Ion Exchange in Environmental Processes

Fundamentals, Applications and Sustainable Technology
Wiley (Verlag)
  • erschienen am 10. August 2017
  • |
  • 496 Seiten
E-Book | ePUB mit Adobe DRM | Systemvoraussetzungen
978-1-119-42129-0 (ISBN)
Provides a comprehensive introduction to ion exchange for beginners and in-depth coverage of the latest advances for those already in the field
As environmental and energy related regulations have grown, ion exchange has assumed a dominant role in offering solutions to many concurrent problems both in the developed and the developing world. Written by an internationally acknowledged leader in ion exchange research and innovation, Ion Exchange: in Environmental Processes is both a comprehensive introduction to the science behind ion exchange and an expert assessment of the latest ion exchange technologies. Its purpose is to provide a valuable reference and learning tool for virtually anyone working in ion exchange or interested in becoming involved in that incredibly fertile field.
Written for beginners as well as those already working the in the field, Dr. SenGupta provides stepwise coverage, advancing from ion exchange fundamentals to trace ion exchange through the emerging area of hybrid ion exchange nanotechnology (or polymeric/inorganic ion exchangers). Other topics covered include ion exchange kinetics, sorption and desorption of metals and ligands, solid-phase and gas-phase ion exchange, and more.
* Connects state-of-the-art innovations in such a way as to help researchers and process scientists get a clear picture of how ion exchange fundamentals can lead to new applications
* Covers the design of selective or smart ion exchangers for targeted applications--an area of increasing importance--including solid and gas phase ion exchange processes
* Provides in-depth discussion on intraparticle diffusion controlled kinetics for selective ion exchange
* Features a chapter devoted to exciting developments in the areas of hybrid ion exchange nanotechnology or polymeric/inorganic ion exchangers
Written for those just entering the field of ion exchange as well as those involved in developing the "next big thing" in ion exchange systems, Ion Exchange in Environmental Processes is a valuable resource for students, process engineers, and chemists working in an array of industries, including mining, microelectronics, pharmaceuticals, energy, and wastewater treatment, to name just a few.
1. Auflage
  • Englisch
  • Somerset
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  • USA
John Wiley & Sons
  • 32,87 MB
978-1-119-42129-0 (9781119421290)
1-119-42129-2 (1119421292)
weitere Ausgaben werden ermittelt
Arup K. SenGupta, PhD is the P.C. Rossin Professor in the Department of Civil and Environmental Engineering and Department of Chemical Engineering at Lehigh University. Over the last 35 years he has studied, learned, taught and conducted extensive research into nearly every facet of ion exchange. Dr. SenGupta is recognized as the inventor of hybrid ion exchange nanotechnology (HIX-Nano) that offers enhanced separation through the Donnan Membrane Principle. HIX-Nano materials are currently in use in six different countries including the USA to remove arsenic, fluoride and phosphate from contaminated water and waste water. In 2004, Dr. SenGupta received the International Ion Exchange Award at Cambridge University in England. He was the North American Editor of the Reactive and Functionalized Polymers Journal from 1996-2006.
  • Cover
  • Title Page
  • Copyright
  • Contents
  • Preface
  • Acknowledgment
  • Chapter 1 Ion Exchange and Ion Exchangers: An Introduction
  • 1.1 Historical Perspective
  • 1.2 Water and Ion Exchange: An Eternal Kinship
  • 1.3 Constituents of an Ion Exchanger
  • 1.4 What is Ion Exchange and What is it Not?
  • 1.5 Genesis of Ion Exchange Capacity
  • 1.5.1 Inorganic
  • 1.5.2 Organic/Polymeric Ion Exchanger
  • Agreement and Anomaly
  • 1.5.3 Strong-Base Type I and Type II Anion Exchanger
  • 1.6 Biosorbent, Liquid Ion Exchanger, and Solvent Impregnated Resin
  • 1.6.1 Biosorbent
  • 1.6.2 Liquid Ion Exchange
  • 1.6.3 Solvent-Impregnated Resins
  • 1.7 Amphoteric Inorganic Ion Exchangers
  • 1.8 Ion Exchanger versus Activated Carbon: Commonalities and Contrasts
  • 1.9 Ion Exchanger Morphologies
  • 1.10 Widely Used Ion Exchange Processes
  • 1.10.1 Softening
  • 1.10.2 Deionization or Demineralization
  • Summary
  • References
  • Chapter 2 Ion Exchange Fundamentals
  • 2.1 Physical Realities
  • 2.2 Swelling/Shrinking: Ion Exchange Osmosis
  • 2.3 Ion Exchange Equilibrium
  • 2.3.1 Genesis of Non-Ideality
  • 2.4 Other Equilibrium Constants and Equilibrium Parameters
  • 2.4.1 Corrected Selectivity Coefficient
  • 2.4.2 Selectivity Coefficient, KIXse
  • 2.4.3 Separation Factor (aAB)
  • 2.4.4 Separation Factor: Homovalent Ion Exchange
  • 2.4.5 Separation Factor: Heterovalent Exchange
  • 2.4.6 Physical Reality of Selectivity Reversal: Role of Le Châtelier's Principle
  • 2.4.7 Equilibrium Constant: Inconsistencies and Potential Pitfalls
  • 2.5 Electrostatic Interaction: Genesis of Counterion Selectivity
  • 2.5.1 Monovalent-Monovalent Coulombic Interaction
  • 2.6 Ion Exchange Capacity: Isotherms
  • 2.6.1 Batch Technique
  • 2.6.2 Regenerable Mini-Column Method
  • 2.6.3 Step-Feed Frontal Column Run
  • 2.7 The Donnan Membrane Effect in Ion Exchanger
  • 2.7.1 Coion Invasion or Electrolyte Penetration
  • 2.7.2 Role of Cross-linking
  • 2.7.3 Genesis of the Donnan Potential
  • 2.8 Weak-Acid and Weak-Base Ion Exchange Resins
  • 2.8.1 pKa Values of Weak Ion Exchange Resins
  • 2.8.2 Weak-Acid and Weak-Base Functional Groups
  • Weak-Acid Ion Exchange Resin
  • Weak-Base Ion Exchange Resin
  • 2.9 Regeneration
  • 2.9.1 Selectivity Reversal in Heterovalent Ion Exchange
  • 2.9.2 pH Swings
  • 2.9.3 Ligand Exchange with Metal Oxides
  • 2.9.4 Use of Co-Solvent
  • 2.9.5 Dual-Temperature Regeneration
  • 2.9.6 Carbon Dioxide Regeneration
  • 2.9.7 Regeneration with Water
  • 2.10 Resin Degradation and Trace Toxin Formation
  • 2.10.1 Formation of Trace Nitrosodimethylamine (NDMA) from Resin Degradation
  • 2.11 Ion Exclusion and Ion Retardation
  • 2.11.1 Ion Exclusion
  • 2.11.2 Ion Retardation
  • 2.12 Zwitterion and Amino Acid Sorption
  • 2.12.1 Interaction with a Cation Exchanger: Role of pH
  • 2.13 Solution Osmotic Pressure and Ion Exchange
  • 2.14 Ion Exchanger as a Catalyst
  • Summary
  • References
  • Chapter 3 Trace Ion Exchange
  • 3.1 Genesis of Selectivity
  • 3.2 Trace Isotherms
  • 3.3 Multi-Component Equilibrium
  • 3.4 Agreement with Henry's Law
  • 3.5 Multiple Trace Species: Genesis of Elution Chromatography
  • 3.5.1 Determining Separation Factor from Elution Chromatogram
  • 3.6 Uphill Transport of Trace Ions: Donnan Membrane Effect
  • 3.7 Trace Leakage
  • 3.8 Trace Fouling by Natural Organic Matter
  • 3.9 Ion Exchange Accompanied by Chemical Reaction
  • 3.9.1 Precipitation
  • 3.9.2 Complexation
  • 3.9.3 Redox Reaction
  • 3.10 Monovalent-Divalent Selectivity
  • 3.10.1 Effect of Charge Separation: Mechanistic Explanation
  • 3.10.2 Nitrate/Sulfate and Chloride/Sulfate Selectivity in Anion Exchange
  • 3.10.3 Genesis of Nitrate-Selective Resin
  • 3.10.4 Chromate Ion Selectivity
  • 3.11 Entropy-Driven Selective Ion Exchange: The Case of Hydrophobic Ionizable Organic Compound (HIOC)
  • 3.11.1 Focus of the Study and Related Implications
  • 3.11.2 Nature of Solute-Sorbent and Solute-Solvent Interactions
  • Interaction during Desolvation of PCP-
  • Interaction during PCP- Sorption onto the Polymeric Exchanger
  • 3.11.3 Experimental Observations: Stoichiometry, Affinity Sequence, and Cosolvent Effect
  • 3.11.4 Energetics of the Sorption Process
  • 3.11.5 Unifying Hydrophobic Interaction: From Gas-Liquid to Liquid-Solid System
  • 3.11.6 Effect of Polymer Matrix and Solute Hydrophobicity
  • 3.12 Linear Free Energy Relationship and Relative Selectivity
  • 3.13 Simultaneous Removal of Target Metal Cations and Anions
  • 3.14 Deviation from Henry's Law
  • 3.14.1 Ions Forming Polynuclear Species
  • 3.15 Tunable Sorption Behaviors of Amphoteric Metal Oxides
  • 3.16 Ion Sieving
  • 3.16 Example S3.1
  • 3.16 Example S3.2
  • 3.17 Trace Ion Removal
  • 3.17.1 Uranium(VI)
  • 3.17.2 Radium
  • 3.17.3 Boron
  • 3.17.4 Perchlorate (ClO4-)
  • 3.17.5 Emerging Contaminants of Concern and Multi-Contaminant Systems
  • 3.17.6 Arsenic and Phosphorus: As(V), P(V), and As(III)
  • 3.17.7 Fluoride (F-)
  • Summary
  • References
  • Chapter 4 Ion Exchange Kinetics: Intraparticle Diffusion
  • 4.1 Role of Selectivity
  • 4.2 State of Water Molecules inside Ion Exchange Materials
  • 4.3 Activation Energy Level in Ion Exchangers: Chemical Kinetics
  • 4.3.1 Activation Energy Determination from Experimental Results
  • 4.4 Physical Anatomy of an Ion Exchanger: Gel, Macroporous and Fibrous Morphology
  • 4.4.1 Gel-Type Ion Exchanger Beads
  • 4.4.2 Macroporous Ion Exchanger Beads
  • 4.4.3 Ion Exchange Fibers
  • 4.5 Column Interruption Test: Determinant of Diffusion Mechanism
  • 4.6 Observations Related to Ion Exchange Kinetics
  • 4.6.1 Effect of Concentration on Half-time (t1/2)
  • 4.6.2 Major Differences in Ion Exchange Rate
  • 4.6.3 Chemically Similar Counterions with Significant Differences in Intraparticle Diffusivity
  • 4.6.4 Effect of Competing Ion Concentrations: Gel versus Macroporous
  • 4.6.5 Intraparticle Diffusion during Regeneration
  • 4.6.6 Shell Progressive Kinetics versus Slow Diffusing Species
  • 4.7 Interdiffusion Coefficients for Intraparticle Diffusion
  • 4.8 Trace Ion Exchange Kinetics
  • 4.8.1 Chlorophenols as the Target Trace Ions
  • 4.8.2 Intraparticle Diffusion inside a Macroporous Ion Exchanger
  • 4.8.3 Effect of Sorption Affinity on Intraparticle Diffusion
  • 4.8.4 Solute Concentration Effect
  • 4.9 Rectangular Isotherms and Shell Progressive Kinetics
  • 4.9.1 Anomalies in Arrival Sequence of Solutes
  • 4.9.2 Quantitative Interpretation
  • 4.10 Responses to Observations in Section 4.6
  • 4.10.1 Effect of Concentration on Half-time (t1/2)
  • 4.10.2 Slow Kinetics of Weak-Acid Resin
  • 4.10.3 Chemically Similar Counterions: Drastic Difference in Intraparticle Diffusivity
  • 4.10.4 Gel versus Macroporous
  • 4.10.5 Intraparticle Diffusion during Regeneration
  • 4.10.6 Shrinking Core or Shell Progressive Kinetics
  • 4.11 Rate-Limiting Step: Dimensionless Numbers
  • 4.11.1 Implications of Biot Number: Trace Ion Exchange
  • 4.12 Intraparticle Diffusion: From Theory to Practice
  • 4.12.1 Reducing Diffusion Path Length: Short-Bed Process and Shell-Core Resins
  • 4.12.2 Development of Bifunctional Diphonix® Resin
  • 4.12.3 Ion Exchanger as a Host for Enhanced Kinetics
  • Summary
  • References
  • Chapter 5 Solid- and Gas-Phase Ion Exchange
  • 5.1 Solid-Phase Ion Exchange
  • 5.1.1 Poorly Soluble Solids
  • 5.1.2 Desalting by Ion Exchange Induced Precipitation
  • 5.1.3 Separation of Competing Solid Phases
  • 5.1.4 Recovery from Ion Exchange Sites of Soil
  • 5.1.5 Composite or Cloth-like Ion Exchanger (CIX)
  • 5.1.6 Heavy Metals (Me2+) with Solids Possessing High Buffer Capacity
  • 5.1.7 Ligand-Induced Metal Recovery with a Chelating Exchanger
  • 5.2 Coagulant Recovery from Water Treatment Sludge
  • 5.2.1 Development of Donnan IX Membrane Process
  • 5.2.2 Alum Recovery: Governing Donnan Equilibrium
  • 5.2.3 Process Validation
  • 5.3 Gas Phase Ion Exchange
  • 5.3.1 Sorption of Acidic and Basic Gases
  • 5.3.2 CO2 and SO2 Capture with Weak-Base Anion (WBA) Exchanger
  • 5.3.3 Effect of Ion Exchanger Morphology
  • Gel versus Macroporous
  • Ion Exchange Fibers
  • 5.3.4 Redox Active Gases: Hydrogen Sulfide and Oxygen
  • 5.4 CO2 Gas as a Regenerant for IX Softening Processes: A Case Study
  • Summary
  • References
  • Chapter 6 Hybrid Ion Exchange Nanotechnology (HIX-Nanotech)
  • 6.1 Magnetically Active Polymer Particles (MAPPs)
  • 6.1.1 Characterization of MAPPs
  • 6.1.2 Factors Affecting Acquired Magnetic Activity
  • 6.1.3 Retention of Magnetic Activity and Sorption Behavior
  • 6.2 Hybrid Nanosorbents for Selective Sorption of Ligands (e.g., HIX-NanoFe)
  • 6.2.1 Synthesis of Hybrid Ion Exchange Nanomaterials
  • 6.2.2 Characterization of Hybrid Nanosorbents
  • 6.2.3 Parent Anion Exchanger versus Hybrid Anion Exchanger (HAIX-NanoFe(III)): A Comparison
  • 6.2.4 Support of Hybrid Ion Exchangers: Cation versus Anion
  • Donnan Membrane Equilibrium and Coion Exclusion Effect
  • 6.2.5 Efficiency of Regeneration and Field Application
  • 6.2.6 Hybrid Ion Exchange Fibers: Simultaneous Perchlorate and Arsenic Removal
  • 6.3 HAIX-NanoZr(IV): Simultaneous Defluoridation and Desalination
  • 6.3.1 Field-Scale Validation
  • 6.4 Promise of HIX-Nanotechnology
  • Summary
  • References
  • Chapter 7 Heavy Metal Chelation and Polymeric Ligand Exchange
  • 7.1 Heavy Metals and Chelating Ion Exchangers
  • 7.1.1 Heavy Metals: What are They?
  • 7.1.2 Properties of Heavy Metals and Separation Strategies
  • 7.1.3 Emergence of Chelating Exchangers
  • 7.1.4 Lewis Acid-Base Interactions in Chelating Ion Exchangers
  • 7.1.5 Regeneration, Kinetics and Metals Affinity
  • 7.2 Polymeric Ligand Exchange
  • 7.2.1 Conceptualization and Characterization of the Polymeric Ligand Exchanger (PLE)
  • 7.2.2 Sorption of Polymeric Ligand Exchangers
  • 7.2.3 Validation of Ligand Exchange Mechanism
  • Summary
  • References
  • Chapter 8 Synergy and Sustainability
  • 8.1 Waste Acid Neutralization: An Introduction
  • 8.1.1 Underlying Scientific Concept
  • Weak-Acid Cation Exchangers
  • Weak-Base Anion Exchangers
  • 8.1.2 Mechanical Work through a Cyclic Engine
  • 8.2 Improving Stability of Anaerobic Biological Reactors
  • 8.2.1 Potential Use of Selective Ion Exchanger
  • 8.2.2 Ion Exchange Fibers: Characterization and Performance
  • 8.3 Sustainable Aluminum-Cycle Softening for Hardness Removal
  • 8.3.1 Current Status and Challenges
  • 8.3.2 Sodium-Free Approaches and Alternatives to Na-Cycle Softening
  • 8.3.3 Underlying Scientific Approach of Al-cycle Cation Exchange
  • 8.3.4 Comparison in Performance: Na-Cycle versus Al-Cycle
  • Softening with SAC-Na Resins
  • Softening with SAC-Al Resins
  • SAC-Al Regeneration and SEM-EDX Mapping
  • 8.3.5 Regeneration Efficiency and Calcium Removal Capacity
  • 8.3.6 Sustainability Issues and New Opportunities
  • 8.4 Closure
  • Summary
  • References
  • Appendix A Commercial Ion Exchangers
  • Appendix B Different Units of Capacity, Concentration, Mass, and Volume
  • B.1 Capacity
  • B.2 Concentration (Expressed as CaCO3)
  • B.3 Mass
  • B.4 Volume
  • Appendix C Table of Solubility Product Constants at 25°C
  • Appendix D Acid and Base Dissociation Constants at 25°C
  • Index
  • EULA

Chapter 1
Ion Exchange and Ion Exchangers: An Introduction

1.1 Historical Perspective

Evolution is traditionally viewed to occur in a slow but continuous manner for living organisms and creatures gradually acquiring new traits. To the contrary, many areas of "science" undergo periods of rapid bursts of fast development separated by virtual standstill with no significant activity. The first historically recorded use of ion exchange phenomenon is from the Old Testament of the Holy Bible in Exodus 15:22-25 describing how Moses rendered the bitter water potable by apparently using the process of ion exchange and/or sorption. Another often quoted ancient reference is to Aristotle's observation that the salt content of water is diminished or altered upon percolation through certain sand granules. From a scientific viewpoint, however, the credit for recognition of the phenomenon of ion exchange is attributed to the English agriculture and soil chemists, J.T. Way and H.S. Thompson. In 1850, these two soil scientists formulated a remarkably accurate description of ion exchange processes in regard to removal of ammonium ions from manure by cation exchanging soil [1, 2]. They essentially simulated the following naturally occurring cation exchange reactions as follows:

1.1 1.2

Some of the fundamental tenets of ion exchange resulted from this work: first, the exchange of ions differed from true physical adsorption; second, the exchange of ions involved the exchange in equivalent amounts; third, the process is reversible and fourth, some ions were exchanged more favorably than others.

As often with many groundbreaking inventions, the findings of Way and Thompson cast doubts, disbeliefs and discouragement from their peers. In the following years, these two soil scientists discontinued persistent research in this field. As a result, the evolution of ion exchange process progressed rather slowly due to the difficulties in modifying or manipulating naturally occurring inorganic clayey materials with low cation exchange capacities.

Inorganic zeolites (synthetic or naturally occurring aluminosilicates) later found wide applications in softening hard waters, that is, removal of dissolved calcium and magnesium through cation exchange. However, the anion-exchange processes remained unexplored and practically unobserved. Even at that time, it was not difficult to conceptualize that the availability of both cation exchangers and anion exchangers in the ionic forms of hydrogen and hydroxyl ions, respectively, would create a new non-thermal way to produce water free of dissolved solids as indicated below:


The biggest obstacle to realize this concept was to identify and/or synthesize ion exchangers which will be chemically stable and durable under the chemically harsh environments at very high and low pH. The immense potential of ion exchange technology scaled a new height when the first organic-based (polymeric) cation exchanger was synthesized by Adams and Holmes [3]. In less than ten years, D'Alelio prepared the first polymeric, strong/weak cation and anion exchangers [4-6]. Since then, synthesis of new ion exchangers never seemed to slow down and application of ion exchange technology in industries as diverse as power utilities, biotechnology, agriculture, pharmaceuticals, pure chemicals, microelectronics, etc. are continually growing. No specialty grows in isolation; ion exchange fundamentals, ion exchange resins and ion exchange membranes continue to find new and innovative applications globally. Figure 1.1 includes the number of ion exchange related US patents issued during the last three decades, illustrating continued inventions in new products and processes.

Figure 1.1 Number of patents per year for "anion exchange" and "cation exchange" per a Google Patents search.

Source: Data taken with permission from Google [7, 8].

Ironically, the Second World War and, more specifically, the race for nuclear technology helped catalyze the growth and maturity of the field of ion exchange at an accelerated pace. Ion exchange was found to be a viable process for separating some of the transuranium elements and, for understandable reasons, its application aroused a great deal of interest. In fact, some of the most fundamental works on ion exchange equilibria and kinetics were carried out during the Second World War period by Boyd et al. and reported afterwards in the open literature [9-11]. All along, the scientific understanding of ion exchange fundamentals consistently lagged well behind its applications. Table 1.1 attempts to summarize milestones in regard to the development and application of ion exchange technology over time.

Table 1.1 Historical milestones in ion exchange

Year Description Patent # Authors 1850 Discovery of ion exchange properties of soil N/A Thompson and Way [1, 2] 1876 Zeolites or aluminosilicates recognized for base exchange and equivalence of exchange is proved N/A Lemberg [12, 13] 1906-1915 Industrial manufacture of sodium permutit for hardness removal 914,405;
1,131,503 Gans [14] 1934 Invention of sulfonated condensation polymers as cation exchangers 2198378A Ellis 1935 First synthetic organic ion exchangers 2104501A,
2151883A Adams and Holmes [15] 1938 Mixed-bed ion exchange process or duplex ion exchanger 2275210A Stemen, Urbain, and Lewis 1939 Invention of sulfonated polystyrene polymerization as cation exchangers
Invention of aminated polystyrene polymerization as anion exchangers 2283236A
2304637A Soday
Vernal 1942 Cation exchange resin beads made from polymerized acrylic acids
Cation exchange resins with sulfonated, polymerized poly-vinyl aryl parent resin
Anion exchange resins with aminated, polymerized poly-vinyl aryl parent resin 2340110A, 2340111A
2366008A D'Alelio 1947 Element 61 (Promethium) was discovered by ion exchange of the by-products of fission N/A Marinsky, Glendenin, and Coryell [16] 1953 Use of zeolites as molecular sieves
Magnetic ion exchange resin for NOM removal (MIEX process)
Invention of weak acid cation exchangers
First countercurrent ion exchange using suspended/agitated beds of resin 2882243A
N/A Milton
Swinton and Weiss [17] 1954 Higgins countercurrent ion exchange contactor invented 2815322A Higgins [18] 1955 Ligand exchange 2839241A Albisetti 1956 Pellicular ion exchange resin 2933460A Richter and McBurney 1958 Agitated bed contactor for semicontinuous ion exchange
Ion exchange in drug delivery N/A
2990332A Arden, Davis, and Herwig [19]
Keating 1958 (publicly released) Uranium separation, intraparticle diffusion (Manhattan Project) 2956858A Powell 1959-1960 The book on "Ion Exchange" by Friedrich Helfferich was printed and laid the theoretical foundations for the field of ion exchange N/A Helfferich [20] 1962-1971 Cloete-Streat countercurrent contactor invented 3551118A (1962)
3738814A (1969)
3957635A (1971) Cloete and Streat [21] 1964 Cellulosic ion exchange fibers synthesized 3379719A Rulison 1965 Sirotherm process - thermally regenerable ion exchange resins 274-029; 59,441/65
(Australia) Bolto, Weiss, and Willis Partially functionalized cation exchange (shallow-shell technology) 3252921A Hansen and McMahon 1966 Macroporous ion exchange resin 3418262A Grammont and Werotte 1968 Boron selective resin 20110108488A1 Chemtob 1969 Development of poly(methyl methacrylate) anion exchange resins or macroreticular polymers that reduced fouling by natural organic manner N/A Kressman and Kunin [22, 23] 1971 Continuous moving bed ion exchange 3751362A Probstein, Schwartz, and Sonin 1972 Phenolic ion exchange fibers 3835072A Economy and Wohrer 1973 Iminodiacetic acid chelating resin


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