temperature or pH, which
Cross-References makes them particularly interesting for being
employed in biomedical separations or
Fouling in Membranes DNA-based nanodevices (Bhattacharyya
Irreversible Fouling et al. 2013). Incorporating the aptamer into an
Membrane Fouling adequate porous structure, the aptamer conforma-
tional change upon target recognition can give rise
to a hindered pore ow, modulating in this way
References the overall membrane permeability. Aptamer-
Lakowicz JR (2006) Principles of uorescence spectros-
target interactions can be highly specic, target
copy, 3rd edn. Springer, New York concentration dependent, and do not involve the
Peiris RH, Budman H, Moresoli C, Legge RL (2010a) formation of chemical bonds but are physical. As a
Understanding fouling behavior of ultraltration mem- consequence, membranes functionalized with
brane processes and natural water using principal
component analysis of uorescence excitation-
aptamers change their permeability depending on
emission matrices. Water Sci Technol Water Supply the target concentration and in a reversible manner.
11(2):179185 Figure 1 depicts the concept of a membrane pore
Aptamer Membrane Functionalization 103

Aptamer Membrane Functionalization, Fig. 1 Scheme of a stimulus-responsive aptamer-functionalized membrane

c
a

3. Amino functionalized
Aptamer

100 nm 10 nm HN

b 120 O

100 2. GMBS crosslinker


O
80
Intensity

N
O
60

40
S
1. Thiol Addition
20 via silanization

0 Si
O O
150 160 170 180 190 200 210 220 O
Average Size (nm) Silica Surface

Aptamer Membrane Functionalization, Fig. 2 Mesoporous particles (a), their size distribution (b), and the
functionalization of mesoporous silica with an aptamer (c)

functionalized with a DNA-aptamer hairpin struc- open and the membrane permeability maximum.
ture which changes its conformation upon a molec- Upon interaction with AMP, the aptamer undergoes
ular stimulus such as adenosine 50 -monophosphate a conformational change which signicantly
(AMP). In the absence of the target AMP, the reduces the pore ow and, hence, overall membrane
aptamer-functionalized membrane pores remain permeability.
104 Aptamer Membrane Functionalization

Aptamer Membrane Functionalization, change upon target recognition (b), and function to release
Fig. 3 Sequence of a DNA-aptamer hairpin that binds in a reversible, specic, and concentration-dependent fash-
selectively to ATP (a), scheme of its conformational ion cargo molecules (c)

For the conformational change to take effect, conformation. It could be shown that the thickness
the pore diameter needs to be of the same order of change of a DNA-aptamer hairpin lm amounts
magnitude. Therefore, mesoporous structures are up to about 2 nm upon interaction with the target
preferably employed that furthermore possess a (Serrano-Santos et al. 2012). Hence, mesoporous
high degree of isoporosity. Aptamer-modulated structures with a pore diameter between 2 and
pore ow has been thoroughly studied for 3 nm have been found to be a suitable base mate-
mesoporous particles that are used as controlled rial for aptamer-functionalized particles and mem-
delivery devices (zalp and Schfer 2011). branes (zalp and Schfer 2011).
Figure 2 shows the immobilization strategy for
modifying mesoporous silica particles with
aptamers and Fig. 3 the concept of how such an
aptamer can serve as a reversibly opening lid in References
order to liberate cargo molecules upon target rec-
ognition (here: ATP). Bhattacharyya D, Schfer T, Wickramasinghe RR, Daunert
S (eds) (2013) Responsive membranes and materials.
A key parameter for the functioning of Wiley, Hoboken
aptamer-functionalized membranes is the ne- zalp VC, Schfer T (2011) Aptamer-based switchable
tuning of the pore size within which the aptamer nanovalves for stimuli-responsive drug delivery.
conformational change takes place. Pores too Chem Eur J 11:98939896
Serrano-Santos MB, Llobet E, zalp VC, Schfer T (2012)
large would not result in any aptamer-modulated
Characterization of structural changes in aptamer lms
permeability, while pores too narrow would hin- for controlled release nanodevices. Chem Commun
der the aptamer from freely changing its 48:1008710089
Aptamer Screening 105

against a given target (i.e., protein, small mole-


Aptamer Screening cules, or even whole cells) by an iterative process
that involves (i) library/target interaction, A
Thomas Schfer (ii) selection of the sequences that bind to the target
Institute for Polymer Materials (Polymat), and removal of no binders, (iii) enrichment of the
University of the Basque Country (UPV/EHU), selected sequences by PCR, and (iv) after several
Donostia-San Sebastin, Spain screening rounds, cloning and sequencing to iden-
tify individual sequences. Finally, bioinformatic
analysis is required to determine the most promis-
Aptamer screening or selection, also called sys- ing motifs or sequences. Next, the candidate
tematic evolution of ligands by exponential enrich- sequences are evaluated to conrm their binding
ment (SELEX), is a combinatorial chemistry capability. SELEX technology could be compared
method by which aptamers (single-stranded DNA to antibody production; however, SELEX offers
or RNA) are selected. SELEX is an evolutionary interesting features that overcome some limitations
method driven by the binding of oligonucleotide of the antibody production, such as fast in vitro
sequences to a specic target based on their partic- performance, no need for cells or animals, ease of
ular tridimentional structure, which confers high selection under physiological or nonphysiological
afnity and specicity. The selection process starts conditions, no limitation for target selection, and
with a random oligonucleotide library consisting of batch-to-batch reproducibility.
a random region anked by xed primer regions Since the rst report of SELEX in 1992 by two
required for PCR amplication. The random region independent groups (Tuerk and Gold 1990;
confers outstanding variability, derived from the Ellington and Szostak1990), several modica-
number of possible sequences in the library. tions of the standard method have been reported
The variability of the library can be calculated to improve its performance. Nowadays, a signi-
with the expression 4n, where 4 is the number of cant number of aptamers have been selected and
possibilities at each position (A, T, C, or G) and used as recognition molecules for environmental,
n is the length of the random region. SELEX food, diagnosis, and therapeutic applications
allows the screening of oligonucleotide libraries (Fig. 1).

Aptamer Screening,
Library Design by regions
Fig. 1 Aptamer selection
fixed random fixed Cloning, Sequencing
process from library
and Bioinformatics

Library
Interaction
Library/Target
Target

iteration
Selection of Target
Binders

Removal of
no binders

Enrichment of
selected binders
106 Aptamers

References intermolecular interactions creates unique binding


pockets. Hence, along with a remarkable afnity,
Ellington AD, Szostak W (1990) In vitro selection of RNA aptamers are generally characterized by high
molecules that bind specic ligands. Nature
specicity. One of the most noteworthy examples
346:818822
Tuerk C, Gold L (1990) Systematic evolution of ligands by is the anti-theophylline aptamer which can dis-
exponential enrichment: RNA ligands to bacteriophage criminate between theophylline and caffeine,
T4 DNA polymerase. Science 249:505510 two related molecules that only differ by a methyl
group of the imidazole ring, having about 11,000
times higher afnity for the former. Similarly,
aptamers have been reported to discriminate
Aptamers between enantiomers, macromolecules, proteins,
and whole cells.
Thomas Schfer Apart from their high afnity and specicity,
Institute for Polymer Materials (Polymat), aptamers possess unique chemical and biochemi-
University of the Basque Country (UPV/EHU), cal characteristics which clearly set them apart
Donostia-San Sebastin, Spain from other receptors. For example, aptamers are
exceptionally stable: they may undergo denatur-
ation, but the process is fully reversible within
Aptamers (from Latin aptus, to t) are articial minutes; hence, temperature changes or long-
ligands binding with high afnity and specicity term storage does not affect their functionality.
to their cognate target, selected through a Furthermore, the well-known chemistry of
Darwinian-like evolution method referred to as aptamers allows for site-directed chemical modi-
SELEX. Aptamers generally consist of structured cations and competitive production costs. New
single-strand nucleic acid molecules such as RNA functional groups can be introduced a
and ssDNA; however, dsDNA and peptide priori within the SELEX process using mod-
aptamers have been described as well (Colas ied nucleic acid libraries or a posteriori modify-
et al. 1996; Patel et al. 1997). ing a selected DNA/RNA through chemical
Aptamers can be selected against virtually any synthesis. While the rst approach relies on the
target and under nonphysiological conditions compatibility of the modication adopted with the
because no animal host is required. Hitherto, enzymatic amplication necessary for selection,
aptamers were selected against a broad range of the latter approach is streamlined by detailed
target molecules, such as amino acids, peptides, knowledge of the structure of both the aptamer
proteins, drugs, organic and inorganic molecules, and the aptamer-target complex. Since their rst
or even whole cells, with afnities often compa- appearance in the early 1990s, aptamers have
rable to those of monoclonal antibodies. received constantly increasing attention, reected
The binding proprieties of aptamers are due to in their use as diagnostic reagents and therapeutic
the formation of specic aptamer-target com- compounds.
plexes stabilized by non-covalent interactions.
The latter are a combination of van der Waals
forces, hydrogen bonds, and electrostatic interac-
References
tions. Binding of an aptamer to its cognate target
can trigger an adaptive folding in which the target Colas P, Cohen B, Jessen T, Grishina I, McCoy J, Brent
promotes and stabilizes the secondary and tertiary R (1996) Genetic selection of peptide aptamers that
structures of aptamers. The dynamic conforma- recognize and inhibit cyclin-dependent kinase 2. Nature
tions of free aptamers, consisting of labile 380(6574):548550
Patel DJ, Suri AK, Jiang F, Jiang L, Fan P, Kumar RA,
knots, loops, and stems, turn into stable architec- Nonin S (1997) Structure, recognition and adaptive
tures within the aptamer-target complexes binding in RNA aptamer complexes. J Mol Biol
where noncanonical base pairing along with 272(5):645664
Aquaporin-Incorporated Biomimetic Membranes 107

aquaporin-incorporated materials onto a porous


Aquaporin-Incorporated Biomimetic support, or (3) autopainting membrane (APM)
Membranes method. A
LB and LS monolayer transfer (Sun et al. 2012):
Chung Tai-Shung Neal1, Honglei Wang2, The rst monolayer of amphiphilic materials
Guofei Sun3, Hoang Hanh Phuoc Duong4 and (lipids or copolymers) is deposited onto a solid
Pei Shan Zhong5 support by the LB method. The second monolayer,
1
National University of Singapore, Singapore, which contains aquaporin-incorporated amphi-
Singapore philic materials, is subsequently deposited onto
2
Department of Chemical and Biomolecular the rst layer by the LS method.
Engineering, jMedtech Pte Ltd, Singapore, Vesicle rupture: Aquaporins are rst incorpo-
Singapore rated into liposomes (Borgnia et al. 1999; Wang
3
Chemical and Biomolecular Engineering, et al. 2011) or polymersomes (Kumar et al. 2007)
Aquaporin Asia Pte. Ltd, Singapore, Singapore through a typical transmembrane protein incorpo-
4
King Abdullah University of Science and ration method (Borgnia et al. 1999). Subse-
Technology (KAUST), Biological and quently, these aquaporin-incorporated vesicles
Environmental Science and Engineering Division are ruptured onto a porous support via charge
(BESE), Thuwal, Saudi Arabia interaction (Wang et al. 2011; Kaufman
5
Functionalized Materials and Nanostructures/ et al. 2010; Li et al. 2012) or covalent conjugation
Global Research Centre Singapore (GMM/F), between the vesicles and the support
BASF South East Asia Pte Ltd., Singapore, (Wang et al. 2012; Zhong et al. 2012; Duong
Singapore et al. 2012).
APM method: Free-standing aquaporin-
incorporated lipid/polymeric membranes can be
formed analogous to the conventional black lipid
Aquaporin, a transmembrane protein, has membrane preparation method (Hansen
attracted attention globally since its serendipitous et al. 2009; Gonzlez-Prez et al. 2009).
discovery by Peter Agre in 1992 (Agre 2006). Its A mixed solution of aquaporins and amphiphilic
facilitation in rapid and selective water transport materials is smeared across the hydrophobic
has inspired many scientists to utilize this unique arrays apertures in electrolyte conditions. The
function for water treatment applications membranes are spontaneously formed on the
(Kaufman et al. 2010; Wang et al. 2012). Much apertures at the interface of organic and aqueous
effort has been devoted to build and overcome the phases.
challenges faced in fabricating the synthetic bio-
mimetic membrane housing the water channel
(Kumar et al. 2012). It is envisioned that this Aquaporin Biomimetic Membrane
technology will bring about higher efciency for Designs
desalination (Kaufman and Freger 2011) and
hence lower cost. According to their conformations, the designs of
aquaporin-embedded biomimetic membranes can
be classied into two categories, namely, (1) free-
standing lipidic/polymeric membranes (Fig. 1)
Membrane Preparation Methods and (2) supported lipidic/polymeric membranes
(Fig. 2).
Aquaporin-incorporated membranes can be The free-standing lipidic/polymeric membrane
prepared via the (1) Langmuir-Blodgett is fabricated by assembling black lipid/block
(LB) and Langmuir-Schaefer (LS) monolayer copolymer domains across multiple apertures in
transfer techniques, (2) vesicle rupture of the ethylene tetrauoroethylene (ETFE) scaffolds
108 Aquaporin-Incorporated Biomimetic Membranes

(about 300 mm diameter each aperture) (Hansen Characterization of Water Transport


et al. 2009; Gonzlez-Prez et al. 2009; Rein Through the Aquaporin-Incorporated
et al. 2011). This membrane array can be stabi- Membranes
lized with the support of a highly permeable
hydrogel layer (Lander et al. 2011; Ibragimova The permeability of reconstituted aquaporin in ves-
et al. 2012). icles is characterized mainly by the stopped-ow
The supported lipidic/polymeric membranes spectroscopy technique. In a stopped-ow experi-
with aquaporins have been designed for ment, the osmotic permeability Pf (m3/m2/s)
several applications, such as forward osmosis can be calculated by using the equation
(FO), nanoltration (NF), and reverse osmosis (Borgnia et al. 1999)
(RO). Detailed information on the materials and
preliminary performance is summarized in Pf k=Cosm V w So =V o
Table 1.
where k is the rate constant obtained from light
scattering signal and So(m2) and Vo(m3) are the
initial surface area and volume of the vesicle,
respectively. Vw is the molar volume of water
(18  106 m3/mol) and Cosm is the osmolarity
difference that drives the vesicle shrinkage.
The hydraulic permeability coefcient Lp (m/s/
bar) represents the rate of water movement across
a given area, per unit of osmotic gradient, and can
be calculated from the equation (Hillyard 2012):

Lp Pf V w =RT

where R and T are gas constant and temperature,


respectively. When the biomimetic membrane
transforms from a sphere to a at surface, the
intrinsic water volume ux Jv (m3/s) can be
obtained by using equation (Hillyard 2012):

J v ALp slRTDC  DP
Aquaporin-Incorporated Biomimetic Membranes,
Fig. 1 Schematic graph of free-standing lipidic/polymeric where A is the membrane area, in m2. s is the
membranes reection coefcient and is assumed to be 1. l is

Aquaporin-Incorporated
Biomimetic Membranes,
Fig. 2 Schematic graph of
supported lipidic/polymeric
membranes incorporated
with aquaporins
Aquaporin-Incorporated Biomimetic Membranes 109

Aquaporin-Incorporated Biomimetic Membranes, Table 1 Demonstration of aquaporin-incorporated biomimetic


membranes
Material of active layer and support Membrane performance Reference
A
PMOXA-PDMS-PMOXAa (with acrylate ends), aquaporin FO Wang et al. (2012)
Z (molar ratio 1:50) Draw solution: 2M NaCl
Methacrylate-functionalized PCTE support (average pore size Feed solution: water
50 nm) Water ux: >100 L/m2/h
Salt reverse ux: <10 g/m2/h
PMOXA-PDMS-PMOXAa (with acrylate ends), aquaporin NF Zhong et al. (2012)
Z (molar ratio 1:50) Feed: 200 ppm NaCl
Methacrylate-functionalized CA support (average pore size Pressure: 5 bar
19 nm) PWPb: 34 L/m2/h/bar
Salt rejection: 32 %
PMOXA-PDMS-PMOXAa (with disulde ends), aquaporin NF Duong et al. (2012)
Z (molar ratio 1:100) Feed: 200 ppm NaCl
Gold-coated porous alumina support (average pore size 55 nm) Pressure: 5 bar
Water ux: 8 L/m2/h/bar
Salt rejection: 45 %
DOPCc and DOTAPd RO Li et al. (2012)
Aquaporin Z (molar ratio 1:200) Feed: 1 mM NaCl
Commercially available NF-270 support Pressure: 1 bar
Water ux: 3 L/m2/h/bar
Salt rejection: 20 %
a
Poly(2-methyloxazolineb-dimethylsiloxane-b-2-methyloxazoline)
b
Pure water permeability
c
1,2-dioleoyl-sn-glycero-3- phosphocholine
d
1,2- dioleoyl-3-trimethylammonium-propane (chloride salt)

the molecularity. DP is the hydrostatic pressure establishment of functional lipid bilayer arrays.
difference across the membrane, in bar. DC is J Micromech Microeng 19:025014
Hillyard SD (2012) Sensing meets separation: water trans-
concentration difference across the membrane, in port across biological membranes. In: Hlix-Nielsen
mol/m3. C (ed) Biomimetic membranes for sensor and separa-
tion applications. Springer, Netherlands, pp 24
Ibragimova S, Stibius K, Szewczykowski P, Perry M,
Bohr H, Helix-Nielsen C (2012) Hydrogels for in situ
References encapsulation of biomimetic membrane arrays. Polym
Adv Technol 23(2):182189
Agre P (2006) The Aquaporin water channels. Proc Am Kaufman Y, Freger V (2011) Supported biomimetic mem-
Thorac Soc 3:513 branes for pressure-driven water purication. On biomi-
Borgnia MJ, Kozono D, Calamita G, Maloney PC, Agre metics. InTech. http://www.intechopen.com/books/on-
P (1999) Functional reconstitution and characterization biomimetics/supported-biomimetic-membranes-for-press-
of AqpZ, the E. coli water channel protein. J Mol Biol ure-driven-water-purication
291:11691179 Kaufman Y, Berman A, Freger V (2010) Supported lipid
Duong PHH, Chung TS, Jeyaseelan K, Armugam A, bilayer membranes for water purication by reverse
Chen Z, Yang J, Hong M (2012) Planar biomimetic osmosis. Langmuir 26:73887395
aquaporin-incorporated triblock copolymer mem- Kumar M, Grzelakowski M, Zilles J, Clark M, Meier
branes on porous alumina supports for nanoltration. W (2007) Highly permeable polymeric membranes
J Membr Sci 409410:3443 based on the incorporation of the functional water
Gonzlez-Prez A, Stibius KB, Vissing T, Nielsen CH, channel protein Aquaporin Z. Proc Natl Acad Sci U S
Mouritsen OG (2009) Biomimetic triblock copolymer A 104:2071920724
membrane arrays: a stable template for functional Kumar M, Payne MM, Poust SK, Zilles JL (2012)
membrane proteins. Langmuir 25(18):1044710450 Polymer-based biomimetic membranes for desalination.
Hansen JS, Perry M, Vogel J, Vissing T, Hansen CR, In: Hlix-Nielsen C (ed) Biomimetic membranes for
Geschke O, Emnus J, Hlix-Nielsen C (2009) Devel- sensor and separation applications. Springer, Nether-
opment of an automation technique for the lands, pp 4362
110 Aquaporins (AQPs) or Water Channels

Lander MR, Ibragimova S, Rein C, Vogel J, Stibius KB, intracellular pH. As with any membrane transport
Geschke O, Perry M, Helix-Nielsen C (2011) Biomi- facilitator, aquaporins have evolved to be highly
metic membrane arrays on cast hydrogel supports.
Langmuir 27:70027007 selective for their transported substrate without
Li X, Wang R, Tang C, Vararattanavech A, Zhao Y, binding water so strongly that transport is
Torres J, Fane T (2012) Preparation of supported lipid inhibited. On the basis of their selectivity,
membranes for Aquaporin Z incorporation. Colloids aquaporins can be divided into two groups: the
Surf B: Biointerfaces 94:333340
Rein C, Pszon-Bartosz K, Stibius K, Bjrnholm T, Helix- ordinary aquaporins, permeable to water only, and
Nielsen C (2011) Free-standing biomimetic polymer aquaglyceroporins which also permit transport of
membrane imaged with atomic force microscopy. small solutes such as glycerol and urea. A number
Langmuir 27(2):499503 of other compounds have also been reported to be
Sun G, Zhou H, Li Y, Jeyaseelan K, Armugam A, Chung
TS (2012) A novel method of Aquaporin transported through aquaporins, including CO2,
Z incorporation via binary-lipid Langmuir monolayers. NH3, and arsenite (Kreida and Tornroth-
Colloids Surface B 89:283288 Horseeld 2015). AQPs are transmembrane chan-
Wang H, Chung TS, Tong YW, Meier W, Chen Z, Hong M, nels; thus the ability of a molecule to cross an
Jeyaseelan K, Armugam A (2011) Preparation and
characterization of pore-suspending biomimetic mem- AQP channel depends on its own characteristics
branes embedded with Aquaporin Z on carboxylated (size, polarity, charge) and on the features of the
polyethylene glycol polymer cushion. Soft Matter AQP involved (Di Giorgio et al. 2014). They have
7:72747280 a similar basic structure; AQPs are monomers of
Wang H, Chung TS, Tong YW, Jeyaseelan K, Armugam A,
Chen Z, Hong M, Meier W (2012) Highly permeable about 30 kDa and, in general, contain six
and selective pore-spanning biomimetic membrane membrane-spanning helical segments and two
embedded with Aquaporin Z. Small 8:11851190 shorter helical segments that do not span the entire
Zhong PS, Chung TS, Jeyaseelan K, Armugam A (2012) membrane. The AQPs generally form stable tet-
Aquaporin-embedded biomimetic membranes for
nanoltration. J Membr Sci 407408:2733 ramers in membranes, although each monomer
contains a separate water pore. High-resolution
structural data show that the membrane-spanning
helical domains surround cytoplasmic and extra-
cellular vestibules that are connected by a narrow
Aquaporins (AQPs) or Water aqueous pore. Structural data and molecular
Channels dynamics simulations suggest that water mole-
cules move through this narrow aqueous pore
Fabio Bazzarelli and Lidietta Giorno and that steric and electrostatic factors are respon-
Institute on Membrane Technology, National sible for the water selectivity of AQPs. The pore is
Research Council of Italy, ITM-CNR, Rende, less constricted in the aquaglyceroporins than in
Italy the water-selective AQPs (diameter of 3.4 ver-
sus 2.8 , respectively) and is lined by more
hydrophobic residues (Papadopoulos and
Aquaporins (AQPs) or water channels are a Verkman 2013). An important property of
family of integral membrane proteins that form aquaporin-mediated water transport is its ability
hydrophilic pores in the cellular membrane. They to be regulated in response to cellular or environ-
are involved in the water transport through the mental signals. This is achieved by controlling
membrane. water transport at the individual protein level
All cells depend on their ability to maintain through a conformational change, so-called gat-
water homeostasis. This is achieved through the ing, or by altering the aquaporin density of a
action of aquaporins, membrane-bound water particular membrane. These proteins are present
channels that facilitate water ow across cellular in all kingdoms of life, demonstrating their central
membrane along osmotic gradients, while exclud- role in maintaining normal physiology of all
ing the passage of ions and protons. It is required organisms. The rst member of this family,
for maintenance of the membrane potential and AQP1, was identied in erythrocytes in 1991.
Aromatic and Nonaromatic Separation by Membrane Operations 111

This discovery led to homology cloning of hun- of aquaporin function by integrating evolutionary and
dreds of AQPs homologues from throughout the functional analyses. J Membr Biol 247:107125
Kreida S, Tornroth-Horseeld S (2015) Structural insights
animal and plant kingdoms, as well as from lower into aquaporin selectivity and regulation. Curr Opin A
organisms. Struct Biol 33:126134
In humans there have been identied Papadopoulos MC, Verkman AS (2013) Aquaporin water
13 aquaporins (AQP012) with specic organ, channels in the nervous system. Nat Rev Neurosci
14:265277
tissue, and cellular localization. Thus, different
members of the AQPs family are expected to
function in virtually all physiological processes
that involve water transport across the membrane.
The AQPs are expressed in many cell types
involved in uid transport, including epithelia Aromatic and Nonaromatic
and endothelia in the kidney, lung, exocrine Separation by Membrane Operations
glands, eyes, and gastrointestinal tract. However,
aquaporins are also expressed in cells that do not Lan Ying Jiang
have an obvious role in uid transport, such as School of Metallurgy and Environment, Central
erythrocytes and some leukocytes, adipocytes, South University, Changsha, China
and muscle. In addition, these are also expressed
in astrocytes throughout the central nervous sys-
tem and in supportive cells. Aquaporins have been Synonyms
linked to a number of pathological conditions,
including brain edema, renal disease, obesity, Dearomatization by membrane operations
and cancer, raising their attractiveness as drug
targets. Efcient separation of aromatics/nonaromatics
Given the key role played by aquaporins in the (generally referred to as dearomatization) is of
kidney, for recovering water permeated together great interest and signicance to the chemical
with other ions and molecules through the rst and petrochemical industries (Kung et al. 2010).
part of the glomerulus, they have been investi- Aromatic hydrocarbons such as toluene, benzene,
gated for developing biohybrid membranes able ethylbenzene, and xylenes are important feed-
to desalinate seawater. The biohybrid membranes stock in petrochemical industry; therefore, puri-
containing aquaporins showed very high water cation of aromatics is desired after they are
selectivity and permeability. Technological chal- produced through catalytic reforming, cracking,
lenges for productive application include or other processes (Sittig 1976). Nonaromatics
biohybrid membrane preparation on a large also have a wide range of applications (e.g., sol-
scale, aquaporin stability under operating condi- vents, fuels). They are generally derived from
tions or during membrane module cleaning, and aromatics/nonaromatics mixed feed, which neces-
maintenance operation. Development of synthetic sitates the separation of aromatic and nonaromatic
water channels mimicking aquaporins is a new hydrocarbons. For example, removal of aromatic
strategy under investigation. Highly selective hydrocarbons is needed to enhance the thermal
and permeable water channels are very interesting and oxidation stability, viscosity, and color of
for the development of seawater desalination plant lube oils. Aromatics such as benzene is carcino-
operating with very low energy input. genic; it is regulated by law that the levels of
aromatics in petrol and solvents must be con-
trolled (Singh et al. 2003). Removal of aromatics
References by-products will facilitate the improvement in the
production efciency of some petrochemical pro-
Di Giorgio J, Soto G, Alleva K, Jozefkowicz C, cesses, such as ethylene production through steam
Amodeo G, Muschietti JP, Ayub ND (2014) Prediction cracking (Corma et al. 2005).
112 Aromatic and Nonaromatic Separation by Membrane Operations

Presently, great interest from academia and content, while total ux is correspondingly
industry is given to studying the separation of aro- reduced. This is because PBI has stronger polarity,
matic/nonaromatic by membrane process, which is tighter and more rigid structure, as well as
pervaporation specically due to the dense structure enhanced anti-swelling property.
of its membrane capable of discriminating A pervaporation process alone might not be an
molecular-level difference as encountered in hydro- economical choice for aromatic/nonaromatic sep-
carbon mixtures. The separation in this process is aration. In the comparison among a conventional
based on the differential sorption and diffusion of extractive distillation process alone, a
permeating components inside membrane matrix, pervaporation system alone, and a hybrid system
coupled with the intrinsic volatility difference of consisting of the two processes in benzene/cyclo-
permeating components. It is the involvement of hexane separation, it is found that a hybrid system
selective membrane that makes pervaporation pro- is more economical than either of the two single
cess independent of the vaporliquid equilibrium processes (Rautenbach and Albrecht 1985). The
and therefore more energy efcient and environ- feed solution used for the evaluation is 1:1
ment friendly than classical distillation, rectica- (mol/mol) benzene/cyclohexane, and the target is
tion, extraction, and crystallization. to separate this mixture into two streams: 99.5 mol%
Numerous polymeric materials and some inor- benzene and 99.2 mol% cyclohexane. In both
ganic materials as well as their derivatives by extractive distillation process and hybrid process,
chemical (e.g., grafting, cross-linking) or physical furfural was used to break the benzene/cyclohex-
modications (e.g., polymer blending, inorganic ane azeotrope in the rst stage. The product from
lling) have been applied in preparing this stage is a cyclohexane-rich stream and a mix-
pervaporation membrane for aromatics/ ture of benzene/furfural. The benzene impurity in
nonaromatic separation (Smith et al. 2004). Aro- the cyclohexane-enriched stream is then removed
matics have double-bond-related p-electrons, by pervaporation, and the benzene/furfural mix-
hence having afnity toward membrane matrix ture is separated by distillation to get furfural and
containing polar functional groups. Size selection highly puried benzene. The advantage of hybrid
also favors the aromatics in the separation of some system is more striking when higher purity is
aromatic/nonaromatic pairs. A typical pair is ben- demanded of the products.
zene/cyclohexane wherein the former has smaller
molar volume. All of the organic and inorganic
materials utilized show preferential transport References
toward aromatics. Carbon-modied nylon
6 exhibited an extremely high separation factor Corma A, Melo FV, Sauvanaud L, Ortega F (2005) Light
cracked naphtha processing: controlling chemistry for
of more than 400. Commercialized polyvinyl
maximum propylene production. Catal Today
alcohol composite membrane also presents rec- 107108:699706
ommendable separation factor and ux. As an Kung G, Jiang LY, Wang Y, Chung TS (2010) Asymmetric
effort toward practical application, integrally hollow bers by polyimide and polybenzimidazole
blends for toluene/iso-octane separation. J Membr Sci
skinned asymmetric polymeric membranes for
360:303314
toluene/iso-octane separation were fabricated Rautenbach R, Albrecht R (1985) The separation potential
from blends of commercially available polybenzi- of pervaporation Part 2. Process design and economics.
midazole (PBI) and polyimide (PI) Matrimid J Membr Sci 25:2554
Singh AP, Mukherji S, Tewari AK, Kalsi WR, Sarpal AS
using dry-jet wet spinning followed by (2003) Determination of benzene and total aromatics in
non-solvent-induced phase inversion (Kung commercial gasolines using packed column GC and
et al. 2010). The best performance achieved is a NMR techniques. Fuel 82:2333
separation factor of 200 and a ux of 1.35 kg/m2-h Sittig M (1976) Aromatic hydrocarbons: manufacture and
technology. Noyes Data Corp, Ridge Park
in separating toluene/iso-octane (50/50 wt%).
Smith B, Suhany D, Sridhar S, Ramakrish M (2004) Sepa-
Separation factor for the selective transport of ration of organicorganic mixtures by pervaporationa
toluene increases with higher polybenzimidazole review. J Membr Sci 241:121
Artificial Blood Cell 113

They have a long shelf life. Unlike donated


Artificial Biological Membrane blood that breaks down after 1 month, articial
blood can be stored for over a year or more and A
Bioarticial Synthetic Membrane it can be stocked and easily shipped where
needed (Suman 2008; Cohn 2000; Nucci and
Abuchowski 1998; Lesley 2001).

Artificial Blood Cell A brief history. Though popular folklore sug-


gests that Maya Empire was trying to nd a blood
Antonietta Messina and Loredana De Bartolo substitute, it is only after William Harvey discov-
Institute on Membrane Technology, National ered and described the blood pathways and circu-
Research Council of Italy, ITM-CNR, Rende, lation throughout the body, in 1616, that medical
Italy practitioners tried numerous substances such as
milk, beer, plant resins, urine, and animal blood
as a substitute for blood. Therefore, the rst suc-
The expression articial blood refers to articial cessful human blood transfusion was done in
substitutes or articial surrogates purposely 1667. Only in 1868, researchers found that solu-
designed in laboratory in order to mimic and fulll tions containing hemoglobin isolated from red
two specic functions of the biological blood: the blood cells could be used as blood replacements.
transport of oxygen and carbon dioxide through- Therefore, the most important turning point in the
out the body and the maintenance of the hemosta- development of articial blood was made in 1883
sis inducing the blood clotting. Actually, the and 1890s with the development of the Ringer's
blood is a special type of connective tissue com- solution and the discovery by Karl Landsteiner of
posed of four different components in charge of a the human blood groups (A, B, AB, and O)
variety of functions. The white cells, responsible according to the capacity of their red cells to
for the immune defense; the red cells, responsible express on their membrane surface specic anti-
for the transportation of oxygen and carbon gens (Suman 2008; Nucci and Abuchowski
dioxide throughout the body; the platelets, 1998).
involved in the hemostasis process; and the As already said, there are two different prod-
plasma, an extracellular component made up of ucts under development as blood substitutes.
water, salts, and various proteins that, along with They differ primarily in their functions: they
platelets, encourages blood to clot. Actually, due carry oxygen or induce the blood clotting.
to this complex composition, it is not possible to Red blood cell substitutes. They are classied
reproduce the blood articially and only two of its in hemoglobin-based and peruorocarbon (PFC)-
components are laboratory designed: the red based substitutes. Hemoglobin-based products.
blood cells and the platelet substitutes. The arti- Derived from different sources (animal, human,
cial blood products have advantageous charac- recombinant) all hemoglobin products carry oxy-
teristics nowadays: gen by taking advantage of the natural hemoglo-
bin function. The natural hemoglobin products are
They are safe and biocompatible and lacking of obtained from human or animal blood. The human
the membrane antigens; therefore they are substitutes, in particular, are derived from blood
usable for all patient blood types. and red cells collected during plasma donations.
They are able to transport oxygen throughout The synthetic products, on the contrary, are the
the body and release it where needed. results of amino acids specic combinations or the
They possess a great level of safety. They can outcome of the recombinant biochemical technol-
be processed by ltration and pasteurization to ogy, which allow to derive hemoglobin harvested
remove all disease-causing agents such as from an E. coli bacteria strain. Independently on
viruses and microorganisms. the sources, the protein breaks down easily into
114 Artificial Blood Cell

smaller, toxic compounds. Then once obtained, it Platelet substitutes, they represent an essential
must undergo purication and partial modica- component of the thrombogenic response to
tion in order to decrease (i) the rapid formation bleeding through the adhesion to the damaged
of dimers and monomers that freely diffuse into vessel lining and releasing several coagulation
renal tubules causing renal failure and (ii) its factors. Platelet-Derived Products. Frozen plate-
strong afnity for factors (i.e., NO) causing vaso- lets and cold liquid-stored platelets have been
constriction, hypertension, and bradycardia. tested since 1950s in order to develop a treatment
Among the strategies employed to stabilize hemo- for thrombocytopenia. Despite being the only
globin the main important are the chemically alternative to fresh platelets in clinical use, disad-
cross-linking molecule processes and the encap- vantages as expensiveness with respect to the
sulation technology. Polyethylene Glycol- fresh platelets, morphological defects, and lower
Modied, Liposome-Encapsulated Hemoglobin, functionality directed the research toward new
and Polymersome-encapsulated hemoglobin discoveries. The Lyophilized platelet products
have been produced and commercialized (Enzon were developed since 1950s and are currently
and APEX Bioscience) for the treatment of cancer under animal trials. They are obtained by xing
and stroke patients and for treatment of hypoten- human platelets in paraformaldehyde prior to
sion induced by septic shock respectively (Chang freeze-drying them in an albumin solution with
1998). Moreover, hemoglobin products cova- no inuences on the adhesive properties of the
lently cross-linked with small bridges of sugar cells. The Platelet microparticles are
molecules showed not to induce vasoconstriction microvesicles formed spontaneously during the
in phase III of clinical trials (Gould and Moss storage. Deriving from the platelet membranes,
1996; Danielson et al. 1997). they showed similar hemostatic properties as
Peruorocarbon (PFC) products. PFC-based intact platelets. Cypress Bioscience developed
solutions are synthetic hydrocarbons with halide Infusive Platelet Membranes (IPM; Cyplex,
substitutions able to dissolve up to 50 times more Cypress Bioscience) using outdated human plate-
oxygen than plasma. These biologically inert let that are purposely fragmented, virally
materials allow to avoid the spreading of infec- inactivated, and lyophilized (Lesley 2001). With
tious disease via a blood transfusion. Neverthe- a shelf life of over 2 years these products are in
less, they are not soluble in water solution and phase II of clinical trials and appeared to be able to
require to be emulsied in oils or lipids before stop the bleeding in the 60 % of the patients
being injected into patients blood. Despite that a resulted refractory to platelet transfusion due to
special product, developed by the PFC therapeu- the immune response to HLA or platelet antigens,
tics, is currently in phase III of clinical trials for with no adverse effects or risks of thrombosis. In
use in cardiac and general surgical patients, cur- order to overcome the disadvantages of the plate-
rently these substitutes showed to have a short let processing, storage, and shelf life Platelet Sub-
duration of action, about 24 h, to be very expen- stitutes have been proposed. The Red cells with
sive, and to cause some adverse reactions associ- surface-bound brinogen or RGD peptides have
ated with their long-term usage. Their prolonged been subjected to numerous studies. Fibrinogen is
administration can cause several adverse reactions a free molecule able to bind activated platelets
such as the increase of the blood pressure and of together through the multiple Arginine-Glycine-
the pancreatic proteins, the gastrointestinal Aspartine (RGD) sequences. Bounding to the sur-
dysmobility, thrombocytopenia, u-like syn- face of autologous erythrocytes (red blood cells),
drome, and a quite important oxygen toxicity brinogen, or the RGD fragments, the
(Suman 2008; Cohn 2000; Lesley 2001). thromboerythrocytes obtained showed to be
Platelet substitutes. These articial products hemostatically effective in some animal
are very different from those already described. models of thrombocytopenia. Other important
Classied in Platelet-Derived Products and products are the Fibrinogen-coated albumin
Artificial Brain Model: Biohybrid Membrane System 115

microcapsules/microspheres. These are coated


with brinogen of the human protein albumin. Artificial Brain Model: Biohybrid
Two preparations have been evaluated in preclin- Membrane System A
ical trials: SynthocytesTM (Andaris Group Ltd,
Nottingham, UK) and ThrombospheresTM Sabrina Morelli
(Hemosphere, Irvine, Calif). The latter, due to Institute on Membrane Technology, National
their smaller mean diameter, showed in in vivo Research Council of Italy, ITM-CNR, Rende,
to have a long duration of action. Last, two Italy
Liposome-based agents have been studied: the
plateletsomes, which are lipid vesicles with plate-
let glycoproteins on their surface, and the factor Articial brain, in membrane operation, is a
Xa with phospholipid vesicles. Both demon- biohybrid membrane system which provides suit-
strated to be hemostatically effective in vitro and able conditions for the creation of a biomimetic
in some animal models, but problems of high microenvironment for neuronal tissue engineering
toxicity must be overcome in order to pass the resembling in vivo neuronal tissue properties and
clinical trials. functions.
Despite that numerous new discoveries and In the last decade, neuronal cell behavior on
products showed to be useful as blood substitutes, biomaterial such as membrane has become of
the current articial blood technology is limited great interest since it offers the advantage of
by the short-term shelf life, the costs, and the developing neuronal tissue that may be used for
toxicity problems clinically proved. Then new the in vitro simulation of human brain function
materials able to carry oxygen in the body and substitute. This could provide further insights not
to induce the blood clot must be found and only into the cell but also in developing therapies
longer-lasting products should be developed in neurodegenerative disorders such as
(Suman 2008; Lesley 2001; Lee and Blajchman Parkinsons or Alzheimers diseases. A biohybrid
1998). system using neurons could also represent a
useful instrument for predictive drug testing or
constitute a future model of a bioneuronal
References network device. To accomplish this task the
articial membrane must exhibit a specic micro-
Chang TMS (1998) Modied hemoglobin blood substi- architecture able to stimulate neuronal regenera-
tutes: present status and future perspectives. Biotechnol tion, therefore supporting axonal regrowth and
Annu Rev 4:75112
affecting cellular orientation and differentiation in
Cohn SM (2000) Blood substitutes in surgery. Surgery
127:599602 a positive way.
Danielson C, Ryder K, Glick M, Limiac A (1997) This biohybrid articial system consisting of
Hemoglobinbased blood substitutes in the blood bank. neurons and membranes offers a valuable tool for
Lab Med 28(2):131134
studying neuronal cell behavior and fundamental
Gould SA, Moss GS (1996) Clinical development of
human polymerized hemoglobin as a blood substitute. questions in neuroscientic research, and it also
World J Surg 20:12001207 could be used in a wide range of biotechnological
Lee DH, Blajchman MA (1998) Novel platelet applications.
products and substitutes. Transfus Med Rev
Several works in the literature show evidence
12:175187
Lesley K (2001) Articial blood: an update on current red that semipermeable polymeric membranes in at
cell and platelet substitutes. Proc (Bayl Univ Med Cent) and hollow ber congurations, thanks to their
14(2):158161 highly selective structural, physicochemical, and
Nucci ML, Abuchowski A (1998) The search for blood
transport properties, allow the successful in vitro
substitutes. Sci Am 278(2):7277
Suman S (2008) Articial blood. J Crit Care Med reconstruction of neuronal tissue reproducing a
12(3):140144 tissue model for studying metabolic diseases and
116 Artificial Brain Model: Biohybrid Membrane System

drug effects (De Bartolo et al. 2008; Zhang The importance of FC membrane culture sub-
et al. 2005 Morelli et al. 2014; Piscioneri et al. strates toward the highlighting of the effects of
2015). highly preferred GABAAR a2,5 agonists and
For typical neuronal tissue-engineered con- inverse agonists on the successful elongation of
structs, the properties of the material components neuronal processes and transcriptional activities
relevant to the tissue response include the surface of hamster hippocampal Gluergic cells was dem-
microgeometry, the MWCO, the electrical prop- onstrated for the rst time (Giusi et al. 2009).
erties, possibly the bioactive factors that are A biohybrid system composed of neuronal
loaded and sustainedly released through the chan- cells and silicon-supported nanoporous mem-
nel wall, and the degradation rate for biodegrad- branes has been designed to facilitate control of
able materials. The wettability of the membrane the biochemical environment of neuronal net-
surface has proved to be a factor that affects the works with cellular resolution. Nanoporous mem-
growth of neurons modulating the adsorption of branes may be used to interface with biological
adhesion proteins contained in the culture materials in a biohybrid system, for example, as
medium or secreted by cells that mediate the an articial chemical synapse interface (Wolfrum
adhesion of cells to the substrate. et al. 2006).
Advances in polymer chemistry have facili- Compared to traditional two-dimensional
tated the engineering of synthetic membranes (2D) culture systems, 3D in vitro cultures of neu-
that can be specically manipulated with regard ronal cells appear to better mimic in vivo neuronal
to their physical and mechanical characteristics, microenvironments representing a great potential
which may affect the interactions with cells. for building 3D neuronal circuits as well as for
The inuence of topographical features on creating tissue-based biosensors and for promot-
neuronal cell adhesion and differentiation has ing systemic restoration of severe nerve injuries.
been studied by using patterned adhesive areas In this context, several studies have been
that provide only a fraction of the surface for cell performed toward the determination of differ-
adhesion while the rest is cell repellent or by using ences between 2D and 3D environments for neu-
contact guidance cues in combination with also ronal function in order to provide great benet to
nerve growth factors or an electric eld. Topo- neuroengineering efforts. Recently, a complete
graphic guidance of neuritis outgrowth has been 3D neural tissue-like structure has been assembled
explored in vitro with a culture substrate in vitro using primary hippocampal cells and PAN
containing etches, microchannels, nanotubes, or HF membranes. As a consequence, this advanced
microgrooves. Micro-patterned biodegradable model system could allow the mimicking of hip-
poly(L-lactic acid) membranes directly improved pocampal neuronal events in order to study natu-
the guidance of neurite extension and thereby ral neurobiological properties of these cells, such
enhanced their orientation with a consequently as memory and learning processes, or the induc-
highly ordered neuronal cell matrix, which may tion of disease pathologies, allowing testing of
have strong bearings on the elucidation of regen- new therapies on the resolution of these states
eration mechanisms (Morelli et al. 2010). (Morelli et al. 2012).
Hippocampal neurons exhibited a different In the last decade, with rapid advances in bio-
morphology in response to varying the properties material technology, several types of natural and
of the membrane surface. Indeed, cells grown on synthetic biodegradable polymer, including colla-
the smoother membranes such as uorocarbon gen, chitosan, poly(glycolic acid), poly(L-lactic
(FC) and PES membranes displayed a large num- acid), poly(L-lactide-co-glycolide), poly
ber of neuritis with consequent formation of bun- (caprolactone), and polyurethane, have been
dles. The density of axonal network increases the reported as suitable for nerve regeneration,
neurites to become more elaborate and highly although the ideal physicochemical compositions,
branched on the smoother surfaces. surface structure, and functionalization of such
Artificial Kidney 117

materials have not yet been found. It was recently


reported that polycaprolactone-based membranes Artificial Kidney
successfully supported outgrowth and differentia- A
tion of human neuronal cells (Morelli et al. 2015). Sabrina Morelli
Institute on Membrane Technology, National
Research Council of Italy, ITM-CNR, Rende,
References Italy

De Bartolo L, Rende M, Morelli S, Giusi G, Salerno S,


Piscioneri A, Gordano A, Di Vito A, Canonaco M,
Drioli E (2008) Inuence of membrane surface proper-
Articial kidney, a synonym for hemodialyzer, is
ties on the growth of neuronal cells isolated from hip- an extracorporeal device through which blood
pocampus. J Membr Sci 325:139149 may be circulated for removal of elements that
Giusi G, Facciolo RM, Rende M, Alo R, Di Vito A, normally are excreted in the urine.
Salerno S, Morelli S, De Bartolo L, Drioli E, Canonaco
The articial kidney is used to rid the blood of
M (2009) Distinct a subunits of the GABAA receptor
are responsible for early hippocampal silent neuron- metabolic products, to correct electrolyte-water
related activities. Hippocampus 19:11031114 and acid-alkaline balances in acute and chronic
Morelli S, Salerno S, Piscioneri A, Papenburg BJ, Di renal insufciency, to remove dialyzing toxic sub-
Vito A, Giusi G, Canonaco M, Stamatialis D,
stances in cases of poisoning, and to remove
Drioli E, De Bartolo L (2010) Inuence of micro-
patterned PLLA membranes on outgrowth and orienta- excess water in cases of edema. In 1913 the Amer-
tion of hippocampal neurites. Biomaterials ican scientist Abel created an apparatus for dialy-
31:70007011 sis that was the basis for the articial kidney;
Morelli S, Piscioneri A, Salerno S, Rende M, Campana C,
Tasselli F, Di Vito A, Giusi G, Canonaco M, Drioli E,
Dr. Willem Kolff, a Dutch physician, constructed
De Bartolo L (2012) Flat and tubular membrane sys- the rst functioning articial kidney. He treated
tems for the reconstruction of hippocampal neuronal his rst patient in 1943, and in 1945 he was rst
network. J Tissue Eng Regen Med 6:299313 able to save a patients life with hemodialysis
Morelli S, Piscioneri A, Messina A, Salerno S, Al-Fageeh
treatment.
MB, Drioli E, De Bartolo L (2015) Neuronal growth
and differentiation on biodegradable membranes. The articial kidney operates on the princi-
J Tissue Eng Regen Med. 9:106117 ple of the dialysis of substances through a
Morelli S, Piscioneri A, Salerno S, Al-Fageeh M, Drioli E, semipermeable membrane. Dialysis is a result
De Bartolo L (2014) Neuroprotective Effect of
of the differences in the concentrations of sub-
Didymin on H2O2-Induced Injury in Neuronal Mem-
brane System. Cells Tissues Organs 199:184200 stances in the blood and in the dialyzing solu-
Piscioneri A, Morelli S, Mele M, Canonaco M, Bilotta E, tion, which contains glucose and the principal
Pantano P, Drioli E, De Bartolo L (2015) electrolytes of the blood in nearly physiological
Neuroprotective effect of human mesenchymal stem
concentrations without containing any of the
cells in a compartmentalized neuronal membrane sys-
tem. Acta Biomaterialia 24:297308. substances that must be removed from the
Wolfrum B, Mourzina Y, Sommerhage F, Offenhausser body (urea, creatinine, uric acid, sulfates, phos-
A (2006) Suspended nanoporous membranes as inter- phates). Proteins, formed elements of the blood,
faces for neuronal biohybrid systems. Nano Lett
bacteria, and substances with a molecular
6:453457
Zhang N, Yan H, Wen X (2005) Tissue-engineering weight of more than 30,000, do not pass
approaches for axonal guidance. Brain Res Rev through the membrane. During hemodialysis
49:4864 the patients blood is drawn off through a cath-
eter by a pump from the inferior vena cava and
passed inside the chambers of membranes of
the dialyzer; these chambers are washed outside
Artificial Functional Organ by the dialyzing solution, which is supplied by
another pump. Partially puried, the blood is
Membrane Articial Organs returned to one of the surface veins.
118 Artificial Kidney

The membrane used during hemodialysis has reduced induction of inammatory mediators.
evolved signicantly since the earliest reports. While observational studies suggest that high-
Early membranes were natural materials, such as ux hemodialysis is associated with lower and
cellulose, or simple synthetic compositions, such dialysis-related amyloidosis, individual random-
as polysulfone, with symmetric structures and ized controlled trials have not conrmed that
good performance for small solute passage high-ux hemodialysis improves clinical out-
(Fleming 2011). comes. High-ux dialysis membranes have
However, these membranes include signicant larger pore sizes that may increase transportation
interactions with the complement pathway and of dialysate impurities or contaminants from the
immune response. Modifying the hydroxyl dialysate to the bloodstream even when the dial-
groups on cellulose membranes gives similar per- ysate quality complies with acceptable stan-
formance characteristics and less bioactivity and dards, although some evidence suggests that
includes cellulose diacetate and hemophan mem- high-ux membranes may actively absorb endo-
branes. With improvements in chemical engineer- toxins and impede their back transfer from dial-
ing and manufacturing, cellulose-based ysate into the bloodstream (Palmer and Strippoli
membranes have yielded to synthetic membranes. 2013).
The most popular membranes in use today are Although dialysis is currently an available
polyacrylonitrile and polysulfone; however, poly- treatment for chronic renal disease, it replaces
amide, polycarbonate, and polymethyl- only the ltration function of the kidneys, and
methacrylate are available. These materials have thus, it is associated with a number of complica-
improved biocompatibility and reduce comple- tions and is not a permanent solution. Kidney
ment activation; however, they may enhance pro- transplantation performed in a heterotopic loca-
tein adsorption to the membrane in the absence of tion is the only denitive solution for end-stage
further modication. Despite the improved com- renal failure. A potential solution to ease the
patibility of synthetic membranes, the most recent demand for donor kidneys may be the use of tissue
large review does not demonstrate benets con- engineering techniques that could be used to
veyed by biocompatibility. The ultrastructure of develop functional kidneys. A primary challenge
membranes is predominantly the capillary design, in renal tissue engineering, however, is the pro-
or hollow ber structure, in which blood ows duction of tissues with the functional complexity
through a series of small tubes held together in a required for kidney transplantation. The rst step
bundle. This allows for a low-resistance, high in achieving this aim could be to produce acellular
surface area membrane. Membrane properties kidney matrices for use as biological scaffolds that
such as charge, wall thickness, and pore size affect support cell growth and facilitate new tissue for-
function. The radius of the pore is related to the mation by potentiating cellcell interaction. Sev-
ultraltrate ow through the membrane, but over- eral groups have used different perfusion-based
all uid transfer is a function of the mean pore decellularization protocols to produce naturally
size. The number or density of pores and the derived kidney scaffolds (Arenas-Herrera
radius of the pore affect solute transfer in diffusive et al. 2013).
clearances. Membrane characteristics such as ux In the last decade, several studies have been
and permeability to water are determinants of pore performed on the development of the implantable
characteristics and wall thickness (Vigano articial kidneys, but these studies reported only
et al. 2008). developmental concepts, in vitro or in vivo studies
As dialysis membrane technology has using small animals. It is difcult to control cer-
improved, high-ux membranes with larger tain research aspects of an implantable articial
pore sizes have been developed to allow greater kidney to a preclinical level, and these aspects
clearances of larger retention molecules with include long-term maintenance of the
Artificial Liver, Membrane Operations 119

antithrombogenic properties of the systems and


each of its components, and the function of an Artificial Liver, Membrane
implanted, miniaturized system, whose function Operations A
must be maintained for a years duration. Further
progress in nanotechnology and biotechnology is Antonietta Messina and Loredana De Bartolo
required to realize a treatment with an implantable Institute on Membrane Technology, National
kidney (Saito et al. 2011). Research Council of Italy, ITM-CNR, Rende,
New directions in dialysis research include Italy
cheaper treatments, home-based therapies, and
simpler methods of blood purication. These
objectives may be probably obtained with inno- The expression of articial liver denes all the
vations in the eld of articial kidney through the supporting membrane systems able to substitute
utilization of new disciplines such as miniaturiza- or integrate the liver functions when it reaches
tion, microuidics, and nanotechnology. This the 30 % critical threshold of the normal hepatic
research may lead to a new era of dialysis in activity. The liver is the biggest glandular organs
which the new challenges are transportability, in the human body. Placed in the upper section of
wearability, and why not the possibility to develop the abdominal cavity, this dark red organ is well
implantable devices (Ronco et al. 2011). known to be able to self-regenerate from partial
injuries doubling its mass in 1 day. Therefore,
acute or chronic hepatic insufciencies caused
by viral pathology, drug abuse, intoxications, or
References pathological decompensation can result in severe
liver failure (LF). Though implying the inability
Arenas-Herrera JE, Ko IK, Atala A, Yoo JJ of the liver to completely carry out its metabolic,
(2013) Decellularization for whole organ bioengineer-
ing. Biomed Mater 8:014106. doi:10.1088/1748-6041/
excretory, and detoxifying functions, both the
8/1/014106 acute and chronic hepatic insufciency (ALF,
Fleming GM (2011) Renal replacement therapy review. ACLF) can potentially be reversible if one third
Past, present and future. Organogenesis 7:212 of the organ is still functioning; then liver activity
Palmer SC, Strippoli G (2013) High-ux versus low-ux
can return to good levels. However, the LF leads
haemodialysis membranes for end-stage kidney dis-
ease. Nephrology 18:313314 to an accumulation of water-soluble and albumin-
Ronco C, Davenport A, Gura V (2011) The future of the bounded toxins that cause encephalopathy and a
articial kidney: moving towards wearable and minia- multi-organ dysfunction. The solely long-term
turized devices. Nefrologia 31:916
therapy to stem a hepatic insufciency is the
Saito A, Sawada K, Fujimura S (2011) Present status and
future perspectives on the development of bioarticial orthotopic transplantation that ensures a notable
kidneys for the treatment of acute and chronic renal recovery of hepatocytes in number and function-
failure patients. Hemodial Int 15:183192 ality. Actually, due to the limited number of
Vigano SM, Di Filippo S, Manzoni C, Locatelli F (2008)
donors, only a narrow circle of patients in waiting
Membrane characteristics. In: Ronco C, Cruz DN (eds)
Hemodialysis-from basic research to clinical trials, list can be transplanted according to the severity
vol 161, Contribution of nephrology. Karger, Basel, of their disease. Thus, in order to improve
pp 162167 patients prognosis and survival, articial extra-
corporeal liver assist devices have been developed
either bridging the patient to transplantation and
temporarily supporting the failing organ until it is
Artificial Liver able to regenerate. Basically, three different types
of supportive therapies are nowadays available:
Bioarticial Liver bio-articial, articial, and hybrid liver support
120 Artificial Liver, Membrane Operations

systems. Therefore, between them, the articial articial support system for treating the LF. The
systems are the most used in clinic due to the cellular components of the blood are separated
lower costs and their easier handling. Articial from the plasma using a hollow ber lter
liver support systems are cell-free membrane (cellulose diacetate or polyethylene) able to
devices aimed to temporally replace native liver remove toxins and supply lacking components as
detoxication functions through processes of albumin or coagulation factors. However, this
adsorption and ltration in order to improve the method has a disadvantage: it requires a large
clinical state of the patient. The most of articial plasma stock with ensuing higher costs and
liver devices use membrane separation associated bears the risk of infections. Moreover, most of
with columns or suspensions of sorbents (e.g., the toxins that accumulate in the plasma of
charcoal, anion-exchange or cation-exchange patients with liver insufciency are protein
resins) that selectively remove toxins and/or bound; then these methods are not able to ade-
regenerate dialysate or plasma ltrate (Carpentier quately eliminate them. This is the reason why
et al. 2009; Naruse et al. 2007). Conventional new dialysis systems have been developed using
dialysis techniques, such as hemoltration, albumin as scavenger to clear the toxins involved
hemodialysis, or hemodialtration, have been in the physiopathology of the failing liver.
used for the removal of the low molecular weight Between the different albumin dialysis modalities,
water-soluble metabolites. The hemodialysis the single-pass albumin dialysis (SPAD) has
allows to remove water-soluble metabolites, to shown some positive results. The patients blood
re-equilibrate the acid-basic and the electrolytic passes a high-ux dialysis membrane, while an
values in the blood, and to reduce also the ammo- albumin solution streams counter-directionally to
nia concentrations. The hemoltration is carried the ltering blood membrane, accepting toxins
out by ltrating cellulose or polysulfone mem- from the plasma. Therefore, the system works at
branes with a MWCO of 50 KDa. These mem- a very high cost due to the high concentration of
brane devices remove toxic and natural albumin needed in the dialysate to perform the
substances through connective transport allowing plasma detoxication (Naruse et al. 2007;
to partially recover from the hepatic encephalop- Onodera et al. 2006). At present, there are only
athy. The hemoperfusion is performed through two articial extracorporeal liver support systems
extracorporeal devices constituted by active used in clinic: the Molecular Adsorbents
charcoal adsorbing elements covered by a cellu- Recirculating System (MARS1) from Gambro
lose or polysulfone hemocompatible lm. and Fractionated Plasma Separation and Adsorp-
Adsorbing a variety of water-soluble toxins in tion (FPSA), which was designed by Fresenius
the low and middle molecular weight range, the Medical Care (Bad Homburg, Germany) and
hemoperfusion has a signicant disadvantage; in commercialized as Prometheus1 (Carpentier et al.
fact it has been demonstrated that the resulting 2009; Evenepoel et al. 2006).
patients plasma can be highly impoverished of MARS is the most used articial liver support
important biological substances causing impor- system. Introduced in clinics in 1993, it consists of
tant decompensation in patients metabolism. In three components: (A) a conventional dialysis
order to improve the specicity of the detoxica- machine that guides the extracorporeal blood cir-
tion process, membrane reactors containing cuit (MARSFLUX), (B) a supplementary device
immobilized enzymes have been developed. for the albumin circuit made of two different
Hepatic enzymes are denitively linked onto hol- adsorption columns (MARS AC250, MARS
low ber membranes or enclosed in microcap- IE250), and (C) a dialysate circuit for low ux
sules and showed to be able to enhance the dialysis (Rademacher et al. 2011). How it works:
recovery of the patients mental state; hence, the the patients blood is pumped in the blood circuit
percentage of surviving patients does not increase, throughout a double-lumen central venous cathe-
and the clinical application is very limited. The ter. Here a rst column, the MARSFLUX system,
plasma exchange/plasmapheresis is another contains a polysulfone membrane with MWCO of
Artificial Liver, Membrane Operations 121

50 KDa that lters the blood and allows the pas- In the last decades, other dialysis albumin cir-
sage through the membrane of the water-soluble cuits have been developed for LF treatment, such
molecules and the free toxins, retaining the albu- as the continuous veno-venous hemodialysis A
min due to its higher dimension. In the meantime, (CVVHD) and the continuous veno-venous
the second circuit pushes in counter direction with hemodialtration (CVVHDF); therefore, though
respect to blood ux, a 20 % albumin solution that being able to decrease the load of water-soluble
induces the dissociation of the protein-bounded toxins, they cannot provide the complete plasma
toxins freeing the albumin of the plasma. The treatment. The last available articial liver is
dialysate albumin, now saturated, is then restored named selective plasma ltration therapy system
passing through two adsorption columns in the (SEPET). In this system, the patients blood
second circuit: the MARS AC250 lled with passes through a single-use cartridge constituted
active charcoal that retains high molecular weight by hollow bers with MWCO of 100 kDa
molecules (bilirubin) and the MARS IE250 lled allowing molecules with a molecular weight
with the anion-exchange resin cholestyramine that close to 100 kDa to pass the membrane in only
retains the negative-charged molecules. Albumin limited amounts, while albumin, HGF, and several
solution of the second circuit is then restored and clotting factors are retained. Main characteristic of
can be used for a new cycle of treatment. The this process is that a plasma fraction is completely
MARS is recommended for treating both acute discarded during the ltration procedure. This
and chronic liver failure, despite the survival of fraction contains accumulated small molecular
patients is only partially increased. Therefore, weight toxins and free pro-inammatory cyto-
many positive clinical results have been recorded kines; then, to replace the uid loss, a mixture
for the patients in the last years such as the composed of electrolyte solution, human albumin
increase of the arterial pressure values and the solution, and fresh frozen plasma is added to the
systemic vascular resistance index, the attenua- system and collected to the patients blood. This
tion of hyperdynamic circulation, and the signi- SEPET system is designed for use with any com-
cant decrease not only for bilirubin but also mercially available kidney dialysis unit and/or
for creatinine and urea (Evenepoel et al. 2006; plasma apheresis system utilizing hollow ber
Rozga 2006). cartridges (Carpentier et al. 2009; Rozga 2006).
The Prometheus articial system realizes the Many other attempts in developing articial liver
combined removal of the albumin-bounded and systems are conducted nowadays in order to
the water-soluble toxins by means of adsorption improve methods and clinical results. The ulti-
and fractionated plasma separation. It was devel- mate goal is then to develop a liver support device
oped by Falkenhagen in 1999, and the system is that will grant patients a substantial survival ben-
based on FPSA combined with hemodialysis and et compared to standard intensive care now
consists of two circuits (Falkenhagen et al. 1999). available.
In the rst one, the blood is collected through the
double-lumen catheter and allowed to ow through
a polysulfone membrane. Its MWCO of 250 KDa References
allows either the free toxins or the plasma albumin-
bounded toxins to pass through the membrane Carpentier B, Gautier A, Legallais C (2009) Articial and
reaching the second circuit. Here the plasma is bioarticial liver devices: present and future. Gut
58:16901702
puried by a direct adsorption process into the Evenepoel P, Laleman W, Wilmer A, Claes K, Kuypers D,
same two columns of MARS: the anion-exchange Bammens B, Nevens F, Vanrenterghem: Y (2006) Pro-
column and the neutral resin column. Then the metheus versus molecular adsorbents recirculating sys-
blood is recombined with the non-treated fraction tem: comparison of efciency in two different liver
detoxication devices. Artif Organs 30(4):276284,
and dialyzed completely in a high-ux device for Blackwell Publishing, Inc.#
the water-soluble molecules removal (Evenepoel Falkenhagen D, Strobl W, Vogt G, Schre A, Linsberger I,
et al. 2006; Rozga 2006). Gerner FJ, Schoenhofen M (1999) Fractionated plasma
122 Artificial Lung

separation and adsorption system: a novel system for Membrane oxygenators can be used in two
blood purication to remove albumin bound sub- principal modes: to imitate the function of the
stances. Artif Organs 23(1):8186
Naruse K, Tang W, Makuuchi M (2007) Articial and lungs in cardiopulmonary bypass (CPB) and to
bioarticial liver support: a review of perfusion treat- oxygenate blood in longer-term life support,
ment for hepatic failure patients. World J Gastroenterol termed extracorporeal membrane oxygenation
13(10):15161521 (ECMO). A membrane oxygenator consists of a
Onodera K, Sakata H, Yonekawa M, Kawamura A (2006)
Articial liver support at present and in the future. thin gas permeable membrane separating the
J Artif Organs 9:1728 blood and gas ows in the CPB circuit; oxygen
Rademacher S, Oppert M, Jrres A (2011) Articial extra- diffuses from the gas side into the blood, and
corporeal liver support therapy in patients with severe carbon dioxide diffuses from the blood into the
liver failure. Exp Rev Gastroenterol Hepatol
5(5):591599 gas for disposal.
Rozga J (2006) Liver support technology an update. Preliminary efforts to design, fabricate, and test
Xenotransplantation 13:380389 membrane articial lungs have been reported
since the 1950s. The early articial lungs used
relatively impermeable polyethylene or Teon
homogeneous membranes, and when more highly
Artificial Lung permeable silicone rubber membranes were intro-
duced in the 1960s (and as hollow bers in 1971),
Loredana De Bartolo and Sabrina Morelli the membrane oxygenator became commercially
Institute on Membrane Technology, National successful. The introduction of microporous hol-
Research Council of Italy, ITM-CNR, Rende, low bers with very low resistance to mass trans-
Italy fer revolutionized the design of membrane
modules, as the limiting factor to oxygenator per-
formance became the blood resistance (Martin
The articial lung is a medical device used to take and Zwischenberger 2013).
over or supplement the function of the lung which Current designs of oxygenator typically use an
is to oxygenate the blood and remove carbon extraluminal ow regime, where the blood ows
dioxide. outside the gas-lled hollow bers, for short-term
Such a device can replace entirely the pulmo- life support, while only the homogeneous mem-
nary gas exchange or assist the decient gas trans- branes are approved for long-term use.
fer capacity of the natural organ, either The key design considerations in blood oxy-
temporarily, with the hope that the healing process genators include minimizing the resistance to
will eventually repair the diseased organ, or per- blood ow, reducing the priming volume, ensur-
manently, when irreversible lung damage leaves ing easy debubbling at setup, and minimizing
the patient permanently disabled. blood activation and thrombogenicity.
Articial lung can be used as a bridge to lung The fabrication or wrapping of the ber bundle
transplantation, as a support device immediately in a blood oxygenator can be important as the
post-lung transplant, and as a rescue and/or sup- geometry obtained impacts diffusional boundary
plement to mechanical ventilation during the layers, secondary ows, and gas exchange
treatment of severe respiratory failure (Diaz- efciency.
Guzman et al. 2013; Javidfar and Bacchetta Looking ahead, current challenges in
2012). bioarticial lung engineering include creation of
Current articial lungs are also known as blood ideal scaffold materials, differentiation and
oxygenators and are modules composed of bun- expansion of lung-specic cell populations, and
dles of hollow ber membranes designed to bring full maturation of engineered constructs to pro-
blood and gas phases in intimate contact separated vide graft longevity after implantation in vivo
by only the thin walls of the hollow bers. (Sond and Ott 2012).
Asymmetric Ceramic Hollow Fiber Membranes 123

References

Diaz-Guzman E, Hoopes CW, Zwischenberger JB


(2013) The evolution of extracorporeal life support as A
a bridge to lung transplantation. ASAIO J 59:310
Javidfar J, Bacchetta M (2012) Bridge to lung transplanta-
tion with extracorporeal membrane oxygenation sup-
port. Curr Opin Organ Transplant 17:496502
Martin JT, Zwischenberger JB (2013) Articial lung and
novel devices for respiratory support. Semin Thorac
Cardiovasc Surg 25:7075
Song JJ, Ott HC (2012) Bioarticial lung engineering. Am
J Transplant 12:283288

Asymmetric Ceramic Hollow Fiber Membranes,


Fig. 1 An asymmetric aluminum oxide hollow ber
Assisted Transport micro-ltration membrane with an outer diameter of
1.8 mm
Facilitated Transport

extrusion, the most common method of fabrica-


tion involves the incorporation of phase inversion
Asymmetric Ceramic Hollow Fiber to create asymmetric structures during the extru-
Membranes sion process. In this method, a mixture of polymer
binder and ceramic material, suspended in a suit-
Benjamin F. K. Kingsbury able solvent, is extruded through a spinneret into
Imperial College London, London, UK contact with a uid that leads to precipitation of
the polymer phase. As the polymer binder pre-
cipitates, the polymer-ceramic suspension is
Asymmetric ceramic hollow ber membranes are converted into a polymer-ceramic mixed matrix
ceramic tubes with outer diameters typically rang- ceramic hollow ber precursor. The precursor is
ing from 0.5 to 2 mm, utilized for separation then heated to remove the polymer binder and
processes. To be classied as asymmetric, a hol- consolidate the ceramic material by sintering to
low ber must have a nonuniform cross-sectional yield the nal product. Very small hollow ber
structure consisting two or more different mor- diameters can be achieved using this fabrication
phologies. They may be formed from a wide technique with asymmetric cross-sectional struc-
range of ceramic materials depending on their tures consisting of conical micro-channels as well
purpose and may be either dense or porous as a porous ceramic matrix (Fig. 1). Moreover,
according to the type of separation process for multiple layers can be extruded simultaneously to
which they are designed. When combined form asymmetric cross-sectional structures which
together in a module, hollow ber geometry also contain layers of different materials.
gives rise to extremely high membrane surface Asymmetric ceramic hollow ber membranes
area per volume leading to compact membrane can be broadly categorized as either porous or
module designs. Asymmetric membranes offer dense. The former operate on a size exclusion
improved performance by combining a thin sepa- basis usually at low to moderate temperatures
ration layer with a support layer which has high and are commonly fabricated from inert ceramic
permeability. Although asymmetric structures can materials such as aluminum oxide. Asymmetric
be achieved by depositing additional layers on a structures such as that shown in Fig. 1 (Kingsbury
symmetric ceramic hollow ber formed by screw and Li 2009) are prepared in a single step and
124 Asymmetric Hollow Fiber Membranes

consist of a support layer formed from micro- membrane reactors and solid oxide fuel cells. In:
channels and an outer porous separation layer. Basile A, Nunes SP (eds) Advanced membrane science
and technology for sustainable energy and environmen-
The development of asymmetric morphologies tal applications, 1st edn. Woodhead, Cambridge,
such as that shown in Fig. 1 allows for ltration pp 496540
membranes with high ux to be fabricated in a
cost-effective way, with the additional benet of
integrated separation and support layers, leading
to a robust and durable structure. Dense asymmet-
ric ceramic hollow ber membranes operate at Asymmetric Hollow Fiber
higher temperatures with separation occurring by Membranes
lattice diffusion. Membranes fabricated from pro-
ton conducting, ionic conducting, and mixed ionic Lan Ying Jiang
and electronic conducting materials have a num- School of Metallurgy and Environment, Central
ber of potential applications such as oxygen sep- South University, Changsha, China
aration from air, solid oxide fuel cells, and the
partial oxidation of methane to synthesis gas.
For example, an asymmetric hollow ber oxygen The asymmetric membranes can be formed into
separation membrane can be formed from a different geometries such as the at sheet and the
perovskite material, by extruding a hollow ber hollow bers, by choosing the fabricating or cast-
in which a region of micro-channels supports a ing equipment. Hollow bers have annulus cross
thin outer oxygen separation layer (Zydorczak sections with the inner and outer circular skins of
et al. 2009). The micro-channels formed during the membranes being concentric. The outer diam-
the extrusion process provide mechanical strength eter of a hollow ber is less than 1 mm. Their
while at the same time greatly reducing the resis- advantages associated with practice usage include
tance to oxygen permeation compared to a sym- large membrane area per unit volume, self-
metric hollow ber structure. Asymmetric contained mechanical support, good exibility,
multilayer structures formed by co-extrusion and easy handling during the module fabrication
have been developed for solid oxide fuel cells and in the operation, etc. (Matsuura 1994, Peng
and membrane reactor applications in which et at. 2012). These facts have contributed to the
each layer has a different function. Examples lower fabrication cost and higher-performance
include the co-extrusion of an anode and electro- efciency of hollow ber membrane modules.
lyte as an asymmetric hollow ber in a single step By far, the most technically used hollow ber
(Othman et al. 2010), and the co-extrusion of a is produced by phase inversion: non-solvent-
dual-layer hollow ber membrane reactor for induced phase inversion (NIPS), (solvent)
partial oxidation of methane to synthesis gas evaporation-induced phase inversion (EIPS),
comprised of a dense oxygen separation mem- VIPS (vapor sorption-induced phase inversion),
brane on a porous catalytically active support and TIPS (thermally induced phase inversion)
(Wu et al. 2011). (Ulbricht 2006). In single-layer hollow ber
asymmetric membrane formation by NIPS, there
are two coagulations taking place in hollow ber
spinning (shell and lumen surfaces), while there is
References
only one major coagulation surface for an asym-
Kingsbury BFK, Wu Z, Li K (2011) Inorganic hollow ber metric at sheet membrane. The mass exchange
membranes for chemical reaction. In: Basile A, between internal coagulation liquid and lumen
Gallucci F (eds) Membranes for membrane reactors: surface for a hollow ber starts immediately
preparation, optimization and selection, 1st edn. Wiley,
Chichester, pp 117153
after liquid extrusion from the conduit of a spin-
Wu Z, Othman MHD, Kingsbury BFK, Li K (2011) Func- neret. For the contact of shell surface of nascent
tional ceramic hollow ber membranes for catalytic ber and the external coagulation bath, two
Asymmetric Hollow Fiber Membranes 125

different concepts are used. In some cases, there is 3. By adjusting the dope solution concentration,
an interval between nascent membrane extrusion hollow bers with ultrahigh pressure resistance
and immersing in the external coagulant. This can be produced A
contact at the external boundary could also syn- 4. The formation of composite membranes is
chronize with that at the internal boundary by more straightforward and cost effective
directly immersing the spinneret inside the exter- 5. Higher uxes are obtained by circumventing
nal coagulant. The former has a name of dry-jet pore penetration occurring in dip coating.
wet spinning. The mass transfer associated with
the dry step during the nascent bers residence Recently, an idea of immiscibility induced
time in the air gap is short under commercial phase separation (I2PS) was proposed (Ong and
spinning conditions but important in membrane Chung 2013). Phase separation of two immiscible
structure control. Solvent evaporation in the dry dopes renders the formation of a selective layer
step can cause polymer concentration at dope/air between the inner layer and outer layer. The
interface increase. This situation is favorable for degree of swelling of selective layer by feed liquid
forming a relatively compact skin and is often can be moderated as a result of its being shielded
practiced in fabricating membranes for gas sepa- from direct contact with the feed mixture by the
ration or pervaporation. One can easily create this outer layer.
situation by making the temperature of the spin
dope close to the boiling point of the volatile
solvent or non-solvent (Jiang et al. 2004). Rheo-
logical aspect is another choice in ne-tuning
References
hollow ber membrane morphological character-
istics to meet the requirement of separation tasks. He T, Mulder MHV, Strathmann H, Wessling M (2002)
Depending on the polymer intrinsic rheological Preparation of composite hollow ber membranes:
characteristics, air gap and take-up speed are co-extrusion of hydrophilic coatings onto porous
hydrophobic support structures. J Membr Sci
adjusted to deliver polymer chain orientation or
207:143156
more ordered arrangement along the elongation Jiang LY, Chung TS, Li DF, Cao C, Kulprathipanja
direction that improves selectivity of gas separa- S (2004) Fabrication of Matrimid/polyethersulfone
tion membranes (Kneifel and Peinemann 1992). dual-layer hollow ber membranes for gas separation.
J Membr Sci 240(12):91103
Shearing effect that occurs inside the spinneret
Jiang LY, Wang Y, Qiao XY, Chung TS, Lai JY
can also induce orientation, which motivates (2009) Polyimides membranes for pervaporation and
many design strategies of conduit channel near biofuels separation. Prog Ploys Sci 34(11):11351160
the exit (Widjojo et al. 2007). Kneifel K, Peinemann YV (1992) Preparation of hollow
ber membranes from polyetherimide for gas separa-
Composite hollow bers are mostly formed by
tion. J Membr Sci 65:295307
dip coating, interfacial polymerization, etc., as an Matsuura T (1994) Synthetic membranes and membranes
additional step to the porous hollow ber formed separation processes. CRC press, Boca Raton
by phase inversion. Presently, the type of dual- Ong YK, Chung TS (2013) Pushing the limits of high
performance dual-layer hollow ber fabricated via
layer composite asymmetric hollow bers pro-
I2PS process in dehydration of ethanol. AIChE
duced by co-extrusion through a triple-orice J 59:30063018
spinneret represents a new direction Peng N, Widjojo N, Sukitpaneenit P, Teoh MM, Lipscomb
(He et al. 2002). Compared to the single-layer G, Chung TS, Lai JY (2012) Evolution of polymeric
hollow bers as sustainable technologies, Prog Polym
asymmetric hollow bers, the dual-layer hollow
Sci 37:14011424
bers are more advantageous due to the following Ulbricht M (2006) Advanced functional polymer
reasons (Jiang et al. 2009): membranes. Polymer 47:22172262
Widjojo N, Chung TS, Krantz WB (2007)
A morphological and structural study of Ultem/P84
1. Material cost saving by more than 95 %
copolyimide dual-layer hollow ber membranes with
2. Possibility to employ brittle (engineering delamination-free morphology. J Membr Sci
infeasible) but advanced material 294:132146
126 Asymmetric Membrane

step from one material. Phase inversion is a pro-


Asymmetric Membrane cess wherein the thermodynamically stable poly-
mer solution is converted into the instable one by
Lan Ying Jiang changing dope composition. The resultant mem-
School of Metallurgy and Environment, Central branes exhibit graded morphology with a gradual
South University, Changsha, China transition from relative dense structure at one side
of the membrane to fully porous structure on the
other side, in consistence with the characteristics
For almost all the membrane process, ux is one of phase inversion course. In a simplied manner,
of the essential process parameters. The advan- this type of membranes is often described as hav-
tages associated with high ux are small mem- ing a thin skin supported by a porous support. The
brane area and efcient system footprint. These thin skin layer carries out the separation, while the
two factors are often considered by chemical engi- substrate generally presents negligible resistance
neers or managers in their decision-making about to the transport of penetrants. This so-called skin
setting up processes using membrane separation. layer is nonporous for gas separation, reverse
The thinner the required membrane structure, the osmosis, pervaporation, and nanoltration mem-
higher the membrane ux. However, mechanical branes. There also exist several other techniques
strength will be reduced with decreasing mem- pertaining to phase inversion. They are thermally
brane thickness. or pressure induced. The membranes generated
One of the solutions to this problem was asym- have a rather isotropic cross-section morphology.
metric membrane. Loeb and Sourirajan in 1963 To fulll the same target but avoid the disad-
(Loeb and Sourirajan 1964) invented integrally vantages of the integrally skinned asymmetric
skinned asymmetric membrane for reverse osmo- membranes, a series of other types of membrane
sis. They are produced by non-solvent-induced are developed. Figure 1 shows the schematic of
liquid-liquid phase separation processes, in the dense membrane and ve principle types of
which the entire structures are generated in one membranes that are currently used (Paul and

a d
Selective layer
Dense film
(tens of m) Microporous
skin layer
(porosity>1%)

Defect-free
Selective layer
skin layer
b (0.11m) e
Gutter layer

Microporous
substrate Microporous
(100300m) support

c Sealing layer f Selective


(0.11m) asymmetric
layer (material A)
Selective
skin layer
(porosity <104%) Microporous
support
(material B)

Asymmetric Membrane, Fig. 1 Schematic of dense and composite, (d) single-layer composite, (e) multilayer com-
asymmetric membranes. (a) Dense lm, (b) integrally posite, (f) asymmetric composite
skinned asymmetric, (c) multicomponent (caulked)
Atomic Force Microscopy (AFM) 127

Yampolskii 1994): (a) homogeneous dense mem- nonporous skin, has been hindered by the difcul-
brane, (b) integrally skinned asymmetric, ties of obtaining simultaneously the good selec-
(c) caulked, (d) single-layer composite, tivity and the high productivity. In other words, A
(e) multilayer composite, and (f) asymmetric com- the intrinsic property of some advanced material
posite membranes. Usually, a homogeneous cannot be expressed efciently in their asymmet-
membrane is prepared through solution casting. ric membranes. Various physical or chemical
This type of membrane is used for the lab-scale treatments can make the skin layer more perfect
investigation to fundamentally understand the (Jiang et al. 2009). One of the breakthroughs
intrinsic properties of polymers. Various tech- conquering this problem in the membrane devel-
niques are available in the formation of composite opment was made in 1980s by Henis and Tropidi
membranes. They can also be categorized as (Henis and Tripodi 1980). Their invention of coat-
asymmetric membranes morphologically. The ing asymmetric polysulfone membranes with sil-
multilayer composite (Fig. 1d) is an extension of icon rubber effectively sealed the pinholes and led
single-layer composite, and the asymmetric com- to rst generation of commercial gas separation
posite (Fig. 1e) is the combination of the integrally membrane, Prism or Prism Separator.
skinned asymmetric and composite approaches.
In addition to decreasing selective layer thickness,
one of the most attractive aspects of the composite References
membranes is their potential for minimizing mate-
rials cost, because only the selective layer must Guliants VV, Carreon MA, Lin YS (2004) Ordered
mesoporous and macroporous inorganic lms and
use a high-performance while more expensive
membranes. J Membr Sci 235:5372
material. The freedom in material choice and Henis JMS, Tripodi M (1980) Multicomponent mem-
membrane formation technique selection with branes for gas separation. US Patent 4,230,463
composite membranes facilitates the development Jiang LY, Wang Y, Qiao XY, Chung TS, Lai JY
(2009) Polyimides membranes for pervaporation and
of organic/inorganic layered structure that ef-
biofuels separation. Prog Polym Sci 34(11):11351160
ciently combines the characteristics of single Loeb S, Sourirajan S (1964) High ow porous membranes
organic or inorganic material and expands the for separating water from saline solutions. US Patent
application area of membrane separation. The 3,133,132
Paul DR, Yampolskii YP (1994) Polymeric gas separation
aforementioned asymmetric or composite struc-
membranes. CRC Press, Boca Raton
ture can be formed into different geometries such Ulbricht M (2006) Advanced functional polymer mem-
as the at sheet, the hollow bers, etc., by appro- branes. Polymer 47:22172262
priately choosing the fabricating or casting
equipment.
Today, extensive knowledge exists on how to
control the asymmetric membranes structure
including cross-section morphology by the selec- Atomic Force Microscopy (AFM)
tion of material and membrane formation condi-
tions. The polymeric composite membranes are Nidal Hilal and Daniel Johnson
usually made by solution coating, interfacial poly- Centre for Water Advanced Technologies and
merization, and plasma polymerization methods Environmental Research (CWATER), College
on the surface of a prefabricated porous support or of Engineering, Swansea University, Swansea,
by co-extrusion of two or more solutions (Ulbricht Wales, UK
2006). For composite membrane using inorganic
materials, they are prepared by various techniques
from solvent evaporation, in situ growth from The atomic force microscope is a versatile tool
solution, and other alternative methods (Guliants increasingly used for the physical characterization
et al. 2004). The work at commercializing asym- of surfaces and is of great interest for the visual-
metric membranes, especially those having ization and analysis of process surfaces including
128 Atomic Force Microscopy (AFM)

those of membranes used for ltration. It is capa-


ble of resolving features from the micrometer mm
0.20
down to the subnanometer scale and can operate 0.10
in air and liquid environments, allowing mem- 0.00
branes to be studied in environments matching 3

those encountered during their operation (Hilal


et al. 2004; Hilal and Johnson 2010), which 2
mm
allows assessment of effects of, for instance, pH,
ionic strength, and effects of additives on 1
3
membrane structure, a feature not available with 2
0 1 mm
other high resolution imaging applications. In 0
addition, the surface needs no special preparation, 25
providing it remains clear of unwanted contami-
nation, and does not need to be electrically con-
20
ductive, limitations found with some imaging
techniques.
The AFM consists of a sharpened probe 15
% of pores
mounted at the end of a exible cantilever. The
tip of the probe is then used to feel the underly- 10
ing membrane surface, producing a three-
dimensional map of the sample topography. 5
There are three basic imaging modes: contact
mode, where the tip maintains constant contact
0
with the surface, while feedback loops adjust its 0.10 0.15 0.20 0.25 0.30 0.35
height to maintain cantilever deection and hence Pore size, m
force; tapping mode, where the cantilever is
Atomic Force Microscopy (AFM), Fig. 1 3D image of
vibrated close to the resonant frequency and inter- cyclopore microltration membrane and pore-size distri-
mittently contacts the surface with decreased lat- bution for same membrane obtained by AFM
eral forces compared with contact mode; and
noncontact mode in which the probe tip interacts
with attractive forces very close to the surface but
is kept away from hard repulsive interactions. electrical and electrochemical, mechanical, adhe-
Noncontact mode is capable of extremely high sive, frictional and magnetic properties of surfaces
resolution but is the most difcult to attain in of interest.
practice. From the imaging data, several quantita- As well as providing this information, the
tive parameters of interest to membrane technol- AFM probe can be used as a force sensor by
ogists can be obtained including: surface moving the probe into and out of contact with
roughness, pore size, pore-size distribution, as the sample surface and monitoring deection in
well as showing in ne detail the morphology of the microcantilever arm. Through careful calibra-
fouled and unfouled membrane surfaces and the tion of the system this deection can be converted
effects of chemical modication of membrane into force, directly measuring the interaction force
surfaces (Johnson et al. 2012; Kochkodan as a function of probe tip sample separation
et al. 2013). Figure 1 shows a typical image of a distance (Gibson et al. 2004). This allows the
cyclopore microltration membrane and a detection of DLVO, hydrophobic, hydrostatic
resulting pore-size distribution (Bowen and steric interactions, membrane stiffness, and
et al. 1996; Bowen and Hilal 2009). There are a adhesion forces. The sharp tip may be replaced by
large number of expansions for AFM instruments a colloidal particle, which may be functionalized
allowing many other modes allowing mapping of to simulate any of a number of potential
Atomistic Simulations Methods 129

membrane foulants allowing quantitative mea- such as phonon calculations, free-energy optimi-
surements of foulant rejection and attachment zations (molecular mechanics), molecular dynam-
forces. This makes possible the direct quantica- ics (MD), Monte Carlo simulations, and crystal A
tion of membrane fouling properties of different structure prediction, are used to interpret existing
materials under a range of environmental condi- experimental data and predict new phenomena
tions and with only a relatively small sample of and to provide a way forward where experiments
membrane needed. are not yet possible, e.g., under extreme condi-
tions or at atomistic size- and timescales which are
difcult to detect directly (Allen and Tildesley
References
1989; Haile 1992; Frenkel and Smit 2002; Leach
Bowen WR, Hilal N (eds) (2009) Atomic force microscopy 2001; Brenner 2000; Allen 2004; Tocci and
in process engineering. Butterworth-Heineman, Oxford Pullumbi 2011).
Bowen WR, Hilal N et al (1996) Atomic force microscope Molecular modeling is primarily a tool for
studies of membranes: surface pore structures of calculating the energy of a given molecular struc-
cyclopore and anopore membranes. J Membr Sci
110(2):233238 ture, and the goal is to understand and model the
Gibson CT, Johnson DJ et al (2004) Method to determine motion of each atom in the material.
the spring constant of atomic force microscope cantile- Different levels of atomistic simulations exist,
vers. Rev Sci Instrum 75(2):565567 ranging from quantum mechanical models to sta-
Hilal N, Johnson DJ (2010) The use of atomic force
microscopy in membrane characterisation. In: tistical methods. This means solving numerically
Drioli E, Giorno L (eds) Comprehensive membrane the classical or quantum mechanical microscopic
science and engineering. Elsevier Science, Oxford, equations for the motion of interacting atoms or
pp 521538 even deeper electrons and nuclei.
Hilal N, Al-Zoubi H et al (2004) A comprehensive review
of nanoltration membranes: treatment, pretreatment, Quantum mechanical (QM) or ab initio
modelling and atomic force microscopy. Desalination methods describe matter at the electronic level,
170:281308 considering the fundamental particles, electrons
Johnson DJ, Al-Malek SA et al (2012) Atomic force and protons. The equation from which molecular
microscopy of nanoltration membranes: effect of
imaging mode and environment. J Membr Sci properties can be derived is the Schrodinger equa-
389:486498 tion, and various approximations must be intro-
Kochkodan V, Johnson DJ et al (2013) Polymeric mem- duced in order to extend the utility of the method
branes: surface modication for minimizing (bio)col- to polyatomic systems.
loidal fouling. Adv Colloid Interface Sci (in press).
doi:10.1016/j.cis.2013.05.005 Atomistic methods are used to compute molec-
ular properties, which do not depend on electronic
effects; the whole atom is modeled just as a soft
sphere and obeys the laws of statistical mechanics.
Atomistic simulation utilizes analytic potential
Atomistic Simulations Methods
energy expressions (sometimes referred to as
empirical or classical potentials) to describe the
Elena Tocci
systems.
Institute on Membrane Technology, National
The analytic potential energy functions are
Research Council of Italy, ITM-CNR, Rende,
simplied mathematical expressions that
Italy
attempt to model interatomic forces arising
from the quantum mechanical interaction of
Atomistic Simulations electrons and nuclei. Their use is dictated by
the need to model systems with sizes and/or
Atomistic simulations are theoretical and compu- timescales that exceed available computing
tational modeling tools for interpreting what hap- resources, required for quantum calculations,
pens at the atomic scale in solids, liquids, which give no account of the complex elec-
molecules and plasmas. Atomistic simulations, tronic structure of atoms.
130 Atomistic Simulations Methods

Forces between atoms are derived from empir- traditionally split into one-body, two-body,
ical interatomic potentials that are obtained from three-body terms:
tting material properties (e.g., lattice constant,
elastic constants, vacancy formation energy, etc.)  
! ! !
from experimental data or QM calculations. They V nonbonded r 1 , r 2 , . . . , r N
may depend on the distance between atoms, X !  XX ! ! 
angles between bonds, angles between planes, etc. v ri w r i, r j . . .
i i ji
The general form of the total potential of the
N-atom system describes types of interactions,  
!
bonded and non-bonded, and can be written as: The v r i term represents an externally applied
potential eld and describes external force elds
  X  
! ! !
V r 1 , r 2 , . .. , r N V 1 r i
! (e.g., gravitational eld) and external constraining
X   X   elds (e.g., the wall function  for particles

! ! ! ! ! ! ! in a
V2 r i, r j V3 r i, r j, r k . . . chamber). The pair potential w r i , r j w r ij
i, ji i, ji, kj
neglect three-body (and higher order)
interactions.
The part of the potential energy V representing The Lennard-Jones potential is the most com-
bonding interactions will include terms of the monly used form:
following kind:
  
1X r  2 s 12 s6
V intramolecular K ij1 r ij  r eq wLJ r 4e 
2 bonds r r
1 X  2
K yijk yijk  yeq
2 where s is the diameter and e is the depth of the
bend
potential energy well. If electrostatic charges are
angles
present, the appropriate Coulomb potentials are
1 X X f, m   
K ijkl 1 cos mfijkl  gm added:
2 m
torsion
angles Q1 Q2
wCoulomb r
4pe0 r
The bonds
  typically involve the separation
 ! !
r ij  r i  r j  between adjacent pairs of atoms where Q1, Q2 are the charges and e0 the permittiv-
in a molecular framework, and a harmonic form ity of the free space.
with specied equilibrium separation has been To be effective, an analytic potential energy
used, although this is not the only possible type. function must possess the following critical
The bend angles yijk are between successive properties:
! ! ! !
bond vectors such as r i  r j and r j  r k and
involve three atom coordinates. Usually this Flexibility: A potential energy function must be
bending term is quadratic in the angular displace- sufciently exible that it accommodates as
ment from the equilibrium value, although wide a range as possible of tting data.
periodic functions are also used. The torsion Accuracy: A potential should be able to accurately
angles fijkl are dened in terms of three reproduce properties of interest as closely as
connected bonds; hence four atomic coordinates possible.
are used. Transferability: A potential function should be
The part of the potential energy V representing able to study a variety of properties for which
non-bonded interactions between atoms is it was not t.
Autothermal Reforming 131

Computational efciency: Evaluation of the func- steam reforming of the fuel (endothermic reac-
tion should be relatively efcient depending on tion) with the partial oxidation of a small amount
quantities such as system sizes and timescales of the fuel (exothermic reaction) in order to A
of interest, as well as available computing achieve an autothermal reaction that proceeds
resources. without external input of energy (Chang
et al. 2010; Tiemersma et al. 2012).
The major methods are molecular mechanics The most studied autothermal reforming is the
(MM), molecular dynamics (MD), Monte Carlo conversion of methane to hydrogen (Gallucci
(MC), and additionally, there is a whole range of et al. 2009). The overall chemical reactions taking
hybrid techniques which combine features from place in the autothermal reforming of methane
both MD and MC methods. include steam reforming (Eq. 1), water gas shift
(Eq. 2), and total oxidation (Eq. 3). The energy
generated by the oxidation reaction and WGS is
References
used for the SMR:
Allen MP (2004) Introduction to molecular dynamics sim-
ulation computational soft matter: from synthetic poly- CH4 H2 O CO 3H2 (1)
mers to proteins. In: Attig N, Binder K, Grubmuller H,
Kremer K (eds) Lecture notes, John von Neumann CO H2 O CO2 H2 (2)
Institute for computing, Julich, NIC series,
vol 23, ISBN 3-00-012641-4, pp 128
Allen MP, Tildesley DJ (1989) Computer simulation of CH4 2O2 ! CO2 2H2 O (3)
liquids. Clarendon Press, Oxford
Brenner DW (2000) The art and science of an analytic This reaction system can be carried out efciently
potential. Phys Status Solidi B 217:23
Frenkel D, Smit B (2002) Understanding molecular simu-
in a membrane reactor as the extraction of hydro-
lation: from algorithm to applications, 2nd edn. Aca- gen during the reaction shifts the equilibrium
demic, San Diego reactions toward completion at moderate temper-
Haile JM (1992) Molecular dynamics simulation. Wiley, atures, and thus the extent of oxidation reaction to
Chichester
Leach AR (2001) Molecular modelling: principles and
achieve autothermal reforming is moderate.
applications, 2nd edn. Prentice Hall, Harlow One of the problems of autothermal reforming
Tocci E, Pullumbi P (2011) Chapter 1: Multi-scale molec- carried out in membrane reactors is the mismatch
ular modeling approaches for designing/selecting poly- between the oxidation reaction rate and the
mers used for developing novel membranes. In:
Drioli E, Barbieri G (eds) Membrane engineering for
reforming reaction rate. The oxidation is often
the treatment of gases: gas-separation problems with much faster than the reforming, and for this reason
membranes. The Royal Society of Chemistry, Cam- in packed bed membrane reactors, a high-
bridge, UK, pp 128 temperature region is obtained at the beginning
of the bed followed by a low-temperature region
at the end of the bed. This could cause problems to
the membranes that could be damaged by high
Autothermal Reforming temperatures while not working properly (low
ux see Richardson equation) at lower temper-
Fausto Gallucci
atures (Tiemersma et al. 2006; Gallucci et al.
Chemical Process Intensication, Department of
2010).
Chemical Engineering and Chemistry,
To circumvent these problems, uidized bed
Eindhoven University of Technology, Eindhoven,
membrane reactors are often proposed for this
The Netherlands
kind of reaction system, as the solid circulation
inside the reactor allows a virtually isothermal
Autothermal reforming or oxidative steam condition even in case of highly exothermic
reforming is a combination of conventional reactions.
132 Azeotropic Distillation

Examples of autothermal reforming (ATR) 97&partnerID=40&md5=47095694b70255a4e72794


(or oxidative steam reforming) reactions also 5b6ad24016
Tosti S, Borelli R, Santucci A, Scuppa L (2010) Pd-Ag
include the ATR of ethanol and methanol or the membranes for auto-thermal ethanol reforming. Asia
ATR of naphtha (Lin et al. 2010; Tosti et al. 2010; Pac J Chem Eng 5(1):207212, Retrieved from http://
Moreno and Wilhite 2009). All these reactions www.scopus.com/inward/record.url?eid=2-s2.0-77649
have been successfully tested in membrane reac- 116340&partnerID=40&md5=50f41a519d60bbaa07
aa2f96c86792bc
tors for pure hydrogen production.

References
Azeotropic Distillation
Chang H-F, Pai W-J, Chen Y-J, Lin W-H
(2010) Autothermal reforming of methane for produc- Alessandra Criscuoli
ing high-purity hydrogen in a Pd/Ag membrane reactor. Institute on Membrane Technology, National
Int J Hydrog Energy 35(23):1298612992, Retrieved Research Council of Italy, ITM-CNR, Rende,
from http://www.scopus.com/inward/record.url?eid=
2-s2.0-78049471869&partnerID=40&md5=631e9a956f Italy
70441c60cc3fb3987ed76c
Gallucci F, Van Sint Annaland M, Kuipers JAM
(2009) Autothermal reforming of methane with inte-
grated CO2 capture in novel uidized bed membrane Azeotropic distillation is a particular type of dis-
reactors. Asia Pac J Chem Eng 4(3):334344. tillation by which it is possible to separate azeo-
doi:10.1002/apj
tropes (Perry and Green 1984). Azeotropes are
Gallucci F, Van Sintannaland M, Kuipers JAM (2010)
Theoretical comparison of packed bed and uidized mixtures of two or more substances that boil
bed membrane reactors for methane reforming. Int together at a constant temperature. It is, therefore,
J Hydrog Energy 35(13):71427150, Retrieved from impossible to separate them directly by distilla-
http://www.scopus.com/inward/record.url?eid=2-s2.
tion, because a distillate of the same composition
0-77954826477&partnerID=40&md5=569ec26bf5
26471832579c3f965b1d90 of the liquid feed is produced. Azeotropic distilla-
Lin W-H, Liu Y-C, Chang H-F (2010) Autothermal tion is based on the addition of a compound that
reforming of ethanol in a Pd-Ag/Ni composite membrane acts on the volatility of the substances contained
reactor. Int J Hydrog Energy 35(23):1296112969,
into the azeotrope, so that a new azeotrope, made
Retrieved from http://www.scopus.com/inward/record.
url?eid=2-s2.0-78049467904&partnerID=40&md5= of the substances present in the starting azeotrope
0048616ca9b8d29ade703c2eea0ab1bf and the added compound, is formed. The new
Moreno AM, Wilhite BA (2009) Autothermal hydrogen azeotrope can be, then, removed by distillation,
generation from methanol in a ceramic microchannel
and a residual highly rich in one of the substances
network. In: Conference proceedings 2009 AIChE
annual meeting, 09AIChE. Retrieved from http://www. is obtained. A typical example is the distillation of
scopus.com/inward/record.url?eid=2-s2.0-779522829 mixtures of water-ethanol. By classic distillation,
00&partnerID=40&md5=0650ebd8cd9440d3ac32e0 the distillate contains 95 % of alcohol (pure boil-
3b4f859c7d
ing temperature, 78.4  C) and 5 % of water (pure
Tiemersma TP, Patil CS, Sint Annaland MV, Kuipers JAM
(2006) Modelling of packed bed membrane reactors boiling temperature, 100  C), and no further incre-
for autothermal production of ultrapure hydrogen. ments in ethanol purity can be reached, because
Chem Eng Sci 61(5):16021616, Retrieved from this mixture boils, as a unique compound, at
http://www.scopus.com/inward/record.url?eid=2-s2.0-
78.17  C. However, if benzene or cyclohexane is
30344455632&partnerID=40&md5=9fb77a0611e8e6
a89745a4b8625bbebf added to the mixture, a ternary azeotrope is formed
Tiemersma TP, Kolkman T, Kuipers JAM, van Sint that incorporates all the water and has a lower
Annaland M (2012) A novel autothermal reactor con- boiling point than ethanol. Therefore, if the distil-
cept for thermal coupling of the exothermic oxidative
lation is now carried out, the new azeotrope will be
coupling and endothermic steam reforming of methane.
Chem Eng J 203:223230, Retrieved from http://www. recovered as distillate, while practically pure eth-
scopus.com/inward/record.url?eid=2-s2.0-848656377 anol is produced as residue (see Fig. 1). Besides
Azeotropic Distillation 133

Ternary
azeotrope
A
Benzene or
cyclohexane

+ Ternary azeotrope
+ ethanol Distillation

Water-ethanol
azeotrope

Ethanol

Azeotropic Distillation, Fig. 1 Azeotropic distillation of water-ethanol

azeotropic distillation, other methods can be References


also employed for the separation of azeotropes
and, in particular, membrane operations like Perry RH, Green D (1984) Perrys chemical engineers
handbook. McGraw-Hill, Singapore
pervaporation and membrane distillation.
B

b-Lactoglobulin and stabilizer and can be used in the production of


Alpha-Lactalbumin Separation confections (Cayot and Lorient 1997).
There are two types of membrane systems that
Andrew L. Zydney have been explored for the separation of
Department of Chemical Engineering, The b-lactoglobulin and a-lactalbumin: ultraltration
Pennsylvania State University, University Park, and membrane adsorbers (also referred to as mem-
PA, USA brane chromatography). Cheang and Zydney
(2003) demonstrated that b-lactoglobulin and
a-lactalbumin could be separated using commer-
b-Lactoglobulin and a-lactalbumin are the two cial ultraltration membranes by adjusting the
dominant proteins in whey (see Table 1). Although solution pH and ionic strength to enhance the
whey protein concentrates are used as food addi- selectivity. These results were subsequently
tives in the production of a variety of dairy prod- extended to purify b-lactoglobulin and
ucts, meats, and beverages, the unique nutritional, a-lactalbumin from a whey protein isolate using
therapeutic, and functional characteristics of the a two-stage ultraltration process (Cheang and
individual whey proteins are largely unrealized in Zydney 2004).
these whey products. There has thus been consid- Membrane chromatography is of potential inter-
erable commercial interest in the separation of est for the separation of b-lactoglobulin and
b-lactoglobulin and a-lactalbumin to take advan- a-lactalbumin due to the high ow rates that can
tage of their functional and biological properties. be achieved in these systems. For example, Sau
a-Lactalbumin is attractive as a nutraceutical and Fee (2011) examined the use of a mixed mode
because of its high tryptophan content (Cayot and membrane chromatography system containing
Lorient 1997). a-Lactalbumin also provides both cation and anion exchange sites for the frac-
enhanced whippability in meringue-like formula- tionation of whey proteins. b-Lactoglobulin was
tions and may have potential as a contraceptive preferentially bound to the membrane, with the
agent. b-Lactoglobulin is an effective foam a-lactalbumin collected in the ow through.

# Springer-Verlag Berlin Heidelberg 2016


E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-662-44324-8
136 Backwashing

b-Lactoglobulin and Alpha-Lactalbumin Separation, Table 1 Physical characteristics of major whey proteins
(From Zydney 1998)
Protein Concentration (g/L) Molecular weight (g/mol) Isoelectric pH
b-Lactoglobulin 2.7 18,362 5.2
a-Lactalbumin 1.2 14,147 4.54.8
Immunoglobulins 0.65 150,0001,000,000 5.58.3
Bovine serum albumin 0.4 69,000 4.74.9
Lactoferrin 0.1 78,000 9.0
Lactoperoxidase 0.02 89,000 9.5
Glycomacropeptide 7

References pressure membrane systems, i.e., microltration


and ultraltration, while high pressure membrane
Cayot P, Lorient D (1997) Structure-function relationships systems, i.e., nanoltration and reverse osmosis,
of whey proteins. In: Damodaran S, Paraf A (eds) Food
do not employ backwashing to control fouling.
proteins and their applications. Marcel Dekker, New
York, pp 225256 Backwashing is most commonly initiated on a
Cheang B, Zydney AL (2003) Separation of alpha- timed cycle; however, it may also be initiated on
lactalbumin and beta-lactoglobulin using membrane a transmembrane pressure set point or a volume
ultraltration. Biotechnol Bioeng 83:201209
ltered set point (AWWA 2013). Backwashing is
Cheang B, Zydney AL (2004) A two-stage ultraltration
process for fractionation of whey protein isolate. performed in stages through a membrane plant in
J Membr Sci 231:159167 order to ensure that water is being produced at all
Sau SM, Fee CJ (2011) Simultaneous anion and cation times; in other words, there is rotation through
exchange chromatography of whey proteins using a
which individual membrane units will be
customizable mixed matrix membrane. J Chromatogr
A 1218:90039009 backwashed, while the majority, at any given
Zydney AL (1998) Protein separations using membrane time, are still maintained in operation. When
ltration: new opportunities for whey fractionation. Int backwashing is no longer considered effective at
Dairy J 8:243250
controlling membrane fouling, as indicated by a
set point loss in ux, permeate production, or high
TMP value, the membrane system will undergo
Backwashing chemical cleaning. Additionally, a chemically
enhanced backwash (CEB) may be put in place
Onita D. Basu before a membrane unit is taken off-line for a full
Department of Civil and Environmental chemical clean. In the event of a CEB, an oxidant,
Engineering, Carleton University, Ottawa, such as chlorine, and acids or bases, such as citric
Canada acid or sodium hydroxide, are added to the back-
wash water to assist in the removal of foulants
from the membrane pores and membrane surface.
Backwashing of a membrane refers to the reversal Backwashing has been found to be helpful in
of ow through a membrane system in compari- removing cake layer fouling that is particulate in
son to the normal ow direction required for per- nature. However, research has shown that
meate production. The purpose of backwashing is backwashing alone does not remove the majority
to assist with removing or loosening foulants from of the cake layer fouling but instead mainly
the membrane surface and within the membrane increases its porosity, effectively loosening the
pores to control membrane fouling. It is a funda- cake layer against the membrane surface
mental membrane operational step to control the (Ye et al. 2011). Therefore, it is important to
rate of transmembrane pressure (TMP) increase include an air scour or cross-ow velocity step
over time. Backwashing is utilized with low with backwashing to effectively decrease the size
Backwashing Frequency 137

and thickness of the cake layer foulants on the Wu J, Le-Clech P, Stuetz RM et al (2008) Effects of
membrane surface (Remize et al. 2010). However, relaxation and backwashing conditions on fouling in
membrane bioreactor. J Membr Sci 324:232
it is important to keep in mind that pore blocking Ye Y, Chen V, Le-Clech P (2011) Evolution of fouling
results in a faster deterioration of the membrane deposition and removal on hollow bre membrane
ux and is more likely to lead to irreversible during ltration with periodical backwash. Desalina- B
fouling than cake layer fouling. The cake layer tion 283:198205
itself can prevent pore blocking by acting like a
prelter for the membrane surface. Thus, if too
much of the cake layer is removed, the membrane
system will have a faster development of pore Backwashing Frequency
blocking over several cycles of backwashing. As
such it is important to congure an optimized Onita D. Basu
backwash procedure with associated air scour or Department of Civil and Environmental
cross-ow velocity step for a particular membrane Engineering, Carleton University, Ottawa,
and water type. When optimizing a system, it is Canada
important to note that research has found that
backwash duration and backwash ux at low
rates, equal to or less than the permeate ux, are Optimization of backwash frequency is an impor-
not likely to have an impact on fouling rate in low tant consideration in terms of membrane operation
fouling systems, although backwash duration was as it uses produced water for the backwash cycle;
found to have an optimum value associated with therefore, the more frequent the backwash, the
net permeate production (Akhondi et al. 2014). lower the efciency of the membrane system
Other research has shown that too high of a back- overall in terms of produced water. In addition to
wash ux may actually exacerbate fouling by the backwash frequency, which is generally every
potentially removing too much of the cake layer 3090 min, consideration should also be applied
and resulting in more irreversible pore fouling for backwash duration and backwash ux. Back-
occurring (Wu et al. 2008). Given that wash duration is how long a membrane system is
backwashing has been shown to clearly assist in backwashed and is typically between 1 and 3 min.
controlling fouling, it important for all membrane In some cases, backpulsing may also be used, and
plants to monitor the effectiveness of their back- this term refers to short burst cycles for reversing
wash procedures on a regular basis with consid- the ow through the membrane that generally last
eration for changes in water quality over different between 0.5 and 5 s. Backwash ux is the uid
seasons. ow rate through the membrane, and it is gener-
ally equal to the initial operating permeate ux of
the membrane system, although it may be higher.
Backwash frequency is linked to the operating
References membrane ux, with a lower ux resulting in a
lower required backwash frequency, while a
Akhondi E, Wicaksana F, Fane AG (2014) Evaluation of
fouling deposition, fouling reversibility and energy higher ux tends to require a higher backwash
consumption of submerged hollow ber membrane frequency (Wang et al. 2008; Rafn et al. 2011).
systems with periodic backwash. J Membr Sci Backwashing is often considered to control
452:319331
American Water Works Association (AWWA) (2013) Com-
reversible fouling; however, it is also tied to the
mittee report: metrics and methods for MF/UF system control of irreversible fouling as well. Research has
optimization. J Am Water Works Assoc 105(2):6576 demonstrated, for instance, that while backwash
Remize PJ, Guigui C, Cabassud C (2010) Evaluation of frequency may not appear to impact on the rate of
backwash efciency, denition of remaining fouling
and characterisation of its contribution in irreversible
reversible fouling, it can inuence the rate of irre-
fouling: case of drinking water production by versible fouling. Specically, longer periods
air-assisted ultra-ltration. J Membr Sci 355:104111 between backwashes (i.e., 60 min vs. 30 min)
138 Bacteria and Spore Removal

resulted in an increase in the irreversible fouling downside of this is that the product properties
rate (Rafn et al. 2012). The importance of this will be inuenced and this is mostly undesirable.
information is that higher irreversible fouling In this respect, membrane microltration
rates result in higher frequencies of chemical could be an interesting alternative when used for
cleaning for a membrane system, which has both cold sterilization. If the bacterial count is not too
an adverse impact on water production and the high and other components are sufciently
economics of running a membrane system. Of smaller, the removal of bacteria and spores can
course, consideration must be taken for the loss rather easily be carried out using dead-end
of system productivity when increasing the fre- microltration.
quency of backwashing as well. As backwash When the size of bacteria and other compo-
frequency increases, the membrane productivity nents overlap, this separation is far from straight-
is concomitantly decreasing; backwashing can forward. An illustrative example can be found in
result in upwards of a 10 % loss in membrane dairy separation, in which cold sterilization of
productivity. It is, therefore, important to weigh milk has been reported. The components that
out the benets and losses associated with increas- are most important for this separation are the milk
ing backwashing frequency and losing productiv- fat globules (cream; typical sizes from 0.1 to
ity versus decreasing the backwash frequency 15 mm), bacteria (0.55 mm), and casein micelles
and potentially increasing the required chemical (20300 nm). Since cream and bacteria overlap in
cleaning of the membrane system. size, the cream is rst removed by centrifugation.
The resulting skim milk receives the cold sterili-
zation treatment. Various researchers have inves-
tigated how far the bacterial count could be
References reduced as listed in Table 1.
From the table, it is clear that a variety of
Rafn M, Germain E, Judd S (2011) Optimising operation
membranes and process conditions have been
of an integrated membrane system (IMS) a
Box-Behnken approach. Desalination 273:136141 used, ranging from very high to low cross-ow
Rafn M, Germain E, Judd S (2012) Inuence of velocities, and application of a uniform trans-
backwashing, ux and temperature on microltration membrane pressure or frequent back pulsing.
for wastewater reuse. Sep Purif Technol 96:147153
These conditions are clearly aiming at processing
Wang L, Wang X, Fukushi KI (2008) Effects of operational
conditions on ultraltration membrane fouling. Desali- under very different conditions, where frequent
nation 229:181191 back pulsing will control the amount of deposited
material, the uniform transmembrane pressure
concept aims at stable ltration conditions along
the length of the membrane. All approaches have
Bacteria and Spore Removal shown interesting results; the log reductions that
can be achieved are around 4 (10,000-fold reduc-
Karin Schroen tion), although it should be noted that these values
Laboratory of Food Process Engineering, are not as high as obtained after regular heat
Wageningen University and Research Centre, treatment.
Wageningen, The Netherlands The highest log reduction (6.6, which is higher
than for regular pasteurization) was claimed for
microsieves, which are silicon plates with very
Bacteria can be of great inuence on many pro- uniform pores prepared by laser interference
cesses, be it in, for example, food, pharma, fer- lithography (Van Rijn and Elwenspoek 1995).
mentation, or water production. Obviously, Although the bacterial reduction was measured
bacteria (and their spores) can be removed by for dead-end ltration using a 0.5 mm microsieve
heat treatment or addition of specic components and SMUF (simulated ultraltrate) spiked with
that inhibit their growth or even kill them, but the Bacillus subtilis, it is expected that the high log
Bacterial Biofilm Formation 139

Bacteria and Spore Removal, Table 1 Comparison of cold sterilization results from various sources
Process conditions cross-ow/pressure, Log
Membrane type and ux UTP, back pulsing reduction Source
Ceramic 1.4 mm; 1.4104 m/s 50 kPa, 7.2 m/s UTP, skim milk Above 3.5 Saboya and Maubois
2000
B
Reversed asymmetric 0.87 mm; 0.51 m/s; back pulsing frequency Between Guerra et al. 1997
1.4104 m/s 0.21 s1, skim milk 4 and 5
Microsieve 0.5 mm Dead-end ltration of spiked SMUF 6.6 Van Rijn and
Kromkamp 2001
Bactocatch: ceramic membranes 68 m/s, skim milk, UTP Holm et al. 1989

count reduction is a result of its narrow pore size Saboya LV, Maubois JL (2000) Current developments of
distribution of the microsieve. microltration technology in the dairy industry. Lait 80:541
Van Dinther AMC, Schron CGPH, Boom RM
In case of the uniform transmembrane pressure (2011) High-ux membrane separation using uid
concept, reduction of bacteria and spores by skimming dominated convective uid ow. J Membr
microltration is carried out near the critical pres- Sci 371(12):20
sure, at which the amount of particles that is Van Rijn CJM, Elwenspoek MC (1995) Micro ltration
membrane sieve with silicon micro machining for
carried toward that membrane by permeate is industrial and biomedical applications. In: Proceedings
counterbalanced by the amount of particles dif- of micro electro mechanical systems (MEMS), Amster-
fusing away from the membrane to the feed solu- dam, p 83
tion. We expect that this can be even taken one Van Rijn CJM, Kromkamp J (2001) Method for ltering
milk. WO Patent 0,209,527. http://www.spgveco.com/
step further, as indicated in the work of van precision+metal/applications/ltration. Accessed July
Dinther et al. (2011), in which particles that size- 2012
wise correspond to milk fat globules and bacteria
were reported to be separated by uid skimming
and lift effects. For this to occur, rst a nonporous
channel is used to induce particle migration after Bacterial Adhesion
which in a porous area the small particles that are
situated close to the wall can specically be Bacterial Biolm Formation
removed. This process has not been demonstrated
at large scale, but it holds great promise since it
would allow for direct separation of bacteria from
full milk without the need of centrifugation.
Bacterial Biofilm
Besides, the separation is no longer determined
Bacterial Biolm Formation
by the pore size of the membrane; metal sieves
from SPG Veco with uniform pores of around
20 mm were used, but by the process conditions
that determine which part of the feed is removed. Bacterial Biofilm Formation

Lidietta Giorno and Napoleone DAgostino


Institute on Membrane Technology, National
References
Research Council of Italy, ITM-CNR, Rende,
Guerra A, Jonsson G, Rasmussen A, Waagner Nielsen E, Italy
Edelsten D (1997) Low cross ow velocity
microltration of skim milk for removal of bacterial
spores. Int Dairy J 7:849
Holm S, Malmberg R, Svensson K (1989) Method and
Synonyms
plant producing milk with low bacterial content. WO
Patent 8:601687 Bacterial biolm; Bacterial adhesion; Biofouling
140 Bacterial Biofilm Formation

Biolms were observed as early as 1674, when the collectors surface. Although useful as a snap-
Antonie van Leeuwenhoek used his primitive but shot of biolm growth, this type of prole is
effective microscope to describe aggregates of limited when considering the intimate processes
animalcules that he scraped from human tooth of cellsubstrate/cellcell interaction. Characklis
surface (Costerton 1999). Since then, more accu- and Marshal later described an eight-step process
rate descriptions of biolms are made. Bacteria which included the formation of an initial condi-
generally exist in one of two types of population: tioning layer, reversible and irreversible adhesion
planktonic, freely existing in bulk solution, and of bacteria, and the eventual detachment of cells
sessile, as a unit attached to a surface or within the from a mature biolm for subsequent
connes of a biolm (Garrett et al. 2008). colonization.
Biolm is a result of many complicated steps. It Anything that may be present within the bulk
includes the formation of a conditioning lm on a uid can through gravitational force or movement
materials surface, the movement of bacteria, an of ow settle onto a substrate and become part of a
attachment process, the growth on material surfaces, conditioning layer. This layer modies substrata
and the breakdown nally. For bacteria, the advan- facilitating accessibility to bacteria. Surface
tages of biolm formation are numerous. These charge, potential, and tensions can be altered
advantages include: protection from antibiotics favorably by the interactions between the condi-
(Godberg 2002), disinfectants (Peng et al. 2002), tioning layer and substrate. The substrate provides
and dynamic environments (Chen et al. 1998). anchorage and nutrients augmenting growth of the
Over the past few decades, biolm growth has bacterial community.
been observed in many industrial and domestic Initially, planktonic microbial cells are
domains. Many industries suffer the ill effects of transported from bulk liquid to the conditioned
biolm growth of one type or another, which can surface either by physical forces or by bacterial
result in heavy costs in cleaning and maintenance. appendages such as agella. The reversible
Biolms occurring in membrane systems may adsorption of a fraction of the cells reaching the
cause severe loss performance and the use of surface normally occurs. Local environmental
costly cleaning procedures to maintain output variables which contribute to bacterial adhesion
and quality. The fouling is often so severe that are factors such as available energy, surface func-
acceptable operation cannot be maintained and tionality, bacterial orientation, temperature, and
membrane replacements are needed. It is neces- pressure conditions. If repulsive forces are greater
sary to understand the biolm formation mecha- than the attractive forces, the bacteria will detach
nism with the aim to propose a solution to contrast from the surface. The probability of this phenom-
this fouling. enon occurs is higher before the formation of the
Bacteria are capable of colonizing almost any conditioning layer. The activation energy for
surface and have been found at extreme condi- desorption of bacteria is low and so it is likely to
tions such as temperatures from 12  C to 110  C occur, underlining the weakness of the bonds.
and pH values between 0.5 and 13. Physical forces associated to bacterial adhesion
Biolm growth occurs by physical, chemical, include the van der Waals forces, steric interac-
and biological processes. Fletcher described the tions, and electrostatic (double layer) interaction,
accumulation of microorganisms on a collecting collectively known as the DVLO (Derjaguin,
surface as a process of three stages: (i) adsorption, Verwey, Landau, and Overbeek) forces, which
or the accumulation of an organism on a collector originally described the interaction of a colloidal
surface, i.e., substrate (deposition); particle with a surface (Rutter and Vincent 1980).
(ii) attachment, or the consolidation of the inter- According to this theory, the total interaction
face between an organism and a collector, often between a surface and a particle is the summation
involving the formation of polymer bridges of their van der Waals and Coulomb interactions.
between the organism and collector; and (iii) col- Since the van der Waals attractive force is domi-
onization, or growth and division of organisms on nant in the vicinity of a surface, particles adhere
Bacterial Biofilm Formation 141

irreversibly because they cannot separate from the inhibited in sessile species as motility is restricted
surface by Brownian motion. In contrast, the Cou- and no longer necessary. Simultaneously, expres-
lomb interaction becomes dominant at a distance sion of a number of genes for the production
away from the surface because the van der Waals of cell surface proteins and excretion products
force decreases sharply with distance. Other inter- increases. Surface proteins (porins), such as Opr B
actions that DVLO theory takes into consideration C and Opr E, allow the transport of extracellular
are hydrophobichydrophilic and osmotic (Chang products into the cell and excretion materials
and Chang 2002) and have also been described in out of the cell, e.g., polysaccharides (Hancock
terms of thermodynamic interaction (Gallardo- et al. 1990). The structure of many Gram-
Moreno et al. 2002). negative bacterial polysaccharides is relatively
In real time, a number of the reversibly simple, comprising either homopolysaccharides
adsorbed cells remain immobilized and become or heteropolysaccharides (Sutherland 2001).
irreversibly adsorbed. It has been argued that the These molecules impart mechanical stability and
physical appendages of bacteria (agella, m- are pivotal to biolm adhesion and cohesion and
briae, and pili) overcome the physical repulsive evasion from harsh dynamic environmental
forces of the electrical double layer (De Weger conditions. They consolidate the biolm struc-
1987). Subsequently, the appendages make con- ture. Hall-Stoodley and Stoodley identied the
tact with the bulk lattice of the conditioning differences in gene expression of planktonic
layer stimulating chemical reactions such as and sessile cells, and as many as 57 biolm-
oxidation and hydration and consolidating the associated proteins were not found in the plank-
bacteriasurface bond. Some evidence has tonic prole.
shown that microbial adhesion strongly depends The stationary phase of growth describes a
on the hydrophobichydrophilic properties of phase where the rate of cell division equals the
interacting surfaces (Liu et al. 2004). rate of cell death. At high cell concentration, a
As the stationary cells divide (binary division), series of cell signaling mechanisms are employed
daughter cells spread outward and upward from by the biolm, and this is collectively termed
the attachment point to form clusters. Typically, quorum sensing (Bassler 1999). Quorum sensing
such interactions and growth within the develop- describes a process where a number of
ing biolm form into a mushroom-like structure. autoinducers (chemical and peptide signals in
This structure is believed to allow the passage of high concentrations, e.g., homoserine lactones)
nutrients to bacteria deep within a biolm. After are used to stimulate genetic expression of both
an initial stage, a rapid increase in population is mechanical and enzymatic processors of algi-
observed, otherwise described as the exponential nates, which form a fundamental part of the extra-
growth phase. This depends on the nature of the cellular matrix. The death phase sees the
environment, both physically and chemically. The breakdown of the biolm. Enzymes are produced
rapid growth occurs at the expense of the sur- by the community itself which break down poly-
rounding nutrients from the bulk uid and the saccharides holding the biolm together, actively
substrate. At this stage the physical and chemical releasing surface bacteria for colonization of fresh
contribution to the initial attachment ends and the substrates. Alginate lyase produced by Pseudo-
biological processes begin to dominate. Excretion monas uorescens and Pseudomonas aeruginosa,
of polysaccharide intercellular adhesin (PIA) N-acetyl-heparosan lyase by Escherichia coli, and
polymers and the presence of divalent cations hyaluronidase by Streptococcus equi are exam-
interact to form stronger bonding between cells ples of the enzymes used in the breakdown of
(Dunne 2002). the biolm matrix (Sutherland 1999). Simulta-
Differential gene expression between the two neously, the operons coding for agella proteins
bacterial states (planktonic/sessile) is in part asso- are upregulated so that the organisms have the
ciated to the adhesive needs of the population. For apparatus for motility and the genes coding for a
example, the production of surface appendages is number of porins are downregulated, thus
142 Bacterial Biofilm Formation

completing a genetic cycle for biolm adhesion weak hydrogen bonding forces; (ii) viscous
and cohesion. damping due to polymeric friction and hydrogen
Changes in pH can have a marked effect on bond breakage; and (iii) alignment of the poly-
bacterial growth and as such are frequently mers in the shear direction (Klapper et al. 2002).
exploited in the production of detergents and dis- Such properties change with increased tempera-
infectants used to kill bacteria. Bacteria possess ture. Increasing the temperature of polysaccha-
membrane-bound proton pumps which extrude rides produces a gel-like substance which
protons from the cytoplasm to generate a trans- gradually increases in strength until a critical
membrane electrochemical gradient (Rowland point is reached. At the critical point the gel
2003), i.e., the proton motive force. The passive forms a solution (Villain-Simonnet et al. 2000).
inux of protons in response to the proton motive Such behavior affects the viscosity of the poly-
force can be a problem for cells attempting to saccharides which can affect biolm adherence.
regulate their cytoplasmic pH (Booth The optimum temperature for a microorganism is
1985). Large variations in external pH can over- associated with an increase in nutrient intake
whelm such mechanisms and have a biocidal resulting in a rapid formation of biolm
effect on the microorganisms. Bacteria respond (Stepanovic et al. 2003). Enzymes are responsible
to changes in internal and external pH by of nutrient metabolism; then the formation of a
adjusting the activity and synthesis of proteins biolm is dependent on the presence and reaction
associated with many different cellular processes rates of enzymes. Temperature inuences the
(Olsen 1993). Studies have shown that a gradual reaction rate of enzymes having an impact on the
increase in acidity increases the chances of cell development of the cells. Optimum temperatures
survival in comparison to a sudden increase by result in the healthy growth of bacterial
rapid addition of HCl (Li 2001). This suggests that populations. Temperatures away from the opti-
bacteria contain mechanisms in place which allow mum negatively inuence bacterial enzyme reac-
the bacterial population to adapt to small environ- tion rates, and a reduction of bacterial growth
mental changes in pH. However, there are cellular efciency occurs. Fletcher reported the effect of
processes which do not adapt to pH uctuations so temperature on attachment of stationary phase
easily. One such process is the excretion of cells. Findings showed that a decrease in tem-
exopolymeric substances (polysaccharides). Opti- perature reduced the adhesive properties of a
mum pH for polysaccharide production depends marine Pseudomonad. It is believed that the
on the individual species, but it is around pH 7 for effect was due to a decrease in the bacterial
most bacteria. surface polymer at lower temperatures as well
Both mixed species and pure culture biolms as effects such as reduced surface area. How-
behave like viscoelastic uids. Biolms exhibit ever, Herald and Zottola observed that the pres-
both irreversible viscous deformation and revers- ence of bacterial surface appendages was
ible elastic response and recoil (Ohashi and dependent on temperature. At 35  C cells were
Harada 2004). Extracellular polymeric substances shown to have a single agellum, while at 21  C
like alginate, xanthan, and gellan gum aggregate they had two to three agella, and at 10  C, cells
due to hydrogen bonding to form highly hydrated exhibited several agella. This may suggest that
viscoelastic gels (Stoodley et al. 1999). The pres- the initial interaction between the bacteria and
ence of acetylated uronic acids in the bacterial substrate may increase with a lowering of tem-
alginate of P. aeruginosa biolms increases its perature, increasing the likelihood of adhesion.
hydration capacity. These properties provide the Perhaps the more uniform properties of poly-
biolm with mechanical stability (Stoodley et al. saccharides at lower temperatures increase the
2002). possibility of biolm adhesion, because many
The matrix formed by EPS responds to stress microbial polysaccharides undergo transition
by exhibiting (i) elastic tension due to a combina- from an ordered state at lower temperatures
tion of polymeric entanglement, entropic, and and in the presence of ions to a disordered
Bacterial Biofilm Formation 143

state at elevated temperature under low ionic Hall-Stoodley L, Stoodley P (2002) Developmental regu-
environments (Nisbet et al. 1984). lation of microbial biolms. Curr Opin Biotechnol
13:228233
Although there is plenty of information Hancock REW, Siehnel R, Martin N (1990) Outer mem-
describing the effect of temperature on bacterial brane proteins of Pseudomonas. Mol Microbiol
growth in culture, the effect of temperature on the 4:10691075 B
removal of adhered microorganisms is not so well Herald PJ, Zottola EA (1988) Attachment of Listeria
monocytogenes to stainless steel surfaces at
documented. The reports available describe fairly various temperatures and pH values. J Food Sci
radical effects of temperature on adhered bacteria. 53:15491552
Marion-Ferey et al. observed the effect of high Hiemenz PC, Rajagopalan R (1997) Principles of colloid
temperatures (8090  C) on the removal of and surface chemistry. Marcel Dekker, New York
Klapper I, Rupp CJ, Cargo R et al (2002) Viscoelastic uid
biolms. It was discovered that these tempera- description of bacterial biolm material properties.
tures were not effective for biolm removal due Biotechnol Bioeng 80:289296
to baking effects at high temperature, appar- Li Y (2001) Cell density modulates acid adaptation in
ently increasing the adherent nature of the biolm Streptococcus mutans. J Bacteriol 183:68756884
Liu Y, Yang S, Xu H et al (2004) The inuence of cell and
to the surface. substratum surface hydrophobicities on microbial
attachment. J Biotechnol 110:251256
Marion-Ferey K, Pasmore M, Stoodley P et al (2002) Bio-
References lm removal from silicone tubing: an assessment of the
efcacy of dialysis machine decontamination proce-
Bassler BL (1999) How bacteria talk to each other: regu- dures using an in vitro model. J Hosp Infect 53:6471
lation of gene expression by quorum sensing. Curr Marshall KC, Stout R, Mitchell R (1971) Mechanism of the
Opin Microbiol 2:582587 initial events in the sorption of marine bacteria to sur-
Booth IR (1985) Regulation of cytoplasmic pH in bacteria. faces. J Gen Microbiol 68:337348
Microbiol Rev 49:359378 Nisbet BA, Sutherland IW, Bradshaw IJ et al (1984) XM-6:
Chang YI, Chang PK (2002) The role of hydration force on a new gel-forming bacterial polysaccharide. Carbohydr
the stability of the suspension of Saccharomyces Polym 4:377394
cerevisiae application of the extended DLVO theory. Ohashi A, Harada H (2004) Adhesion strength of biolm
Colloids Surf A Physicochem Eng Asp 211:6777 developed in an attached-growth reactor. Water Sci
Characklis WG, Marshal KC (1990) Biolms. Wiley, New Technol 29:281288
York Olsen ER (1993) Inuence of pH on bacterial gene expres-
Chen MJ, Zhang Z, Bott TR (1998) Direct measurement of sion. Mol Microbiol 8:514
the adhesive strength of biolms in pipes by microma- Peng JS, Tsai WC, Chou CC (2002) Inactivation and
nipulation. Biotechnol Tech 12:875880 removal of Bacillus cereus by sanitizer and detergent.
Costerton JW (1999) Introduction to biolm. Int Int J Food Microbiol 77:1118
J Antimicrob Agents 11:217221 Rowland BM (2003) Bacterial contamination of dental unit
De Weger LA, van der Vlugt C, Wijfjes AHM et al (1987) waterlines: what is your dentist spraying into your
Flagella of a plant-growth-stimulating Pseudomonas mouth? Clin Microbiol Newsl 25:7377
uorescens strain are required for colonization of Rutter PR, Vincent B (1980) Microbial adhesion to sur-
potato roots. J Bacteriol 169:27692773 faces. Ellis Horwood, London
Dunne WM (2002) Bacterial adhesion: seen any good Stepanovic S, Cirkovic I, Mijac V et al (2003) Inuence of
biolms lately? Clin Microbiol Rev 15:155166 the incubation temperature, atmosphere and dynamic
Fletcher M (1977) The effects of culture concentration and conditions on biolm formation by Salmonella
age, time, and temperature on bacterial attachment to spp. Food Microbiol 20:339343
polystyrene. Can J Microbiol 23:16 Stoodley P, Lewandowski Z, Boyle J et al (1999) Structural
Fletcher M (1980) Microbial adhesion to surfaces. Ellis deformation of bacterial biolms caused by short-term
Horwood, Chichester uctuations in uid shear: an in situ investigation of
Gallardo-Moreno AM, Gonzalez-Martin ML, Perez- biolm rheology. Biotechnol Bioeng 65:8392
Giraldo C et al (2002) The measurement temperature: Stoodley P, Cargo R, Rupp CJ et al (2002) Biolm material
an important factor relating physicochemical and adhe- properties as related to shear-induced deformation and
sive properties of yeast cells to biomaterials. J Colloid detachment phenomena. J Ind Microbiol Biotechnol
Interface Sci 271:351358 29:361367
Garrett TR, Bhakoo M, Zhang Z (2008) Bacterial adhesion Sutherland IW (1999) Polysaccharases for microbial
and biolms on surfaces. Prog Nat Sci 18:10491056 exopolysaccharides. Carbohydr Polym 38:319328
Godberg J (2002) Biolms and antibiotic resistance: a Sutherland IW (2001) Microbial polysaccharides from
genetic linkage. Trends Microbiol 10:264 Gram-negative bacteria. Int Dairy J 11:663674
144 BAL

Villain-Simonnet A, Milas M, Rinaudo MA (2000) New injected into reservoirs, and the resulting mixture
bacterial exopolysaccharide (YAS34). II. Inuence of generally features stable supersaturated BaSO4,
thermal treatments on the conformation and structure.
Int J Biol Macromol 27:7787 ready to precipitate. While alkaline scales can be
controlled by altering the feed pH prior to ltra-
tion, sulfate scales are insensitive to pH and there-
fore cannot be controlled by acid addition. BaSO4
BAL scales are usually needle shape crystals which can
easily damage the active layer of the membrane,
Bioarticial Liver resulting in loss of integrity (Fig. 1).
Du Pont method is widely applied as predic-
tion method for BaSO4 scale in RO systems
using the salt solubility at 25  C and the solubil-
Barium Sulfate (BaSO4), Fouling ity product, Kc (Boerlage 2001). The Kc
due to expresses the dynamic equilibrium between the
scalant crystal ions in solution and the crystal
Alice Antony and Pierre Le-Clech solid phase, for example, the Kc for BaSO4 is
School of Chemical Engineering, The University expressed as:
of New South Wales, UNESCO Centre for   
Membrane Science and Technology, Sydney, Kc Ba2 SO4 2 at equilibrium
NSW, Australia
Kc is determined graphically as a function of ionic
strength for the desired recovery (Boerlage
Barium sulfate or barite, BaSO4 is a nonalkaline et al. 1999). The relationship between Kc and
scale, particularly problematic in membrane sys- ionic strength is derived from data on the effect
tems due to its extremely low solubility, 105 mol/l of individual monovalent and divalent cations on
(equivalent to 2.33 mg/l) in pure water. Also, this barium solubility. When the scalant concentration
scale is extremely difcult to remove and clean product exceeds Kc, the solution is supersaturated
from membrane surfaces if not detected at an and scaling may occur. Du Pont recommends a
early stage and is allowed to age into a hard adher- recovery such that the scalant concentration prod-
ent layer. BaSO4 could originate from various uct is 20 % below the Kc to prevent scaling. This
sources. In the offshore oil industry for example, ensures a safety factor for concentration polariza-
seawater (containing high level of sulfate) is tion which may occur at the membrane surface,

500

400 S Ba

300 S 0
Ca
Ba Ba
200
Si
100 Si CaCa Ba
Ba Ba
Ba
0
0 1 2 3 4 5 6 7
ke V

Barium Sulfate (BaSO4), Fouling due to, Fig. 1 SEM-EDS images showing BaSO4 scaling on RO membrane treating
cooling water from power plant (Picture provided by Dr Alice Antony, The University of New South Wales, Australia)
Basic Electrochemical Relations in Membrane Processes 145

causing a higher localized concentration than in


the bulk solution (Boerlage 2001). The major Basic Electrochemical Relations
limitation of this index is that it lacks background in Membrane Processes: Electron
information on interactions between ionic species Conductivity, Ion Conductivity,
on saturation concentrations; as a result, it also Ohms Law, and Coulombs Law B
neglects the effects of common and uncommon
ions on solubility of scale forming species and the Lidietta Giorno1 and Heiner Strathmann2
1
interactions between ionic species. Institute on Membrane Technology, National
Addition of antiscalant is the common method Research Council of Italy, ITM-CNR, Rende,
to control the BaSO4 scale formation. However, Italy
2
continuous monitoring of the RO performances Universitt Stuttgart, Institute of Chemical
through conventional techniques lacks the sensi- Process Engineering Stuttgart,
tivity to detect the subtle changes occurring across Baden-Wurttemberg, Germany
the membrane, and in particular, early deposition
of BaSO4. This lack of detailed and timely assess-
ment of the fouling state can result in delay in In certain membrane processes, charged compo-
applying the necessary cleaning strategies, whose nents such as salt solutions are separated by neu-
efciency is limited for fully developed BaSO4 tral membranes or membrane carrying xed
scaling layers, known to be particularly resistant positive or negative charges using an electrical
to conventional cleaning methods. When BaSO4 potential as driving force. The behavior of ions
scaling is observed during autopsy analysis, in solution and in a membrane is rather different
crown ethers and concentrated sulphuric acid from that of uncharged components because of the
are generally recommended as cleaning agents, strong interaction of electrical charges with each
causing partial membrane hydrolysis (Van der other and their surrounding. Therefore some fun-
Leeden 1991). Alkaline chelants have also damental electrochemical relations shall be briey
been reported to be efcient cleaning agents reviewed.
(Chesters 2009).

Electron and Ion Conductivity


References and Ohms Law

Boerlage SFE (2001) Scaling and particulate fouling The transport of electric charges, i.e., an electric
in membrane ltration systems. Swets & Zeitlinger, current, can be achieved by two characteristic
Lisse modes (Kortum 1957), i.e., by:
Boerlage SFE, Kennedy MD, Witkamp JG, Van Der Hoek
PJ, Schippers JC (1999) BaSO4 solubility prediction in
reverse osmosis membrane systems. J Membr Sci Transport of electrons through solid material
159:4759 such as metals
Chesters SP (2009) Innovations in the inhibition and ransport of ions through liquids such as elec-
cleaning of reverse osmosis membrane scaling and
trolyte solutions
fouling. Desalination 238:2229
van der Leeden MC (1991) The role of polyelectrolytes in
barium sulfate precipitation. PhD thesis, Technical The conductivity of electrons, i.e., metal con-
University of Delft, Delft ductors, is generally three to ve orders of mag-
nitude higher than the conductivity of electrolyte
solutions. Furthermore, the conductivity of metals
Further Reading is decreasing with increasing temperature, while
Antony A, Low JH, Gray S, Childress AE, Le-Clech P,
the conductivity of electrolyte solutions is increas-
Leslie G (2011) Scale formation and control in high
pressure membrane water treatment systems: a review. ing with the temperature. The most important
J Membr Sci 383:116 difference between electron and ion conductivity,
146 Basic Electrochemical Relations in Membrane Processes

however, is the fact that ion conductivity is always k


Leq (4)
coupled with a transport of mass, while due to the Cza na zc nc
very small mass of an electron virtually no mass is
transported in an electron conductor. In spite of Here Leq is the equivalent conductivity of an
the basic difference in the transport mode between electrolyte; C is the molar concentration of the
electron and ion conductivity, the electrical cur- electrolyte in the solution; za and zc are the charge
rent can be described in both cases by the same numbers of the anion and cation, respectively; and
mathematical relation which states that the elec- na and nc are the stoichiometric coefcients of the
trical current is proportional to the electrical anion and cation, respectively.
potential driving force. This relation is referred The stoichiometric coefcient gives the num-
to as Ohms law which is given by ber of anions and cations in a mole electrolyte, and
the valence gives the number of charges related to
RI (1) an ion. For example, for NaCl nc and na are iden-
tical and 1 and also za and zc are 1. However, for
Here is the electrical potential between two MgCl2 nc is 1 and na is 2, and zc is 2 and za is 1.
electron sources, e.g., between two electrodes in The equivalent conductivity can be expressed
an electrolyte solution expressed in Volt, I is the as the sum of the contributions from its individual
electrical current between the electron sources ions. Thus
expressed in ampere, and R is the electrical resis-
tance expressed in ohm. Leq la lc (5)
The resistance R is a function of the specic
resistance of the material, the distance between Here Leq is the equivalent conductivity and la and
the electron sources, and the cross-section area lc are the equivalent conductivities of anion and
of the material through which the electric current cation, respectively.
passes. It is given by The electrical current passing through an
electrolyte solution under the driving force of
l an electrical potential gradient is proportional
Rr (2)
q to the concentration of the ions in the solution,
the stoichiometric coefcients for cat- and
Here R is the overall resistance, r is the specic anions, and the number of electrical charges
resistance, l is the length, and q is the cross-section carried by one ion, i.e., its valence and the ion
area of the conducting material. mobility in the electrolyte solution. The number
The reversal of the resistance and of the spe- of electrical charges carried by all ions of an
cic resistance, respectively, is the conductivity electrolyte under the driving force of an elec-
and the specic conductivity and thus is trical potential gradient through a certain area
A is given by
1 1
S and k (3) X X
R r Je zi ui ni C e N A D zi FJ i (6)
i i
Here S is the conductivity and k is the specic
conductivity. Here Je is the ux of electrical charges and Ji that
The conductivity of electrolyte solutions of the individual ions; z, u, and n are the charge
depends on the concentration and the valence of number, the ion mobility, and the stoichiometric
the ions in the solution. It is expressed as the coefcient, respectively; C is the concentration of
equivalent conductivity or molar conductivity the electrolyte; e is the charge of an electron, NA
(Harned and Owen 1958). For a solution of a the Avogadro number, an electrical potential,
single electrolyte, the equivalent conductivity is and the subscript i refers to the ions in the solu-
given by tion; and F is the Faraday constant.
Basic Electrochemical Relations in Membrane Processes 147

The ion mobility u has the dimension be expressed in terms of a relative permittivity er
m2s1V1. The charge of an electron is which is also referred to as dielectric constant of the
e = 1.6019  1019 C, and the Avogadro medium (Atkins 1990). It is given by
number is NA = 6.0232  1023 molecules per
mol or in this case electrical charges per mole. e B
er (9)
The product of e and NA is called the Faraday eo
constant which is F = 96,485 C eq1
(Atkins 1990). Here e, er, and eo are the permittivity of a medium,
The ux of electrical charges represents an the relative permittivity, and the permittivity in the
electrical current, which is for a solution of a vacuum, respectively.
single electrolyte according to Ohms law given Coulombs law describes the interaction
by between two point charges. In some cases it is
desirable to know the force exerted by one
X charge q in a certain distance r to its surrounding.
zi ui ni C F A D
U X i This force is referred to as electric eld. It is
I zi FJ i A (7) given by
R i
l

K
Here I is the current, U is the applied voltage, R is E (10)
the resistance, A is the area through which the q
current passes, D is the voltage difference
Here K is the force, E is the electric eld, and q is
between two points, and l is the distance between
an electrical charge.
the two points.
In determining the electric eld, the direction
of the eld must be taken into account. For a point
electrical charge q, the electric eld is radial sym-
Coulombs Law and the Electric Field
metric (Starzak 1984; Kortum 1957) and given by
Effect on Ions in Solution
q
Electrical charges carried by ions interact with E (11)
each other. Opposite charges attract each other 4pe r 2
and identical charges repel each other. The inter-
action force between two point electrical charges Here E is the electric eld around a point electric
q1 and q2 in a vacuum separated by a distance r is charge q, r is the distance from the electrical
given by charge, and e is the permittivity of the media
surrounding the charge. The electric eld has the
q1 q2 units of newton per Coulomb or volt per distance.
K (8)
4peo r 2 The electric eld around a point charge is illus-
trated in Fig. 1a, which shows the eld strength or
Here K is the interaction force between two point eld density symbolized by density of the lines
electrical charges, q1 and q2 are electrical charges, which is decreasing with the distance from the
r is the distance between the two point electrical point charge. The electric eld between two
charges, and eo is the permittivity of vacuum. point charges of opposite charge is illustrated in
Equation 8 is referred to as Coulombs law and Fig. 1b. In this case the two charges will attract
the electrical charge is expressed in Coulomb. each other. If they carry the same charge, they will
The permittivity depends on the medium repulse each other.
between the electrical charges. In a vacuum The electric eld can be expressed by an elec-
the permittivity is a fundamental constant denoted trical potential gradient. If the electrical potential
as eo. It has the value 8.854  1012 [C2 J1 m1]. varies over a certain distance, the electric eld
If the medium is not a vacuum, the permittivity can associated with this potential is given by the
148 Basic Electrochemical Relations in Membrane Processes

Basic Electrochemical a b
Relations in Membrane
Processes: Electron
Conductivity, Ion
Conductivity, Ohms
Law, and Coulombs Law,
Fig. 1 Schematic drawing
illustrating the electric eld
lines (a) around a point
charge and (b) between a
positive and a negative
point charge

a b

electrical potential
+
+

+
+ +
+
0
+
+ distance from center ion
+ +


of excess charges

+
concentration

+
+ +
+

+

0
distance from center ion

Basic Electrochemical Relations in Membrane Pro- around a center-ion and (b) the potential and the concen-
cesses: Electron Conductivity, Ion Conductivity, tration of excess charges around a center-ion as function of
Ohms Law, and Coulombs Law, Fig. 2 Schematic distance
drawing illustrating (a) the distribution of counterions

derivative in the direction of the electric eld is decreasing exponentially with the distance from
(Kort
um 1957): the center-ion.
The electrical potential surrounding a center-
4p ion is also decreasing with the distance from
div E div grad r (12)
e the center-ion, and it will reach zero at a certain
distance. This distance is called the Debye length
Equation 12 is a special form of the Poisson dif- and marks the outer boundary of the ion
ferential equation which expresses the change of atmosphere.
the electric eld and the potential, respectively,
around a single charge.
The effect of the electric eld around a center- The Electric Double Layer at the Surface
ion on the distribution of other ions in its sur- Membranes
rounding and the decay of the electrical potential
is illustrated in Fig. 2a, b which shows that the When membranes with xed charges at the sur-
concentration of the excess charges around an ion face are immersed into an electrolyte solution
Basic Electrochemical Relations in Membrane Processes 149

Basic Electrochemical a b
Relations in Membrane O

H 2O
Processes: Electron H 2

H 2O
Conductivity, Ion
Conductivity, Ohms
+

O
B

2
H2 O

H
Law, and Coulombs Law,
Fig. 3 Schematic drawing
illustrating (a) the closest O

H 2O
H2
approach of hydrated
+ + Dj

H2O
cations to the negatively

O
xed ions of the surface of a

2
H2 O

H
cation-exchange membrane
and (b) the potential
O

H 2O
dissipation in the double H2
layer according to the
+

H2 O
Helmholtz model
+

O 2
HO

H
2

charge, they will generate an electric eld directed layer in parallel at a certain distance from the
into an adjacent solution and attract, due to the membrane surface. This distance is determined
Coulomb forces, ions with the opposite charge. by the radius of the hydrated counterion as indi-
This leads to a layer on the membrane surface in cated in Fig. 3.
which the concentration of the oppositely charged The Helmholtz model resembles a parallel
ions is higher than in the bulk solution. In many plate capacitor where the charge is determined
aspects the xed charges of the membrane behave by the number of charges at the surface and in a
very similar to the charges surrounding a single plane parallel to the membrane surface.
charge in an electrolyte solution. These ions will The relation between the surface charges, the
form a layer at a certain distance from the mem- potential between the negatively and positively
brane surface, which neutralize the xed charges charged layers, and their distance are given by the
at the membrane surface. This double layer at the same equation, which describes the capacitance of
interface between the ion-exchange membrane a parallel plate capacitor (Starzak 1984), i.e.,
and the adjacent solution is kept in place by the
attraction force of the electrical potential gener- A q
Ce (13)
ated by the xed ions of the membrane and the 4 pd U
dispersing force of the thermal motion. This dou-
ble layer at the interface between the membrane Here C is the capacitance, A is the area of the
and the electrolyte solution, which is important for charge surface, d is the thickness of the Helmholtz
certain electrokinetic phenomena such as electro- layer, and q is the charge.
osmosis or streaming potential, can be described Introducing the surface charge density s which
by several models (Wagenen and Andrade 1980). is given by
The simplest one of these models is the Helmholtz
q
model. s (14)
A

and replacing the voltage U by the potential dif-


The Helmholtz Double Layer Model
ference Dj between the two layers
Helmholtz postulates that all counterions neces-
sary to neutralize the surface charge of an
U D (15)
ion-exchange membrane are aligned in a single
150 Basic Electrochemical Relations in Membrane Processes

excess charges
a b
4 2 1 0
+ +
+
+ + +
+ Dj
+ + + +
+
+
+
+ +

+ +
+

distance distance

Basic Electrochemical Relations in Membrane Pro- double layer as function of the distance from the membrane
cesses: Electron Conductivity, Ion Conductivity, surface and (b) the potential dissipation as function of the
Ohms Law, and Coulombs Law, Fig. 4 Schematic distance from the surface of the membrane
drawing illustrating (a) the excess counterions in the

give a relation between the thickness of the double


O --
layer d, the surface charge, and the potential dif-
ference in the double layer:
104 + +
4p d
D s (16) H H
e
Basic Electrochemical Relations in Membrane Pro-
Here e is the permittivity and s is the surface cesses: Electron Conductivity, Ion Conductivity,
charge density. Ohms Law, and Coulombs Law, Fig. 5 Schematic
drawing illustrating the structure of a water molecule indi-
cating the dipole character due to the uneven distribution of
The Gouy-Chapman Double Layer Model
the electrical charges within the molecule
The Helmholtz model contains a number of rather
drastic simplications. For example, it assumes
that the xed ions form a homogeneous sheet
and that the counterions form a complementary can be calculated by applying the Poisson equa-
parallel sheet not affected by the thermal motion tion which provides a relationship between the
of the solution. In reality this is not the case.
potential and the excess charges at a given point
In the Gouy-Chapman model, the counterions in the solution and under the assumption that the
in the solution are no longer assumed to be aligned system obeys the Boltzmann statistic by
in a sheet but will occupy a nite volume in a
mixture of cat- and anions. The total number of s xD
counterions in this volume is identical to the xed D (17)
e
charges of the membrane surface. Their distribu-
tion, however, is such that the area close to the Here xD is the Debye length which determines the
membrane surface contains the largest excess of thickness of the double layer. The Debye length is
counterions as indicated in Fig. 4 and is very inversely proportional to the ion concentration of
similar to the ion atmosphere around a single the solution. With increasing ion concentration,
charge. the Debye length is decreasing.
In analogy to the potential decay around a The boundary layer at the surface of mem-
single charge, the potential at a certain distance branes carrying xed charges has a signicant
from the membrane surface carrying xed charges effect on the streaming potential and on the
Basic Electrochemical Relations in Membrane Processes 151

Basic Electrochemical a b --
Relations in Membrane
Processes: Electron

+
+ + +
Conductivity, Ion

--
Conductivity, Ohms

+
--

--
+
B

+
Law, and Coulombs Law, --

+
Fig. 6 Schematic drawing

+
illustrating the distribution --

+
of water molecules +

+
--

+
(a) around a cation and --
+

--
(b) around an anion

+
--
+ +

electric osmotic water transport as well as on the molecules as indicated in Fig. 6 (a) showing water
so-called zeta potential (Lyklema 1995). molecules surrounding a cation and (b) water mol-
ecules surrounding an anion.
Another important result of the molecular
Electrical Dipoles and Intermolecular interaction of water dipoles is the formation of
Forces the hydronium ions from protons and water. In
water the proton recombines readily with the
An electrical dipole consists of two opposite charges water molecule to the hydronium ion in which
attached to a molecule and separated by a certain the three H atoms are no longer distinguishable
distance. An attraction of the charges is prevented and carry the positive charge together. The hydro-
by the rigidity of the molecular structure. The poten- nium ion resembles a tripod with the three
tial produced by the dipole is different from that H atoms on one side and all equally apart from
produced by a single charge. The potential of a the oxygen atom. The rapid formation of the
dipole with a single charge is decreasing with the hydronium ion is the reason for the much faster
distance by the square of the distance. The dipole transport of protons compared to other ions in an
momentum of molecules is measured in Debye aqueous solution.
[D] with D = 3.33  1030 A s m. The dipole
momentum varies substantially depending on the
polarity of the molecules. It is 0 for a completely
nonpolar molecule such as CCl4 or H2 and ca. 1.80 References
D for a polar molecule such as water (Atkins 1990).
Atkins PW (1990) Physical chemistry, 4th edn. Oxford
The high dipole momentum of the water is the result
University Press, Oxford
of the water molecule structure in which the hydro- Harned and Owen (1958) The physical chemistry of elec-
gen atoms are attached to one side of the oxygen trolyte solutions, 3rd edn. Reinhold, New York
atom as illustrated in Fig. 5. Kortum G (1957) Lehrbuch der Elektrochemie. Verlag
Chemie, Weinheim
The strong dipole momentum of water is also Lyklema J (1995) Fundamentals of interface and colloid
the reason for its good solubility properties for science, vol II, Solid-Fluid Interfaces. Academic,
salts. The water dipoles tend to break the generally London
strong Coulomb forces between the negatively Starzak ME (1984) The physical chemistry of membranes.
Academic, New York, pp 4464
and positively charged ions of a salt crystal by
Wagenen and Andrade (1980) Flat plate streaming poten-
surrounding the ions. Thus, in an aqueous solu- tial investigations: hydrodynamics and electrokinetic
tion, each ion is surrounded by a shell of water equivalency. J Colloid Interface Sci 76:305
152 Batch Diafiltration

It should be pointed out that the removal of


Batch Diafiltration microsolutes and the concentration of
macrosolutes (i.e., the reduction of the volume
Zoltn Kovcs of process liquor) are both required for most appli-
Department of Food Engineering, Institue of cations. The term batch dialtration, in its broader
Bioengineering and Process Engineering, Szent sense, may stand for a batch ltration process that
Istvan University, Budapest, Hungary is designed to achieve the twin objectives of con-
centrating and purifying a multi-solute system
according to a specic diluant utilization strategy.
Batch dialtration refers to a pressure-driven In this context, batch dialtration is a complex
membrane ltration process in which a diluant process that may involve a sequence of consecu-
(pure solvent) is added into the feed tank in tive operational steps.
order to enhance the degree of separation of A straightforward way of achieving the dual
macrosolutes from microsolutes. In batch objectives of concentration and fractionation is to
dialtration, in contrast to continuous combine CVD with concentration mode opera-
dialtration, the retentate stream is recirculated tional steps (i.e., in which no diluant is added
to the feed tank, and only the permeate stream is into the feed tank). A so constructed typical
collected separately. During the operation, solute- three-step process, also referred to as traditional
free diluant is introduced into the feed tank to dialtration (TD), involves the following phases:
replace solvent losses as schematically illustrated (i) concentration mode to achieve an intermediate
in Fig. 1. The requirement for an effective separa- macrosolute concentration, (ii) constant-volume
tion is the utilization of a membrane which highly dialtration to wash out the microsolute by a
retains the macrosolute but permeable for the pure solvent introduced into the system, and
microsolute. Thus, depending on the application, (iii) further concentration to the nal desired
microltration, ultraltration, nanoltration, or macrosolute concentration. Beside TD, a number
even reverse osmosis membranes can be applied. of alternative strategies have been proposed.
In its strict, original sense, the term batch These include the sequential dilution dialtra-
dialtration refers to a process that aims at remov- tion (SDD), intermittent feed dialtration
ing the microsolutes from the process liquor. The (IFD), variable-volume dialtration (VVD), pre-
standard way of achieving this purication goal is concentration combined with variable-volume
to employ a constant-volume dialtration (CVD) dialtration (CVVD), and dynamic-volume
process that is probably the most common type of dialtration (DVD).
batch dialtration. In CVD, the feed volume is Dialtration techniques differ in controlling
kept constant by continuously adding a diluant at the addition of the diluant in terms of quantity
a rate equal to the permeation rate. and duration. The differences between the various

Batch Diafiltration,
Diluant u(t)
Fig. 1 Schematic
representation of batch Retentate Permeate q(t)
dialtration conguration

Feed
Batch Diafiltration 153

Batch Diafiltration, Table 1 Diluant utilization strate- V represents the feed tank volume. This initial
gies in batch diafiltration value problem describes the evolution in time
Name a - strategy of the feed volume and the feed concentration
Constant-volume a1 of any solute under the assumption that the
dilution diluant is solute-free and the feed tank is B
Traditional a f0, 1, 0g well-mixed. Note that the time-dependent vari-
dialtration
ables (i.e., permeate ux and the solute rejec-
Variable-volume a const, 0 < a < 1
dialtration tions) are, in a general case, a function of feed
Preconcentration a f0, a1 g, a1 const, 0 < a1 < 1 concentrations and may vary with operation
with variable- conditions (temperature, pressure, cross-ow
volume velocity, etc.).
dialtration
  The unique feature of realizing both concen-
Intermittent feed a 0, amax n , 0
dialtration tration and fractionation puts membrane ltra-
  tion in an attractive position and compares
Sequential a amax , 0n
dilution favorably with other separation methods or
dialtration even with a sequence of consecutive unit oper-
Dynamic-volume a at 0  at  amax ations. In comparison with continuous pro-
dialtration
cesses, batch operations are especially suited
n number of repetition to small-scale operations, require less expensive
automatic controls, and enable a reduced mem-
brane area in order to reach the target (Baker
operations are best described by the proportional-
2004). Most batch plants operate under constant
ity factor a (i.e., the ratio of diluant ow d(t) to
mechanistic membrane pressure adjusted sim-
permeate ow q(t)) as a function of operation time
ply by the retentate valve. There exist, however,
(Foley 2006). For instance, TD process is charac-
other types of process control strategies in engi-
terized with a sequence a(t) = {0, 1, 0} with two
neering practice, such as constant ux or con-
unknown switching times at the end of the rst
stant wall concentration control (van Reis
and of the second time interval. Similarly, CVVD
et al. 1997). These are normally employed
process has two phases with constant a levels
when unfavorable side effects (e.g., enhanced
a(t) = {0, a1} and an unknown switching time.
fouling or product quality deterioration) occur
Table 1 shows the diluant control strategies
that can be associated with the high concentra-
applied in batch processing. Note that the best
tion at the membrane wall.
time-varying prole of diluant addition
needs not necessarily be one of the arbitrarily
predened proles. The dialtration process,
that is, designed by the evaluation of the optimal References
time-varying prole of the diluant ow, is referred
to as dynamic-volume dialtration (Paulen Baker R (2004) Membrane technology and applications.
et al. 2012). Wiley, Chichester
The governing differential equations for a gen- Foley G (2006) Ultraltration with variable volume
dialtration: a novel approach to water saving
eralized batch dialtration process are given as in dialtration processes. Desalination 199(13):
220221
dci ci q Paulen R, Fikar M, Foley G, Kovcs Z, Czermak P (2012)
Ri  a, ci 0 ci0 , i 1, 2 Optimal feeding strategy of dialtration buffer in
dt V
dV batch membrane processes. J Membr Sci 411412:
a  1q, V 0 V 0 : 160172
dt van Reis R, Goodrich EM, Yson CL, Frautschy LN,
Whiteley R, Zydney AL (1997) Constant Cwall
where ci is the solute concentration in the feed ultraltration process control. J Membr Sci 130(12):
tank, Ri the rejection of component i, and 123140
154 Bed-to-Wall Mass Transfer Limitations

instance, into the product B, this being repre-


Bed-to-Wall Mass Transfer sentative of all possible reactions. If the reac-
Limitations tion rate is sufciently fast, the transport
through the gas phase becomes limiting and,
Alessio Caravella thus, a signicant concentration/pressure drop
National Institute of Advanced Industrial Science is generated, decreasing in fact the effective
and Technology Research Institute for concentration of species A that can be
Innovation in Sustainable Chemistry, ISC-AIST, involved in the surface reaction with respect
Tsukuba, Ibaraki, Japan to the bulk concentration.
As for the second case (concentration polari-
zation, Fig. 1b), a membrane permeable to both
Bed-to-wall mass transfer limitations. These phe- species A and B is considered, with the species
nomena, also referred to as concentration polar- A being the one to separate and more permeable
ization in the eld of membrane technology (higher transmembrane ux) than the species
(Gallucci et al. 2011), are more generally related B. Because of the effect of the higher ux of the
to the mass transfer resistance that a species species A, the species B is pushed toward the
encounters to reach an active wall. An active membrane wall, generating in this way an obstacle
wall is a surface where physical and/or chemical for the species A to reach the surface. Concentra-
transformations (including adsorption/desorption tion polarization is not desired for two main rea-
phenomenon and solubilization/desolubilization sons. First, it causes a decrease in the permeation
processes) occur. driving force of the species A, as the surface-
The main cases of interest in chemical engi- surface concentration difference is smaller than
neering are reported in Fig. 1. As for the former the bulk-bulk one. Second, it tends to favor the
(Fig. 1a), an impermeable catalytic wall is consid- permeation of the less-permeating species (B),
ered, where the reactant species A reaches the causing the actual membrane separation factor
catalytic surface and is transformed, as an to decrease.

Bed-to-wall mass transfer limitations


Concentration
a b Polarisation
A A
Flux (A) C
Bulk
AB
Bulk

Bulk

Flux (B)
B
B B
Surface
Surface

Surface

Catalytic Wall Membrane Wall


(Impermeable) (Permeable)

Bed-to-Wall Mass Transfer Limitations, reaction takes place and (b) Case of membrane (permeable
Fig. 1 Schematic representations of the two most com- wall) through which all the components can, in general,
mon cases of bed-to-wall mass transfer limitations. (a) pass. Membrane is supposed to be impermeable to the
Case of impermeable catalytic wall on which a chemical species C
Beer Clarification 155

References Beer Clarification, Table 1 Comparison of key


parameters of beer filtered with DE filtration and
Gallucci F, Van Sint Annaland M, Kuipers JAM microfiltration (Lipnizki 2005)
(2011) Modeling of membrane reactors for hydrogen Beer Beer
production and purication. In: Membrane engineering before after DE Beer after
for the treatment of gases. vol 2 Gas separation prob- ltration ltration microltration B
lems combined with membrane reactors, RSC energy Original 11.40 11.37 11.39
and environment series. Roheena Anand Publisher, extract
Books, Cambridge, pp 139, Chapter 10 [%]
Alcohol 3.84 3.83 3.84
[%]
Color 7.20 6.70 7.00
[EBC]
Viscosity 1.62 1.57 1.56
Beer Clarification [MPas]
Turbidity 32.00 0.53 0.41
Frank Lipnizki at 0  C
Alfa Laval Copenhagen, Sborg, Copenhagen, [EBC]
Denmark

3. AlfaBright system by Alfa Laval and


In the traditional brewing process, the beer is Sartorius a process based on the combination
claried after fermentation and before maturation of cassette microltration system with a high-
to remove mainly the remaining yeast but also speed separator as pretreatment
microorganisms and haze. The conventional pro-
cess for beer clarication is the combination of a The membranes established for beer ltration
high-speed separator followed by diatomaceous are all polymeric microltration membranes
earth (DE)/kieselguhr ltration which is based on polyethersulfone with 0.50.65 mm
complemented in some cases by second ltration pores and beer capacities of 0.51.0 hl/(m2 h)
with PVP (polyvinylpyrrolidone) to obtain a very (Buttrick 2007). The resulting beer quality from
clear beer. The major challenge of the conven- the membranes is similar or improved compared
tional process is related to the DE ltration to the DE ltration; in Table 1 a comparison
because the DE can vary in quality and is prob- between beer ltered by DE and microltration
lematic for handling and disposal since it is haz- membranes is given. Other membranes, e.g.,
ardous plus DE ltration generates large amounts ceramic membranes, have been tested for beer
of efuent. Alternatively, from its introduction in ltration but so far have not established them-
2001 (Buttrick 2007) cross-ow microltration selves on the market. The key difference between
has established itself in the brewing industry the three concepts is the use of a high-speed sep-
with over 50 breweries worldwide adopting this arator as pretreatment. In the BMF system a
DE-free beer ltration. Generally, three concepts retentate tank is used to collect the beer solids,
are currently used in the industry: while both the PROFi and the AlfaBright systems
are using high-speed separators as pretreatment
1. Beer Membrane Filtration (BMF) by Pentair before the membrane to remove the beer solids
(previously Norit) a system based on hollow and thus eliminating the need for a retentate tank.
ber microltration cartridges without a high- The systems can be typically run in batch or
speed separator as pretreatment continuous operation depending on the size
2. PROFi Membrane System by Pall and GEA and requirements of the individual brewery. In
Westfalia a combination of hollow ber batch operation, the complete system shifts from
microltration system with a high-speed sepa- ltration into cleaning mode after each batch.
rator as pretreatment Plants with continuous operation are arranged in
156 Beer Dealcoholization

skids/blocks and use sequential cleaning which process based on reverse osmosis can be divided
allows for some skids/blocks to be in standby into four individual operations which are typically
cleaning mode, while other blocks are in ltration carried out in batch mode:
mode. The major challenges for cross-ow mem-
brane beer ltration are the relatively high invest- 1. Pre-concentration: In this step the volume of
ment costs and complexity of the process when the feed beer is reduced. The beer is passed
compared to DE ltration and the increasing through the membrane modules and is then
availability of alternative DE-free lter aids. recycled to the batch tank. The
permeate water and alcohol is removed
from the process, while retentate, concentrated
References beer and avors, is returned to the batch tank.
2. Dialtration: This step is similar to the
Buttrick P (2007) Filtration the facts. Brewer Distiller Int pre-concentration step but dialtration
3(12):1219
water desalted and deoxygenized water is
Lipnizki F (2005) Optimisation and integration of mem-
brane processes in the beverage industry, 10th edn. added to wash out the alcohol. The amount of
Aachener Membran Kolloquium, Aachen, dialtration water added balances the amount
16.-17.03.2005 of permeate removed from the process, and
thus, the level in the batch tank remains con-
stant. This operation is continued until the
desired alcohol concentrations in the beer are
Beer Dealcoholization achieved.
3. Alcohol adjustment: In this step, the taste and
Frank Lipnizki alcohol content is ne-tuned by addition of
Alfa Laval Copenhagen, Sborg, Copenhagen, desalted and deoxygenized water.
Denmark 4. Posttreatment: In order to give the beer its
specic character and to balance taste losses
due to removal of the taste carrier alcohol, the
In the last decades the demand for low alcohol and CO2 levels can be adjusted, and hop extract,
alcohol-free drinks increased, e.g., in Germany syrup, or other avor enhancers are added.
the annual consumption of alcohol-free drinks
nearly doubled from 130.4 l per person in 1980 As an alternative to reverse osmosis, dialysis
to 248.2 l person in 1999, while the annual con- can be used for the dealcoholization of beer. Com-
sumption of alcoholic drinks declined from 179.5 monly, hollow ber modules are used for dialysis
to 156.3 l during the same period (Gebhardt allowing the beer to ow on one side of the mem-
2001). Conventionally beer can be dealcoholized brane and water as dialysate on the other side. The
by distillation, but additionally the membrane process is normally operated in counter-current
process reverse osmosis and dialysis have ow to maximize the concentration gradient over
established themselves for the partial dealcoho- the dialysis membrane and thus the driving force
lization of beer by eight to ten times. The key of the dialysis process. The dialysate is constantly
advantage of membrane processes over distilla- recycled over a steam stripping column to remove
tion is that beer can be dealcoholized at low tem- the alcohols, thus maintaining the driving force of
peratures typically 78  C to minimize the effect of the process while minimizing the dialysate con-
temperature on the beer avor resulting in high- sumption. In addition, in order to minimize CO2
quality low alcohol beer, which can be bottled losses, the feed pressure should be selected close
after nal sterile ltration. to the CO2 saturation pressure, and small amounts
Reverse osmosis is typically carried out in of the CO2 should be added to the dialysate
spiral wound modules, and the dealcoholization (Branyik et al. 2012).
Benzene and Cyclohexane Separation 157

Furthermore, osmotic distillation for beer the fermentation tank volume. In the past this beer
dealcoholization (Russo et al. 2013) and in the tank bottom would be considered lost since
pervaporation for aroma recovery can be consid- it could not be added to the main beer stream.
ered as part of the beer dealcoholization process However, using microltration with tubular
(del Olmo et al. 2012), but so far these processes ceramic membranes or plate-and-frame modules B
are not commercialized. with polymeric membranes, it is possible to
recover a high-quality beer which can be blended
with the main beer stream going toward clarica-
References tion and storage. Using microltration mem-
branes with pores of 0.40.5 mm, it is possible to
Branyik T, Silva DP, Baszczynski M, Lehnert R, Almeida e retain the yeast and allow the beer to pass the
Silva JB (2012) A review of methods of low alcohol
membrane without any major impact on the qual-
and alcohol-free beer production. J Food Eng
2012(108):493506 ity of the beer. In this process, the yeast in the tank
del Olmo A, Blanco CA, Palacio L, Prdanos P, Hernndez bottoms is concentrated from 7 % to 10 % DM to
A (2012) Setting up of a method of pervaporation for approx. 20 % DM and thus 5070 % of the beer in
improving alcohol-free beer. Euromembrane, London,
the tank bottoms can be recovered. The yield of
pp 2327
Gebhardt W (2001) Weltforum der Wein- und recovered extract and alcohols can be further max-
Saftbereitung. F&S Filtrieren Separieren 15(5):229 imized if dialtration water is added. Recovering
Russo P, Liguori L, Albanese D, Crescitelli A, Di Matteo beer from tank bottoms can increase the output of
M (2013) Investigation of osmotic distillation tech-
an average brewery by 1 % of its annual produc-
nique for beer dealcoholization. CEt Chem Eng Trans
32:17351840 tion or 24,000 hl extra for a brewery with an
annual output of 2 million hl (Lipnizki 2005).
The amortization for a microltration beer recov-
ery unit is typically 12 years.

Beer Maturation
References
Frank Lipnizki
Alfa Laval Copenhagen, Sborg, Copenhagen, Lipnizki F (2005) Optimisation and integration of mem-
brane processes in the beverage industry, 10. Aachener
Denmark
Membran Kolloquium, 16.-17.03.2005: preprints. -
Aachen, Mainz, 2005. - 3-86130-409-0.

In the beer production process, the claried and


cooled wort from the brewhouse is transferred
together with yeast to the fermentation tanks for Benzene and Cyclohexane
the primary fermentation which converts the fer- Separation
mentable sugar into alcohol and CO2. The
resulting green beer undergoes a second Tadashi Uragami
fermentation beer maturation under addition Organization for Research and Development of
of sugar or fresh yeasted wort. During the matu- Innovative Science and Technology (ORDIST),
ration, the residual fermentable sugars in the Kansai University, Suita, Osaka, Japan
green beer will be converted to alcohol and the
beer will be saturated with CO2. After the fermen-
tation, the beer is claried and stored in the bright Benzene/Cyclohexane Separation
beer cellar. Remaining in the fermentation tanks
are tank bottoms a mixture of settled yeast cells In the petrochemical industry, the separation of
and beer which are equal approx. 1.52.0 % of benzene (Bz) and cyclohexane (Chx) is the most
158 Benzene and Cyclohexane Separation

feed mixture can preferentially permeate through


the membrane. In a PV process, differences
between the solubility and diffusivity of the mix-
ture components in the polymer membrane and
the relative volatility of the permeants determine
the permeability and selectivity (Binding
et al. 1961; Aptel et al. 1974). In general, PV
exhibits the following characteristics (Uragami
2006, 2010):

1. Selective transport across the nonporous mem-


brane is achieved by a three-step process of
solution, diffusion, and evaporation.
Benzene and Cyclohexane Separation,
Fig. 1 Principle of pervaporation (PV)
2. Because the driving force for permeation is the
vapor pressure for each component rather than
total system pressure, this method is effective
important and difcult processes. Chx is produced for separation of organic liquid mixtures with
in benzene hydrogenation units under Ni or Pd high osmotic pressure.
catalyst. The unreacted Bz is remained in the 3. PV can be applied to the separation and con-
reaction mixture and must be removed to produce centration of mixtures that are difcult to sep-
pure Chx. The separation of benzene and Chx is arate by distillation. For example, it is useful
very difcult by a conventional distillation for the separations of azeotropic mixtures,
because close-boiling point mixtures are formed close-boiling point mixtures, and structural
in the entire range of their compositions. At pre- isomers.
sent, azeotropic distillation and extractive distilla- 4. PV can be used for the removal of certain
tion are applied to this separation. These components in equilibrium reactions.
distillations, however, are complex and need 5. Polymer membrane compaction, a frequent
high energy consumption. In the industry of Chx problem in high-pressure gas separations, is
production, the conventional Bz/Chx separation not encountered in PV because the feed pres-
processes are strongly required. Therefore, many sure is typically low.
studies have investigated the PV properties of
polymer membranes for Bz/Chx separation. A side-chain liquid-crystalline polymer (LCP)
Pervaporation (PV) is a promising membrane was synthesized by the addition of mesogenic
technique for the separation of organic/organic monomer to poly(methylsiloxane) with a Pt cata-
mixtures, as PV can be used to separate organic lyst. When Bz/Chx mixtures were permeated
liquid mixtures such as azeotropic and close- through the LCP membranes by PV at various
boiling point mixtures. The separation mechanism temperatures, the permeation rate increased with
in PV is not based on only relative volatility of increasing benzene concentration in the feed solu-
components in distillation but on the difference in tion and permeation temperature. Although the
sorption and diffusion properties of the feed LCP membranes exhibited Bz/Chx selectivity,
substances. the mechanism responsible for the permeation
Figure 1 illustrates the principles of PV. In this and separation of the Bz/Chx mixtures was differ-
separation process, when a liquid mixture is fed to ent in the glassy, liquid-crystalline state versus the
the upstream side of a polymer membrane and the isotropic state of the LCP membranes. These
downstream side is evacuated, a component in the results suggest that the Bz/Chx selectivity was
Benzene and Cyclohexane Separation 159

moderately inuenced by the change in LCP of 6FDA with various diamines. To obtain high
membrane structure (i.e., a state transformation). permeability as well as high selectivity, a combi-
The balance between the orientation of the nation of the diamines 2,3,5,6-tetramethyl-1,4-
mesogenic groups and the exibility of the silox- phenylene diamine (4MPD), 4,40 hexauoro-
ane chain is very important with respect to perme- isopropylidiene dianiline (6FpDA), and B
ability and Bz/Chx selectivity (Inui et al. 1997, 3,5-diaminobenzoic acid (DABA) as monomers
1998). When benzene/cyclohexane, toluene/ with a crosslinkable group was used. Cross-
cyclohexane, and o-xylene/cyclohexane mixtures linking is necessary to prevent undesirable swell-
were subjected to PV through an LCP membrane ing effects, which generally occur with non-cross-
in the liquid-crystalline state, the permeation rate linked polyimides, especially if high benzene con-
increased with increasing temperature and the centrations are reached during PV. The degree of
LCP membrane exhibited selectivity for the aro- cross-linking was kept constant at 20 %, whereas
matic hydrocarbons. The permeation rate and the ratio of the diamine monomers 6FpDA and
selectivity of the LCP membrane for each mixture 4MPD was varied. The PV experiments were
decreased with increasing molecular size of the performed at 60  C, using Bz/Chx mixtures with
aromatic hydrocarbon in the binary feed mixture benzene concentrations covering the entire con-
(Inui et al. 1998). When Bz/Chx mixtures were centration range. All of the cross-linked polymers
permeated through nematic and smectic side- had excellent chemical and thermal stability in the
chain liquid-crystalline polymer (n- and s-LCP) PV experiments. In all cases, conditioning of the
membranes under various conditions during PV, membrane samples with pure benzene was a suit-
the n- and s-LCP membranes exhibited Bz/Chx able pretreatment to enhance the permeation rate
selectivity. The selectivity of the n-LCP mem- without decreasing the Bz/Chx selectivity signif-
brane changed from solubility-selectivity con- icantly. For the most promising membrane mate-
trolled to diffusion-selectivity controlled upon rial, 6FDA-4MPD/DABA of 4:1 cross-linked
the state transformation of the membrane, induced with ethylene glycol, the PV experiments
by an increase in the permeation temperature. In were performed with a benzene/cyclohexane
contrast, the selectivity of the s-LCP membrane feed mixture of 50/50 (w/w) over a temperature
was governed by diffusion selectivity regardless range between 60  C and 110  C to determine the
of the state of this membrane. At low permeation effect of temperature on the separation
temperatures, the n-LCP membrane in the liquid- characteristics.
crystalline state exhibited lower permeability but
higher selectivity than the s-LCP membrane.
However, at high permeation temperatures, the
relationship between the permeability and References
Bz/Chx selectivity of the n-LCP and s-LCP mem-
Aptel P, Cuny J, Jozenfonvice J, Morel G, Neel J (1974)
branes in the liquid-crystalline state was reversed. Liquid transport through membranes prepared by
These results are a result of differences in the grafting of polar monomer onto poly(tetrauor-
chemical and physical structure of the n-LCP oethylene) lms. II. Some factors determining
pervaporation rate and selectivity. J Appl Polym Sci
and s-LCP membranes (Inui et al. 1998).
18:365
The PV properties of a series of cross-linked Binding RC, Lee RJ, Jennings JF, Mertic EC (1961) Sepa-
4,40 -hexauoro-isopropylidene dianhydride ration of liquid mixtures by pervaporation. Ind Eng
(6FDA)-based copolyimide membranes for the Chem 53:47
Inui K, Miyata T, Uragami T (1997) Permeation and sep-
separation of Bz/Chx mixtures were investigated
aration of benzene/cyclohexane mixtures through
(Ren et al. 2001). The glassy, highly rigid liquid-crystalline polymer membranes. J Polym Sci
copolyimides were obtained by polycondensation Part B Polym Phys 35:699
160 Benzyl-Modified Cellulose

Inui K, Miyata T, Uragami T (1998a) Effect of permeation The benzylation of cellulose can lead to
temperature on permeation and separation of a ben- several useful applications. For example, in
zene/cyclohexane mixture through liquid-crystalline
polymer membranes. J Polym Sci Part B Polym Phys blood hemodialysis, membrane ltration is a
36:281 key process for the replacement of renal func-
Inui K, Miyata T, Uragami T (1998b) Permeation and tion in uremic patients. The hydroxyl groups
separation of binary organic mixtures through a in cellulose can activate complement function,
liquid-crystalline polymer membrane. Macromol
Chem Phys 199:589 which is an undesirable process in hemodialy-
Inui K, Okazaki K, Miyata T, Uragami T (1998c) Effect of sis. A certain amount of the substitution of
mesogenic groups on characteristics of permeation and hydroxyl groups with benzyl groups, being
separation for benzene/cyclohexane mixtures of side- known as synthetically modied cellulose
chain liquid-crystalline polymer membranes. J Membr
Sci 143:93 (SMC), can help minimize the complement
Ren J, Standt-Bickel C, Lichtenthaler R (2001) Separation activation, by balancing the hydrophilic and
of aromatics/aliphatics with crosslinked 6FDA-based hydrophobic domains in the cellulose structure
copolyimides. Sep Purif Technol 223:31 (Hoenich et al. 1997).
Uragami T (2006) Polymer membranes for separation of
organic liquid mixtures. In: Yanpolskii Y, Pinnau I, Another application of benzylation of cellulose
Freeman BD (eds) Materials science of membranes is the fabrication of natural ber composites by
for gas and vapor separation. Wiley, Chichester, the surface modication of cellulose through the
pp 355372 route shown in Fig. 1 (Lu et al. 2004). The ber
Uragami T (2010) Selective membranes for purication
and separation of organic liquid mixtures. In: composites exhibit excellent thermal formability
Drioli E, Georno L (eds) Comprehensive membrane and mechanical properties, enabled by the benzyl
science and engineering, volume 2 membrane opera- cellulose skin layer and natural cellulose core
tions in molecular separations. Elsevier, Amsterdam, (Zhang et al. 2005).
pp 273324
It should be noted that the benzylation of
cellulose, as mentioned above, can produce a
heterogeneous structure with only the skin of
Benzyl-Modified Cellulose the cellulose structure being modied.
A homogeneous benzylation of cellulose has
Hongyang Ma, Benjamin S. Hsiao and been achieved when ionic liquids were used as
Benjamin Chu the solvent for cellulose (Gericke et al. 2012).
Department of Chemistry, Stony Brook N-alkylpyridinium chlorides can be used to
University, Stony Brook, NY, USA dissolve cellulose and then react with benzyl
groups, resulting in benzyl cellulose with a
high degree of substitution. It is possible that
Benzyl-modied cellulose contains covalently the surface modication of brous mats with
bonded benzyl groups in the cellulose structure, benzyl cellulose can be achieved by surface
typically produced by etherication of hydroxyl coating and thereby forming a non-covalently
groups (Bowry and Rintelen 1998) shown in bonded modication approach (Ma et al.
Fig. 1. 2014).

Benzyl-Modified
Cellulose, Cl O
OH
Fig. 1 Synthetically
HO OH HO OH
modied cellulose from O O
O O O
O
benzyl-modied cellulose O NaOH HO OH O
HO OH
by etherication OH n OH n
Bilberry Aroma Recovery by Pervaporation 161

References Inc., California (EEUU), and Agrotechnology &


Food Innovations (A&F) in the Netherlands
Bowry SK, Rintelen TH (1998) Synthetically modied (Willemsen et al. 2004), and theoretical studies
cellulose (SMC) a cellulosic hemodialysis membrane
assessing the recovery and concentration of aroma
with minimized complement activation. ASAIO J 44:
M579M583 compounds by means of PV have demonstrated B
Gericke M, Fardim P, Heinze T (2012) Ionic liquids -prom- the viability of this technology at industrial scale
ising but challenging solvents for homogeneous deriv- (Karlsson et al. 1998; Lipnizki et al. 2002a, b;
atization of cellulose. Molecules 17:74587502
Trifunovic et al. 2006). During the PV, the
Hoenich NA, Wofndin C, Stamp S, Roberts SJ, Turnbull
J (1997) Synthetically modied cellulose: an alterna- aroma compounds contained in a liquid or feed
tive to synthetic membranes for use in haemodialysis? phase permeate selectively through a dense
Biomaterials 18:12991303 hydrophobic membrane due to the chemical
Lu X, Zhang M, Rong M, Yue D, Yang G (2004) The
potential gradient caused by a reduction of the
preparation of self-reinforced sisal ber composites.
Polym Polym Compos 12:297307 component partial pressure in the permeate side.
Ma HY, Hsiao BS, Chu B (2014) Functionalized The aroma compounds are preferentially
electrospun nanobrous microltration membranes transported through the membrane according to
for removal of bacteria and viruses. J Membr Sci
their afnity to the membrane material and their
452:446452
Zhang M, Rong M, Lu X (2005) Fully biodegradable natu- mobility in the membrane matrix, which is the
ral ber composites from renewable resources: all-plant hypothesis of the most accepted mass transport
ber composites. Compos Sci Technol 65:25142525 mechanism in PV known as solution-diffusion.
Bilberry (Vaccinium myrtillus L.) is a species
of shrub and is native from Europe, northwest
Bichromal Particles Synonym: regions of North America, and Northern Asia
Two-Colored Particles (Morton and Macleod 1990). The international
markets demand of bilberrys extract has been
Encapsulation Application steadily growing in the recent years (Foster and
Blumenthal 2012). The major aroma compounds
present in crushed bilberry were identied by gas
chromatography-mass spectroscopy (GC-MS).
Bilberry Aroma Recovery by The results are shown in Fig. 1. Trans-Hex-2-en-
Pervaporation 1-ol was characterized as one of the impact avor
of the bilberry (von Sydow and Anjou 1969).
Immaculada Ortiz and Nazely Diban
Department of Chemical and Biomolecular Membrane Material and Module
Engineering, University of Cantabria, Santander, Configurations
Cantanbria, Spain The most typical organophilic membrane mate-
rials employed in PV of aroma compounds in the
literature are polydimethylsiloxane (PDMS) and
Introduction polyoctylmethylsiloxane (POMS). POMs mem-
branes present higher enrichment factors for
Pervaporation (PV) is a membrane-based technol- aroma compounds than PDMS albeit not signi-
ogy largely studied for aroma compound recovery cantly different. Nonetheless, PDMS membranes
and concentration in the food industry (Pereira are largely more studied due to their stability
et al. 2006). At least two PV pilot plants for during operation and good properties of
aroma compound recovery have been built at processing (Karlsson and Trgardh 1993;
Membrane Technology and Research (MTR) Lipnizki et al. 1999; Urtiaga et al. 1999).
162 Bilberry Aroma Recovery by Pervaporation

kCounts
500

1 4

400

300

200

5
2

100 3

25 50 75 100 minutes

1540 3148 4747 6338 Scans

Bilberry Aroma Recovery by Pervaporation, (4) trans-Hex-2-en-1-ol, and (5) 1-hexadecanol (Adapted
Fig. 1 GC-MS chromatogram of the crushed bilberry: from (Garcia et al. 2008))
(1) trans-hexenal, (2) 2-butyl-1-octanol, (3) 1-hexanol,

With regard to the membrane module congu- (i) The feed composition (ethanol and aroma
rations, plate-and-frame is the most employed compound). The results are presented in
in literature for laboratory scale studies for Fig. 2. As expected, ethanol ux, JEtOH,
their simplicity and versatility for the evaluation increased linearly with higher ethanol con-
of different membrane materials. However, the tent in the feed, while in contrast, aroma
hollow bers membrane (HFM) module congu- compound partial ux, JHex, remained inde-
ration presents important advantages, such as pendent on ethanol concentration but
higher contact area per unit volume of membrane presented a linear dependency with its own
module and thus higher compactness of the equip- concentration in the feed solution. The major
ment and easier operation at industrial scale component ux, water, was independent
(Urtiaga et al. 1999, 2002; Tasselli et al. 2007). on both ethanol and aroma compound com-
position. The enrichment factors found for
Influence of Process Variables the aroma compound, bHex, varied from
Using a model ternary solution (water/ethanol/ 98 to 201.
trans-Hex-2-en-1-ol), the process variables that (ii) The feed temperature, studied in the range
exerted an important inuence on the PV perfor- 35  C < T < 50  C. The components par-
mance of the impact aroma compound (trans- tial uxes (water, ethanol, and trans-Hex-2-
Hex-2-en-1-ol) when using a PDMS HFM mod- en-1-ol) were found to follow an Arrhenius
ule with the characteristics presented at (Garcia dependency with temperature as plotted in
et al. 2008) were: Fig. 3.
Bilberry Aroma Recovery by Pervaporation 163

[Hex] (kg.m3)
a b 0 0.1 0.2 0.3
20 2.00 1.8
18 1.80 1.6
16 1.60 1.4 B
JEtOH (g.m2.h1)

JHex (g.m2.h1)

JHex (g.m2.h1)
14 1.40
1.2
12 1.20
1.0
10 1.00
8 0.80 0.8
6 0.60 0.6
4 0.40 0.4
2 0.20 0.2
0 0.00 0.0
0 2 4 6 0 5 10
[EtOH] (%v/v)
XHex g Hex P0 Hex (Pa)

Bilberry Aroma Recovery by Pervaporation, [Hex] = 0.1 kg.m3, T = 50  C and Re = 772. (b) Effect
Fig. 2 (a) Effect of ethanol concentration in the feed on of trans-hex-2-en-1-ol partial pressure in the feed on its
the permeation ux of the ethanol in () binary water/ permeation ux at 50  C, Re = 772, and [EtOH] = 1%v/v
ethanol and () ternary water/ethanol/Hex mixtures, and (Adapted from (Garcia et al. 2008))
(~) ux of trans-hex-2-en-1-ol in ternary mixtures

Bilberry Aroma Recovery 4.0


by Pervaporation,
3.5
Fig. 3 Effect of the feed
temperature on the partial 3.0
uxes of the components Hex
2.5
when Re = 772,
[Hex] = 0.1 kg.m3, and 2.0 EtOH
[EtOH] = 1%vv (Adapted
In Ji

1.5 Water
from (Garca et al. 2008))
1.0
0.5
0.0
0.5
1.0
3.05 3.10 3.15 3.20 3.25 3.30
1000/T(K1)

In the present application and working under Kanani et al. 2003), similar to the membrane
laminar ow rate conditions, 203<Re<772, thickness herein studied, 196 mm.
the aroma compound transfer ux was indepen-
dent on the feed ow rate. This indicated PV of Multicomponent Systems
that the concentration polarization phenomena PV of multicomponent systems of the bilberry
in the feed boundary layer was negligible in characteristic aroma avor was performed theo-
comparison with the aroma compound mass retically by means of simulation considering the
transfer resistance in the membrane which nor- composition in Table 1 and commercial PDMS
mally occurs with high membrane thickness, HFM modules. The membrane area considered
i.e., 127 and 160 mm (Peng and Liu 2003; was Am = 0.0056 m2 and the membrane
164 Bilberry Aroma Recovery by Pervaporation

Bilberry Aroma Recovery by Pervaporation, Table 1 Feed composition (found in Hirvi and Honkanen 1983), and
simulation results of the permeate composition, enrichment factors, and partial fluxes in the bilberry multicomponent
system after PV with a PDMS HFM module at 30  C and a membrane area Am = 0.0056 m2 (Diban et al. 2008)
Feed composition, CFi Permeate composition, CPi
Component (mg.kg1) (mg.kg1) bi Ji (g.m2h1)
Trans-Hex-2-en-1-ol 0.01 1.21 120.6 3.78  105
n-Hexanol 0.02 4.74 236.9 14.9  105
Trans-Hex-2-en-1-al 0.06 2.78 46.3 8.70  105
Linalool 0.004 0.20 49.3 0.62  105
Phenyl acetaldehyde 0.003 0.02 5.5 0.05  105
Benzyl alcohol 0.08 0.33 4.2 1.05  105
Cis-Hex-3-en-1-ol 0.06 1.64 27.4 5.15  105
Ethanol 7800 106,934 13.7 2.51
Water 992,200 893,057 0.9 20.9

7.00E-05 180
160
6.00E-05
140
JHex(g m2 h1)

5.00E-05
120
4.00E-05 100
bHex

3.00E-05 80
2.00E-05 60
40
1.00E-05
20
0.00E-00 0
0 5 10 15 20 0 5 10 15 20
104 (m) 104 (m)

Bilberry Aroma Recovery by Pervaporation, thickness, d. T = 30  C, [Hex] = 105 kg.m3,


Fig. 4 Change of the partial ux of trans-Hex-2-en-1-ol, [EtOH] = 1%v/v, Re ~6  105, Am = 0.0056 m2
JHex, and enrichment factor, bHex, with the membrane (Adapted from Diban et al. 2008)

thickness, d, was 1.96  104 m. Further details Future Directions


of the simulation conditions can be found in
(Diban et al. 2008). The results of the simulation 1. Experimental assessment of the behavior of
are collected in Table 1. There is a clear change in real solutions to evaluate (i) the interaction
the component prole from the feed solution to between different molecules during PV and
the permeate aroma compound concentrate. (ii) the aroma proles in the permeate.
Moreover, the theoretical evaluation of the 2. Integration of a sensory evaluation of the qual-
inuence of the membrane thickness, d, on the ity of the aroma compound concentrate that,
performance of the PV of trans-Hex-2-en-1-ol independently of the aroma prole, is mainly
was performed. The results are plotted in Fig. 4. affected by the presence of the impact aroma
From these results, it is extracted that a com- compounds in the permeate.
mercially available membrane with a thickness 3. Evaluation of other membrane materials that
of 1.48  104 m led to a compromise situation reduce water mass transfer and enhance the
with important impact aroma compound enrich- aroma compound enrichment factors with
ment factors bHex ~90 and adequate uxes JHex the minimum ux reduction, such
~3  105 g.m2.h1. as POMS.
Bimetallic Electrocatalyst for Fuel Cells 165

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(Vaccinium myrtillus L.) I. Identication of volatile
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pervaporation membrane. Desalination 224:3439 Organophilic pervaporation for aroma isolation-
Foster S, Blumenthal M (2012) The adulteration of industrial and commercial prospects. Membr Technol B
commercial bilberry extracts. J Am Bot Counc 2:510
96:6473
Garca V, Diban N, Gorri D, Keiski R, Urtiaga A, Ortiz
I (2008) Separation and concentration of bilberry
impact aroma compound from dilute model solution
by pervaporation. J Chem Technol Biotechnol
Bimetallic Electrocatalyst for Fuel
83:973982 Cells
Hirvi T, Honkanen E (1983) The aroma of blueberries.
J Sci Food Agric 34:992998 Dmitri Bessarabov
Kanani DM, Mikhade BP, Balakrishnan P, Singh G,
Faculty of Engineering, DST HySA Infrastructure
Pangarkar VG (2003) Recovery of valuable tea aroma
components by pervaporation. Ind Eng Chem Res Center of Competence, North-West University,
42:69246932 Potchefstroom, South Africa
Karlsson HOE, Trgrdh G (1993) Pervaporation of dilute
organic-waters mixtures. A literature review on model-
ing studies and applications to aroma compound recov-
ery. J Membr Sci 76:121146 General Requirements for Fuel Cells
Karlsson HOE, Trgrdh G, Olsson J (1998) The perfor-
mance of pervaporative units: process simulations. Sep Most of the known today fuel cell systems (e.g.,
Sci Technol 33:16291652
automotive, portable applications, backup power,
Lipnizki F, Hausmanns S, Ten PK, Field RW, Laufenberg
G (1999) Organophilic pervaporation: prospects and etc.) have common requirements that include
performance. Chem Eng J 73:113129 reduction in costs, improvement in performance
Lipnizki F, Olsson J, Trgrdh G (2002a) Scale-up of and durability, increase in tolerance toward impu-
pervaporation for the recovery of natural aroma com-
rities in the feed fuel, etc. (Vielstich et al. 2003a;
pounds in the food industry. Part I: simulation and
performance. J Food Eng 54:183195 Debe 2012).
Lipnizki F, Olsson J, Trgrdh G (2002b) Scale-up of
pervaporation for the recovery of natural aroma com-
pounds in the food industry. Part II: optimization and
Pt-based Electrocatalyst: Key
integration. J Food Eng 54:197205
Morton ID, Macleod AJ (1990) Food avours part C. The Component
avor of fruits. Elsevier, Amsterdam
Peng M, Liu SX (2003) Recovery of aroma compounds The platinum-based electrocatalyst used in PEM
from dilute model blueberry solution by pervaporation.
(proton-exchange membrane, also called polymer
Food Eng Phys Prop 68:27062710
Pereira CC, Ribeiro CP, Nobrega R, Borges CP electrolyte membrane) fuel cells, PAFC
(2006)