DEPARTMENT OF CHEMICAL ENGINEERING

FACULTY OF ENGINEERING
UNIVERSITY OF MAIDUGURI

CHE 405
SEPARATION PROCESS II
Ion Exchange
 Understanding Ion Exchange
• Ion exchange is a reversible chemical process in which ions are exchanged
between a solid phase and a liquid phase.
• This exchange typically occurs on the surface of a solid material, called an ion
exchange resin, which contains charged sites capable of attracting and holding
ions of opposite charge from a surrounding solution.
 Ion Exchange Resin
• Ion exchange resin is a solid, insoluble material typically composed of organic
polymers or inorganic materials that have been modified to contain specific
functional groups capable of exchanging ions with surrounding solutions.
• Ion exchanger resin are in the form of small micro-beads (0.25 to 1.43 mm
radius)
 Overview of Ion Exchange Processes
• In an ion-exchange process, ions of positive charge (cations) or negative charge
(anions) in a liquid solution, usually aqueous, replace displaceable ions, called
counterions, of the same charge contained in a solid ion exchanger, which also
contains immobile, insoluble, and permanently bound co-ions of the opposite
charge.
• Thus, ion exchange can be cation or anion exchange.
• For instance lets consider the process of water softening. The process involves a
cation exchanger, in which a reaction replaces calcium ions with sodium ions.
2+ +
𝐶𝑎(𝑎𝑞) + 2𝑁𝑎𝑅(𝑠) 𝐶𝑎𝑅2(𝑠) + 2𝑁𝑎(𝑎𝑞)
• The exchange of ions is reversible and does not cause any permanent change to
the solid ion-exchanger structure.

Schematic cation and anion exchange resin beads

• The ion-exchange concept can be extended to the removal of essentially all
inorganic salts from water by a two-step demineralization process or
deionization.
• Step 1, a cation resin exchanges hydrogen ions for cations such as calcium,
magnesium, and sodium.
• Step 2, an anion resin exchanges hydroxyl ions for strongly and weakly ionized
anions such as sulfate, nitrate, chloride, and bicarbonate.
Deionization, Demineralization and Water Softening
• Cations in the water (e.g., Ca²⁺, Na⁺) exchange with H⁺ ions from the resin
functional groups.
R-SO₃⁻ (Resin) + Ca²⁺ (Solution) ⇌ R-SO₃Ca²⁺ (Resin) + 2H⁺ (Solution)
• Anions in the water (e.g., Cl⁻, SO₄²⁻) exchange with OH⁻ ions from the resin
functional groups.
R-N⁺ (Resin) + Cl⁻ (Solution) ⇌ R-NCl (Resin) + OH⁻ (Solution)
Note: Water softening primarily targets the removal of calcium and magnesium ions to reduce water hardness, demineralization and
deionization processes aim to remove a wider range of ions, resulting in purified or deionized water suitable for specific industrial or laboratory
applications. The primary purpose of deionization is to produce high-purity water by removing both organic and inorganic ions, making it
suitable for various industrial, laboratory, and manufacturing applications where water purity is crucial. Demineralization may not necessarily
remove all types of ions, focusing primarily on mineral salts that contribute to water hardness and other unwanted effects.
 Application of Ion Exchange
Water Purification and Treatment
•Water Softening: Ion exchange resins remove hardness-causing ions like calcium
and magnesium, replacing them with sodium or potassium ions. This results in
softer water, improving efficiency in boilers, pipes, and various cleaning processes.
• Demineralization: By employing a combination of cation and anion exchange
resins, all dissolved salts and minerals can be removed from water, producing high-
purity deionized water. This is crucial for applications like power generation,
electronics manufacturing, and pharmaceutical production.
• Wastewater Treatment: Ion exchange can remove specific contaminants like heavy
metals, radioactive elements, and organic pollutants from wastewater streams.
This allows for cleaner water discharge or reuse in industrial processes.
Chemical Processing
• Purification of Chemicals: Ion exchange helps isolate and purify desired
chemical products from reaction mixtures by selectively removing impurities like
unwanted ions or colored compounds.
• Recovery of Solvents: Solvents used in chemical reactions can be recovered and
reused through ion exchange. This reduces waste generation and production
costs.
• Separation of Metals: Ion exchange resins can be used to separate and
concentrate valuable metals from solutions containing mixtures. This is
important for processes like hydrometallurgy, where metals are extracted from
ores.
Food and Beverage Production
• Decolorization: Ion exchange resins can remove unwanted color compounds
from food and beverage products like juices, syrups, and wine, improving their
appearance and quality.
• Sugar Refining: Ion exchange helps purify sugar solutions by removing impurities
and improving their clarity and sweetness.
Pharmaceutical Industry
• Purification of Drugs: Ion exchange plays a crucial role in isolating and purifying
pharmaceutical drugs from fermentation broths or other reaction mixtures.
• Biomolecule Separation: Ion exchange resins can be used to separate and purify
biomolecules like proteins and enzymes for research and therapeutic
applications.
Other Applications
• Nuclear Industry: Ion exchange is used to remove radioactive contaminants
from water in nuclear power plants and reprocessing facilities.
• Environmental Remediation: Ion exchange can be used to remove pollutants
from contaminated soil and groundwater.
 TYPES OF ION EXCHANGER
Natural Material-Based Ion Exchangers
• Zeolites: These are naturally occurring aluminosilicate minerals with a porous
structure. Zeolites have ion exchange properties and are used in various
applications such as water softening, gas purification, and catalysis.
• Clays: Certain types of clay minerals, such as bentonite, exhibit ion exchange
properties due to their layered structure. They are used in industries for
wastewater treatment, soil improvement, and as adsorbents.
Synthetic Ion Exchange Resins
• Cation Exchange Resins: These resins contain negatively charged functional
groups (e.g., sulfonic acid groups) that selectively exchange positively charged
ions (cations) in solution. They are widely used in water softening, metal
recovery, and chemical synthesis.
• Anion Exchange Resins: Anion exchange resins contain positively charged
functional groups (e.g., quaternary ammonium groups) that selectively exchange
negatively charged ions (anions) in solution. They are utilized in water
purification, chromatography, and wastewater treatment.
• Mixed-Bed Resins: Mixed-bed resins consist of a mixture of cation and anion
exchange resins combined in a single column. They are used for high-purity
water production in industries such as pharmaceuticals, power generation, and
electronics manufacturing.
The construction of synthetic resin involves the following components:
Polymer Backbone Group: The polymer backbone forms the structural framework
of the resin. It provides mechanical strength and stability to the resin beads or
matrix. Common polymers used as the backbone include polystyrene, acrylic,
phenolic, and polyacrylamide.
Cross-linkage Group: Crosslinking agents are molecules that link polymer chains
together, creating a three-dimensional network within the resin structure.
Crosslinking increases the stability and insolubility of the resin beads. Common
crosslinking agents include divinylbenzene, dimethacrylate, and
trimethylolpropane.
Exchange Group: The exchange group is the functional group attached to the
polymer backbone that determines the selectivity and specificity of the resin for
certain ions.
Exchange group, ions removed and the regenerate.
Exchange Groups Ions Removed Regenerant
Sulfonate, SO3- Ca2+, Mg2+, Ra2+, Ba2+, Pb2+ HCL or NaCl

Carboxylate, RCOO- Ca2+, Mg2+, Ra2+, Ba2+, Pb2+ HCL

Quaternary amine, NO3-, SO42-, CIO4-, HAsO32-, NaOH or NaCl
RN(CH3)3+ SeO32-
Tertiary amine, NO3-, SO42-, CIO4-, HAsO32-, NaOH or
RN(CH3)2H+ SeO32- Ca(OH)2
 Sulfonation to a cation exchanger Amination to an anion exchanger

Chloromethylation to an anion exchanger

Fixed and mobile ions in a cation exchanger

Example
A commercial ion-exchange resin is made from 88 wt% styrene and 12 wt%
divinylbenzene. Estimate the maximum ion-exchange capacity in eq/kg resin (same
as meq/g resin). Styrene 104.14, divinylbenzene 130.18, sulfonic acid group 81.07.
 REGENERATION OF RESIN
• Over time, the ion exchange resin becomes saturated with the ions it has
removed from the water, diminishing its effectiveness. Regeneration involves
restoring the resin's capacity to exchange ions by replacing the adsorbed ions
with a concentrated solution of ions of the opposite charge.
• Regeneration of resin is a critical process in ion exchange systems, particularly
for ion exchange resins used in water softening, demineralization, and
deionization.
• The regeneration process typically works as follows:
• Backwashing: Before regeneration, the resin bed is usually backwashed to
remove any accumulated debris, particulate matter that may have accumulated
during the service cycle.
• Regenerant Preparation: A regenerant solution is prepared by dissolving a
chemical compound in water to create a concentrated solution of ions that will
displace the ions adsorbed on the resin beads.
• Regeneration Process: The regenerant solution is introduced into the ion
exchange column or vessel containing the resin bed. The regenerant solution
flows through the resin bed in the opposite direction to the service flow,
allowing the ions in the regenerant solution to exchange places with the ions on
the resin beads.
• Rinse and Conditioning: After regeneration, the resin bed is usually rinsed with
clean water to remove excess regenerant and residual ions from the resin bed.
Depending on the application, the resin may undergo additional conditioning
steps, such as pH adjustment or oxidation, to ensure optimal performance and
longevity.
• Return to Service: Once the regeneration and rinsing steps are complete, the
resin bed is ready to return to service, where it can continue to effectively
remove ions from the water until it becomes saturated again and requires
another regeneration cycle.
• For instance, the softening resin is regenerated with sodium (Na+) ions supplied
by a salt (common salt: NaCl) solution. The regeneration reaction is:

𝑅2 𝐶𝑎 + 2𝑁𝑎𝐶𝑙 2𝑅𝑁𝑎 + 𝐶𝑎𝐶𝑙2

• In the case of demineralization, strong acids such as hydrochloric acid (HCl) or
sulphuric acid (H2SO4) are fully dissociated and can supply H+ ions to replace the
cations that have been exchanged and are sitting in the cation exchange resin
beads at the end of the exhaustion run. The regeneration reaction is:

𝑅2 𝑁𝑎 + 𝐻𝐶𝑙 𝑅𝐻 + 𝑁𝑎𝐶𝑙
 Selectivity
• Selectivity in ion exchange refers to the ability of an ion exchange material to
favorably exchange certain ions from a solution over others.
• In ion exchange processes, selectivity is determined by various factors, including
• The nature of the exchange sites on the resin
• The charge and size of the ions and
• The conditions of the exchange process (such as pH, temperature, and concentration of ions).
• Selectivity is crucial in ion exchange processes as it determines the efficiency and
effectiveness of the separation or purification of ions in a solution
• One commonly used relationship is the selectivity coefficient (α), which
quantifies the preference of an ion exchange material for one ion over another.
𝐾𝐴𝐵
𝛼=
𝐾𝐵𝐴
Where KAB​ is the equilibrium constant for the exchange of ion A for ion B, KBA​ is the equilibrium constant for the
exchange of ion B for ion A
• A selectivity coefficient greater than 1 indicates that the resin has a higher affinity
for ion A over ion B, while a selectivity coefficient less than 1 indicates the opposite.
• Additionally, selectivity in ion exchange can also be described by the distribution
coefficient (Kd), which represents the ratio of the concentration of ions adsorbed on
the resin phase to the concentration of ions remaining in the solution phase at
equilibrium:
𝐶𝑟𝑒𝑠𝑖𝑛
𝐾𝑑 =
𝐶𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
Where Cresin​ is the concentration of ions adsorbed on the resin phase, Csolution​ is the concentration of ions remaining in the solution
phase.

• The selectivity coefficient and distribution coefficient are essential parameters used
to characterize and predict the behavior of ion exchange materials in various
applications
Example
A solution containing calcium (Ca²⁺) and magnesium (Mg²⁺) ions needs to be
treated with an ion exchange resin to selectively remove calcium. The ion
exchange resin has a higher affinity for calcium compared to magnesium.
Given Data:
Initial concentration of Ca²⁺: 1.0 mol/L
Initial concentration of Mg²⁺: 0.5 mol/L
Selectivity coefficient (K): Ca²⁺ / Mg²⁺ = 5
Calculate the equilibrium concentrations of Ca²⁺ and Mg²⁺ in the solution after the
ion exchange process.