Ion Exchange and Solvent Extraction Volume 16

389 Pages·2004·5.754 MB·English

by  Arup K SenGupta, Yizhak Marcus

Ion Exchange and
Solvent Extraction
A Series of Advances
Volume 16
edited by
Arup K. SenGupta
Lehigh University
Bethlehem, Pennsylvania, U.S.A .
Yizhak Marcus
The Hebrew University of Jerusalem
Jerusalem, Israel
Jacob A. Marinsky
Founding Editor
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Preface
In July 2003, one of us (A.S.) attended the Third International Conference on Ion
Exchange(ICIE’03)attheKanazawaInstituteofTechnologyinJapan.Duringthe
courseoftheconference,about75oraland80posterpresentationsfromresearch-
ersaroundtheglobeweremadeondiverseaspectsofionexchange.Thesepresenta-
tions covered a wide range of areas, namely, drug delivery, real-time sensing,
analyticalchromatography,catalysis,polymerandinorganicsyntheses,bioseparation,
biomembranes, and, obviously, water and wastewater treatment. The breadth of
and synergy among many emerging areas with ion exchange as the common link
were indeed mind boggling. This conference and many other ongoing activities
in seemingly disjointed fields clearly demonstrate the continuing advances in the
field of ion exchange. These observations truly bolstered our earlier decision to
continue with the series of advances in ion exchange and solvent extraction. After
publication of volume 14, A.S. collected informal feedback about the size and
content of each volume. The general consensus was that about six or seven com-
prehensive chapters covering subject areas that include both fundamentals and
potentials for future applications are highly desirable. This volume contains six
chapters encompassing a wide gamut of topics; they truly reflect the diversity in
the field of ion exchange.
Itistruethatsyntheticpolymer-basedmaterialsconstitutethemajorityofthe
ion-exchangemarketandthistrendisunlikelytochangeinthenearfuture.Never-
theless, many naturally occurring, biorenewable inexpensive materials exhibit ion-
exchangepropertiesresultingfromthepresenceofavarietyofchemicalfunctional
groups.Chapter1providescomprehensivecoverageofhowactivatedcarbonsand
other carbonaceous materials can be engineered to remove metal ions and organic
micropollutants from water. Engineered activated carbons are quite effective in
iii
Copyright © 2004 by Taylor & Francis Group, LLC
reducing trace toxic metals such as lead and mercury in water as well as synthetic
organic compounds such as PCBs and MTBEs. New technologies are underway
that will help convert biomass and other carbonaceous wastes into activated car-
bon. In this regard, the possibility of controlling the carbon pore structure, which
inturnwillmakeitpossibletocontroltheselectivityandsorptioncapacityoftarget
contaminants, offers challenging application opportunities. Engineered activated
carbons and carbonaceous materials are also likely to be able to remove trace
amounts ofnewly emerging organic pollutants,such asantibioticsand otherdrugs
found in our surface waters.
In general, ion-exchange type favorable sorption processes tend to be
exothermic; i.e., the overall enthalpy change for the reaction is negative. Widely
availableion-exchangesorptiondataattesttothispremise.Ion-exchangebehaviors
ofhydrophobicionizableorganiccompounds,orHIOCs,are,however,somewhat
counterintuitivebecausethey tendtobeendothermic.Manyindustriallysignificant
synthetic organic compounds, such as pentachlorophenate, benzenesulfonates,
naphthalene sulfonates, and quaternary ammonium compounds fall into this cate-
gory of HIOCs. Chapter 2 presents the favorable sorption behaviors of several
environmentally significant aromatic anions, e.g., pentachlorophenate, chlorophe-
nate, and benzene and naphthalenesulfonates, onto polymeric anion exchangers.
Such favorable sorption equilibria are distinctively unique because they are all
endothermic processes and are accompanied by highly positive entropy changes.
ExperimentaldatavalidatethatthesorptionofHIOCsontoion-exchangersfollows
anion-exchangestoichiometry;i.e.,sorptionofanaromaticanionisalwaysaccom-
panied by the desorption of an equivalent amount of other anions from the ion-
exchangerphase.However,theion-exchangeselectivityisdeterminedbyconcurrent
hydrophobic interactions, which are further influenced by the cosolvent polarity
and hydrophobicity of the ion-exchanger matrix. The chapter provides a series of
experimentally determined values of enthalpic and entropic changes for various
HIOCs and different anion exchangers in support of the proposed
sorption=desorption mechanism. In addition, the chapter includes an efficient
regeneration methodology for desorption of HIOCs with high sorption affinities.
During an ion-exchange process, be it during the sorption step or in the
regenerationcycle,theionofinterestcaninteractwiththecounter-ionoftheinitial
ionicformoftheresinorwiththecoionofthedisplacingagent.Inbothcasesthis
interaction may result in the formation of low-solubility substances whose
concentrationexceedstheirsolubilityatagiventemperature.Moreover,thissuper-
saturated solution(SS) may remainstable within the column interstitial space for a
long period of time; this phenomenon is referred to as ion-exchange isothermal
supersaturation(IXISS).ThephenomenonofIXISScanbeexploitedtoovercome
theapparentshortcomingsofmanyion-exchangeseparationprocessesintheareas
of product purification and improved efficiency of regeneration. Chapter 3
provides a comprehensive treatment covering all aspects of IXISS, namely, the
Copyright © 2004 by Taylor & Francis Group, LLC
thermodynamics and kinetics of supersaturation in the presence of ion-exchanger
beads, and a host of application opportunities for bioseparation, desalination,
and inorganic salt syntheses.
Selective removal of heavy or toxic metals from contaminated water and
wastewater streams has been the subjectof innumerable studies around the world.
Ion-exchange resins with chelating or appropriate selective functional groups have
come a long way in attaining this goal. However, current existing ion-exchange
technologies are not capable of separating individual heavy metals leading to their
purification and reuse. Such separation processes are truly challenging and para-
metricpumpingattemptstoofferarationalapproachtowardattainingsuchagoal.
Simply put, parametric pumping is a technique in which a process parameter is
intentionally adjusted for the desirable separation. The majority of the previous
investigations dwelled on using temperature as the adjustable process parameter.
Chapter 4 elaborately discusses the potential of a pH-driven parametric pumping
with judicious combination of water-soluble ligands and commercially available
ion-exchange resins. Included in the chapter is a process flow schematic with a
laboratory-based experimental set-up, a mathematical framework based on stage-
wiseequilibrium,andtheresultsforseparationofcopperandnickelandothertoxic
metal cations.
Industrialization and use of synthetic chemicals have on many occasions
brought unpleasant environmental surprises to communities, especially in deve-
loped countries. The finding of perchlorate in hundreds of groundwater wells in
western states of the United States is a serious environmental concern that needs
to be dealt with immediately. Although hot and concentrated perchloric acid is
an extremely strong oxidizing solution, in dilute concentrations the perchlorate
ionisstableand extremelynonreactive.Theseproperties greatly facilitateitstrans-
port in groundwater. For drinking-water production from contaminated wells,
ion-exchange has been identified as the best potential treatment process. Chapter
5 provides a detailed account of the effects of all important process variables on
perchlorate removal. Specifically, the chapter includes the following: (1) effects
ofmatrix, functionalgroup, andcrosslinking ofanion-exchange resinsonperchlo-
rate removal and the efficiency of regeneration, (2) the effect of temperature on
both the equilibrium and the kinetics of perchlorate uptake, and (3) validation of
equilibrium multicomponent theory in predicting perchlorate breakthroughs and
chloride regeneration using experimental data.
Ultrapure water containing water with no dissolved solutes is an essential
ingredient for electrical utilities and microelectronic industries. The allowable
electrolyte concentration is often less than 20 parts per billion NaCl equivalent.
Theproductionofultrapurewaterisacomplexmultistepprocessinwhichthelast
unit operation invariably involves an ion exchange system containing a mixed bed
of cation- and anion-exchange resins. Both the equilibrium and the kinetics of the
mixed-bed systems are distinctively unique compared to the single cation or anion
Copyright © 2004 by Taylor & Francis Group, LLC
vi Preface
exchange units with high electrolyte concentration in the feed. Chapter 6 provides
comprehensive coverage of the kinetics of the mixed-bed ion-exchange processes.
Since the electrolyte concentrations are extremely low, liquid film diffusion and
water dissociation greatly influence the overall mass transfer coefficient. The
chapter discusses the development of theoretical models using transport
correlationsandstressestheimportanceofvalidatingindividualmodelswithactual
physical performance of the mixed-bed systems.
Arup K. SenGupta
Yizhak Marcus
Copyright © 2004 by Taylor & Francis Group, LLC
Contributors to Volume 16
Christian Bartosch Lurgi Oel Gas Chemie, Frankfurt, Germany
Dennis A. Clifford Department of Civil and Environmental Engineering,
University of Houston, Houston, Texas, U.S.A.
Gary L. Foutch School of Chemical Engineering, Oklahoma State University,
Stillwater, Oklahoma, U.S.A.
Wolfgang H. Ho¨ll Institute of Technical Chemistry, Forschungszentrum
Karlsruhe, Karlsruhe, Germany
Dennis F. Hussey iSagacity, Inc., Half Moon Bay, California, U.S.A.
Ruslan Khamizov Vernadsky Institute of Geochemistry and Analytical
Chemistry, Moscow, Russia
Randolf Kiefer Krupp-Uhde GmbH, Dortmund, Germany
PingLi DepartmentofCivilandEnvironmentalEngineering,LehighUniversity,
Bethlehem, Pennsylvania, U.S.A.
Danish J. Malik Department of Chemical Engineering, Loughborough
University, Loughborough, Leicestershire, United Kingdom
vii
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viii Contributors to Volume 16
Dmitri N. Muraviev Department of Chemistry, Autonomous University of
Barcelona, Barcelona, Spain
BasudebSaha DepartmentofChemicalEngineering,LoughboroughUniversity,
Loughborough, Leicestershire, United Kingdom
ArupK.SenGupta DepartmentofCivilandEnvironmentalEngineering,Lehigh
University, Bethlehem, Pennsylvania, U.S.A.
Cornelia Sto¨hr Sartorius AG, Go¨ttingen, Germany
Michael Streat Department of Chemical Engineering, Loughborough
University, Loughborough, Leicestershire, United Kingdom
Anthony R. Tripp Department of Civil and Environmental Engineering,
University of Houston, Houston, Texas, U.S.A.
Copyright © 2004 by Taylor & Francis Group, LLC
Contents
Prefaceiii
Contributors to Volume 16 vii
Contents of Other Volumes xiii
1. Adsorption and Ion-Exchange Properties of Engineered
Activated Carbons and Carbonaceous Materials 1
Michael Streat, Danish J. Malik, and Basudeb Saha
I. Introduction 1
II. Preparation and Properties of Activated Carbon 4
III. Characterization of the Surface Chemical Groups in
Engineered Carbons 20
IV. Activated Carbon Fibers and Woven Cloths 32
V. Sorption of Trace Metals onto Activated Carbon 35
VI. Summary of Metal Sorption 56
VII. Sorption of Herbicides on Activated Carbon and
Hypercross-Linked Polymers 57
VIII. Summary of Herbicide Sorption on Activated Carbons
and Hypercross-Linked Polymers 77
IX. Future Trends and Concluding Remarks 78
References 81
2. Entropy-Driven Selective Ion Exchange for Hydrophobic
Ionizable Organic Compounds (HIOCs) 85
Ping Li and Arup K. SenGupta
ix
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x Contents
I. Introduction 85
II. Nature of Solute–Sorbent and Solute–Solvent Interactions 87
III. Experimental Section 91
IV. Results and Discussion 95
V. Conclusions 116
References 117
3. Ion-Exchange Isothermal Supersaturation: Concept, Problems,
and Applications 119
Dmitri N. Muraviev and Ruslan Khamizov
I. Introduction 119
II. Main Features of the IXISS Technique 120
III. Areas of Potential Application of the IXISS
Effect—Wasteless Ion-Exchange Processes 122
IV. IXISS of Zwitterlyte Solutions 125
V. Aminecarboxylate Interaction of Zwitterlyte Molecules 138
VI. Application of IXISS of Amino Acids 160
VII. IXISS of Inorganic Substances 165
VIII. IXISS-Based Green Ion Exchange Technologies 179
IX. Concluding Remarks 203
References 205
4. Metal Separation by pH-Driven Parametric Pumping 211
Wolfgang H. Ho€ll, Randolf Kiefer, Cornelia Sto€hr, and Christian Bartosch
I. Introduction 211
II. Basic Principles of pH-Induced Parametric Pumping 212
III. Development of pH-Induced Parametric Pumping 216
IV. Experimental Work 222
V. Application of Strongly Acidic Cation Exchangers 225
VI. Separation with Weakly Basic Anion Exchangers 244
VII. Summary and Outlook 261
List of Symbols 263
References 263
5. Selectivity Considerations in Modeling the Treatment of
Perchlorate Using Ion-Exchange Processes 267
Anthony R. Tripp and Dennis A. Clifford
I. Introduction 267
II. Results and Discussion 274
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