Fundamentals and Applications of Ion Exchange

492 Pages·1985·14.759 MB·English

by  C. Calmon (auth.), Lorenzo Liberti, John R. Millar (eds.)

Fundamentals and Applications
of Ion Exchange
NATO ASI Series
Advanced Science Institutes Series
A Series presenting the results of activities sponsored by the NATO Science
Committee, which aims at the dissemination of advanced scientific and technological
knowledge, with a view to strengthening links between scientific communities.
The Series is published by an international board of publishers in conjunction with the
NATO Scientific Affairs Division
A Lite Sciences Plenum Publishing Corporation
B PhySics London and New York
C Mathematical and D. Reidel Publishing Company
Physical Sciences Dordrecht and Boston
D Behavioural and Martinus Nijhoff Publishers
Social Sciences DordrechtlBoston/Lancaster
E Applied Sciences
F Computer and Springer-Verlag
Systems Sciences Berlin/Heidelberg/New York
G Ecological Sciences
Series E: Applied Sciences - No. 98
Fundamentals and Applications
of Ion Exchange
Edited by
Lorenzo Liberti
Senior Researcher
Water Research Institute
National Research Council of Italy
Associate Professor of Industrial Chemistry
Faculty of Engineering
University of Bari
Bari, Italy
John R. Millar
Formerly Senior Research Scientist
Duolite International Inc
Redwood City, CA 94062, USA
1985 Martinus Nijhoff Publishers
Dordrecht I Boston I Lancaster
Published in cooperation with NATO Scientific Affairs Division
Post-Conference Proceedings of the NATO Advanced Study Institute on Mass
Transfer and Kinetics of Ion Exchange, Maratea, Italy, May 31-June 11, 1982
Library of Congress Cataloging In Publication Data
Main entry under title:
Fundamentals and applications of ion exchange.
(NATO ASI series. Series E, Applied sciences; no~ 98)
"Post-conference proceedings of the NATO Advanced
Study Institute on Mass Transfer and Kinetics of Ion
Exchange, Maritea, Italy, May 31-June 11, 1982"-- P.
"Published in cooperation with NATO Scientific Affairs
Division.1!
1. Ion exchange--Congresses. I. Liberti, Lorenzo.
II. Millar, John R. Ill. NATO Advanced Study Institute
on Mass Transfer and Kinetics of Ion Exchange (1982 :
Maratea, Italy) IV. North At lant ie Treaty Organlzat ion.
Scientific Affaris Divison. V. Series.
QD561.F825 1985 660.2'9723 85-18842
ISBN-13: 978-94-010-8784-1 e-ISBN-13: 978-94-009-5161-7
001: 10.007/978-94-009-5161-7
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Martinus Nijhoff Publishers, P.O. Box 163, 3300 AD Dordrecht, The Netherlands
Copyright © 1985 by Martinus Nijhoff Publishers, Dordrecht
Softcover reprint of the hardcover 1s t edition 1985
v
PREFACE
"Ion exchange", as Dr. Robert Kunin has said, "is a unique
technology since ft occupies a special place in at least three
other scientific disciplines - polymer chemistry, polyelectrolytes
and adsorption. " It may also lay claim to being one of the most
widely used industrially. From its origins in water treatment and
the sugar industry, through hydrometallurgical applications as
diverse as the treatment of plating wastes and the tonnage
production of uranium, to the present-day production of ultrapure
water for the microelectronics industry, the recovery of valuable
materials from sewage effluents and pollution control, the uses of
ion exchange are legion.
As a result, it is well-nigh impossible to prevent infiltration by
the real world of even the most academic of conferences on the
subject. It came as no surprise to the Scientific Board of the
NATO Advanced Study Institute on "Mass Transfer & Kinetics of Ion
Exchange" that one third of the lecturers, and one half of their
advanced students, were from Industry, nor that the two round-table
discussions, which specially featured industrial applications and
future requirements, were well attended and enthusiastically debated.
This volume presents a collection of· the contributions from the
audience which followed the (already published) principal lectures
at each of the five sessions ,and which, so far, have only been
published in abstract. These ranged from theoretical exegesis to
down-to-earth practicality and covered a wide range of topics
inspired by the original idea of the Institute without necessarily
being restricted in content by the academic restraint of its formal
title.
..
In the two and a half years since these papers were originally
delivered the ion exchange world has seen a number of changes, to be
sure, but these have been mainly of economic origin. The state of
the art,: as might be expected of a mature technology, has advanced
but little; the theory, which in ion exchange has usually lagged
behind practical application, remains much as it was discussed, in
congenial company and amid beautiful surroundings, at Acquafredda
di Maratea.
Lorenzo Liberti John R. Millar
VII
TABLE OF CONTENTS
Ion Exchange Towards the Twenty First Century
C. Ca Iroon
The Use of Some Coordinatin~ Copolymers in Hydrometallurgy
Michael J. Hudson 7
The CCS-Ion Exchange Contactor
Kurt Meul i 11
Outlook and Desires of Ion Exchanqe Resin Technolo!ly
Development in the Nuclear Field
F.L. Rizzo 25
Purification of Effluents of Acid Copper and Nickel Plating
Galvanic Processes with Conventional Cation Exchange Resins.
Copper and Nickel Recovery
Robe rto S to rt i n i 34
Anion Resin Kinetics at High Flow Rates
J.R. Emmett 41
Ion Exchange Desulphation of Feedwater to MSF Evaporator.
Full Scale Experience
L. Liberti, R. Pascali, F. Sigon and R. Zannoni 56
Calculation of Economic Indexes for Desalination Plants with
and Without Desulphation Pretreatment System
A. Conti and R. Pascali 75
Kinetic Studies on Gel and Macroporous Anion Exchangers
Using the Uranyl Sulfate/Sulfate Exchange
F.X. McGarvey and E.W. Hauser . 81
Salt Conservation, Selectivity Reversal and Breakthrough
Detection in Ion Exchanoe for Nitrate Removal
Dennis Clifford, Liou-LIang Horng and Chieh-Chien Lin 102
VIII
Equilibrium and Diffusion Rate Effects of Univalent and
Divalent Ions in a Bifunctional Resin
Asaye Mamo, Thomas Heeb and Kent S. Knaebel 116
Analysis of Ion Exchange Phenomena Occurring in Silicate
Glasses Immersed in a Molten Salt Bath
G; Battaglin, M. Berti, G. Della Mea, P. Mazzoldl and
M. Gugl ielmi 128
The Rim-Nut Process for Recovery of NIP Fertilizer From
Sewage. Start-Up of Bari 's Plant
L. Liberti, G. Boari, N. Limoni, C. Longobardi and
R. Passino 134
Ion Exchange for the Recycling of Wastewater Constituents
Brian Bolto and Lucjan Pawlowski 144
Cation Exchange Softening Coupled with Electrodialysis
for High Recovery Desalination
John W. Kaakinen 177
Methods of Reducing Consumption of Sulphuric Acid in
Regeneration of Strong Cation Exchangers in Water Desalination
B.A. Hendry 228
Design Methods for Ion Exchange Equipment
J. Loureiro, C. Costa, M. Di'as, J. Lopes and A. Rodri9ues 245
Future Criteria for the Design and'Manufacturing of Water
Treatment Plants
Pei r Giorgio Bellotti 261
Water Softening for Food Processing
AI bano Ma I agut i 273
Ion Exchange in the Food Industry
Lucio Galeazzi 278
Ion Exchange for the Recovery of Concentrated Ammonium
Sulphate from the Process Condensate of an Ammonia-Urea
Factory
G. Campolo, F. Ciallie and G. Vergerio 294
The Mechanism of Ion Exchange on Microcrystals of Inorganic
Oxide-Hydroxides
Russell Paterson and Habibur Rahman 306
A Useful Method to Summarize Data in Ion Exchange
Influence of Temperature and Ionic Size
E. Hogfeldt, A.V. Mikulich and V.S. Soldatov 312
IX
Reversibility and Performances in Productive lon-Exchange
Chromatography
M. Bai lly and D. Tondeur 319
MOssbauer and Electron Microprobe Studies of Precipitation
Phenomena in Nafion Ion Exchange Membranes
A. Meagher, B. Rodmacq, J.M.D. Coey and M. Pineri 332
Ion Exchange Kinetics in Zeolite A
D. Drummond, A. De Jonge and L.V.C. Rees 345
Kineti'cs of Bulk and Interfacial Ionic Motion:
The Microscopic Basis and Limits fDr the Nernst-Planck-Poisson
System
Richard P. Buck 370
Nernst-Planck or No?
J.C.R. Turner 452
Application of the Stefan-Maxwell Equations to Multicomponent
Ion Exchange
E. Earl Graham 458
Concentration Polarization and Membrane Resistance Evaluation
by Current Transient and Nernst-Planck Equations
G. Ti ravanti, G. Boari and R. Passino 468
ION EXCHANGE TOWARDS THE TWENTY FIRST CENTURY
C. Calmon
511 Ewing Street
Princeton, NJ 08540 USA
TOWARDS DEFINITION OF THE ION EXCHANGE FIELD
Before consideration is given to the future development in ion
exchange, the term "Ion Exchange" must be understood to encompass
many aspects of separation. The classical text on "Ion Exchange"
by Helfferich defines "ion exchangers"'but not the term "ion
exchange". Also, many chapters on the ion exchangers have nothing
to do with ion exchange, as ~an be seen from the following:
1. Ligand exchange - deals with molecular exchange.
2. Electrodialysis - deals with the membranes which act as
selective barriers and <;onductive media.
3. Catalysis - deals with the transformation of organic
molecules.
4. Sorption - involves the sorption of organic molecules
e.g. through ion exclusion.
5. Liquid ion exchangers - are not solid insoluble products,
but these can be incorporated into polymeric matrices to
form extracting resins.
From the above it is evident that the text deals with the
utilization of ion exchangers for many functions often not
involving ion exchange. So the topic for discussion should be
polymeric matrices with functional groups.
2
Basically ion exchange is a separation process which utilizes
functional or active sites on so-called inert matrices. Both from
the fouling of ion exchangers by high-molecular weight organics and
the difficulties involved due to the interaction of certain
organics with the polymeric matrix. it appears that there is no
such thing as an absolute inert matrix. So even the definition for
an ion exchanger as an inert and insoluble solid is rather limited.
trace solubility of ion exchange resins is a problem in the
manufacturing of microcircuits.
The removal of colloids and the filtering out of organisms by
certain ion exchangers with high porosities and the recent
development of microporous membranes with polar groups for removal
of very fine particulates in solution expand the use of entities
with ion exchanger groups. In view of the above can enzymes.
biochemicals. and microbiocells immobilized on polymers be excluded
from ion exchange texts? In addition there are electro and photo
conductive resins in which polar groups attached to polymeric
matrices. So the field has to be expanded beyond ions and beyond
exchange.
The reason for the limited views of ion exchange until
recently was the fact that the early work in ion exchange was done
for water treatment. The application involved the exchange of
damaging or toxic ions for inocuous ions or the partial or total
removal of ionic species. The contributions of the early water
treatment companies and the ion manufacturers were:
1. They showed how to prepare inert polymeric matrices.
2. How to attach polar or active sites to the matrices.
3. The application of these to water and wastewater
treatment and to resource recovery.
However. the leaders in the field today are academicians and in
small companies developing products for the chromatographic and
biochemical fields. Examination of Mathur's (et al) book.
"Polymers as Aids in Organic Chemistry" (Academic Press) and
Hodge's a'nd Sherrington's book. "Polymer-Supported Reactions in
Organic Synthesis" (John Wiely and Sons). will show the tremendous
progress or advancements being made by the synthetic organic and
biochemist in this field.
Naturally. there will arise many specialized divisions in this
field. The question will be how cross fertilization within the
field can take place. In the future the biochemical and
pharmaceutical fields may outstrip the water treatment industry.
resulting in large companies to set up divisions to research the