Optimization of Regeneration Process of Exhausted Cation

Exchange Resin Bed using Sodium Chloride Solution with Chlorine

Dioxide as Additive.
Bernal Kim Geo, Dela Cruz Mark Jed, Dolot Max Julius, Perez, Roi Vincent

INTRODUCTION
1.1 Background of the Study
Over the past centuries, Ion exchange (IX) has become an established unit operation and
serves as a supplement to other unit industrial processes such as filtration, distillation and
adsorption. Industrial plants as well as laboratories accomplish numerous tasks using ion
exchange; from being a basic topic in learning analytical chemistry to large scale
decontamination of cooling water for nuclear reactors. However, the most important application
for Ion exchange is still water purification and demineralization, a task which population growth
and various developments in industry had made more pressing than ever (Hellferich, 1995). In
water distribution systems, Ion exchange is used to soften water for either industrial or
commercial use (Entezari et al., 2008). For water treatment ion exchanger, resin beds based on
a cross-linked polystyrene or acrylic structure is used to soften hard water (Skipton, 2008).
Water softening happens theres an exchange of the calcium (Ca +) and magnesium (Mg+) ions
in hard water with the sodium (Na+) ions in the resin of the IX. This exchange converts the
passing hard water feed into a soft saline solution, leaving the Ca + and Mg+ ions in the resin bed
of the IX. Over time, the resin beds become saturated with the contaminant ions, reducing the
ion exchangers capability to soften water (Maul, Kim, Amini, Zhang, & Boyer, 2014). To
continue the exchangers operation, the exhausted resin bed is then regenerated by
backwashing using a saturated brine solution. The Na+ ions in the brine solution replaces the
Ca+ and Mg+ ions in the resin,

regenerating it for further hard water treatment operation

(Venkatesan et al., 2010). Nowadays, as the population grows exponentially and the industries
expanding, so does the demand for soft water. Thus, a need for researching effective

regeneration of ion exchange resin bed for an efficient way of softening water for both
household and industrial purposes(Jolly, 1973).

1.2 Statement of the Problem

The resin bed in an ion exchanger, through continual use eventually come to be inundated with
Ca+, Mg+ and Fe+ ions that significantly lowers the resins ability to soften water thus making the
resin viable for replacement. The regeneration process of the resin can only regenerate the
exhausted resin up to two-thirds of the total capacity of the virgin resin (Dow Chemical
Company, 1999). The periodical replacement of the resin, lowers the economic efficiency of the
IX process.
1.3 Research Questions

What is the ideal salinity of the brine solution used for rinsing the ion-exchange resin?

Would it be possible to further soften the water even all the way down to zero hardness?

Would the continuous backwashing of the resin of the ion exchange be more economical
than the traditional resin replacement method?

What are the factors affecting the lifespan of the resin?

1.4 Objectives
This research aims to optimize the process of regenerating exhausted cation exchange resin
bed using brine solution as the regenerant with chlorine dioxide as an additive to prolong the life
of the resin in a water softener ion-exchange equipment.
1.5 Significance of the Study
The study is to be conducted in further research of identifying ways to optimize exhausted ion
exchange resins using brine. It will be of help to the industries which are in need of soft water in

their plant processes as this study will instill an economic way of regenerating exhausted resins
to prolong its life. And to serve as a literature for researchers who will be needing this field of
study.
1.6 Scope and Limitations
This research is to be conducted to optimize the process of regenerating exhausted cation
exchange resin using brine with chlorine dioxide as its additive. The study would focus on
identifying ideal salinity of brine to be used, identifying ways on how to increase the regenerated
resins new total capacity and deeper understanding of the economics cation resins. This study
would not dwell on demineralization using both cation and anion exchangers, ways on detecting
exhaustion of resin beds and other alternatives but may give ideas and recommendations for
the ones who would wish to continue on studying the ion exchange processes.
1.7 Definition of Terms
Ions soluble elemental molecules that are electrically charged, can be positive or negative.
Positive ions are called cations and negative ions are called anions.
Hardness the combined amount of calcium (Ca+) and magnesium (Mg+) cations
Brine Solution a solution of water and sodium chloride (NaCl)
Hard Water water containing Ca+ and Mg+ cations
Soft Water water without Ca+ and Mg+ cations
Regeneration the process of removing the Ca+ and Mg+ ions inside the resin
Total CationsTotal of the calcium (Ca++), magnesium (Mg++), sodium (Na+), potassium (K+),
ammonium (NH4+), and hydrogen (H+) ions.

AlkalinityThe total content of bicarbonate (HCO3-) carbonate (C03-), and hydroxyl (OH-),
ions in the water. This is always expressed as the alkalinity percent of total anions.
Magnesium-Calcium RatioThis term may be used to express the magnesium content
percent of the divalent cations. Manufacturers may identify these as magnesium percentage of
total hardness, magnesium percentage of total cations, or calcium percentage of total cations.
Salometer - A hydrometer that measures the density of a sodium chloride brine using a scale
marked for per cent of saturation, 0S to 100S. A 70S brine, for example, is 70% of fully
saturated brine, which at 60F would contain 1.75lbs of NaCl/gallon with a specific gravity of
1.139
Baume scale - An old antiquated method of measurement of a chemicals Specific Gravity. It
was devised a long make time ago and is a scaling on a hydrometer which measures the
Specific Gravity of solutions. There are 2 ways of using this scale, one for liquids that are more
dense than water and one for liquids less dense than water. Liquids with lower S.G. than water,
S.G = 140 / (B + 130 ) Liquids with higher S.G. than water S.G = 145 / (145 B ).
Capacity, Total The ultimate exchange ability of an ion-exchange resin. Total capacity is
determined experimentally using large dosages of analytical grade regenerant on small
amounts of resin. Results are often expressed in milli-equivalents per milliliter of resin.
Capacity, OperatingThe portion of the total exchange capacity of an ion-exchange resin
volume that is used in a practical ion-exchange operation. Operating capacity is determined
both experimentally and empirically under a given set of fixed conditions, such as regenerant
dosage and endpoint leakage. Values are usually expressed as kilograms of calcium carbonate
(CaCO3) removed per cubic foot of resin.

LeakageIons that are not fully removed during passage through a regenerated ion-exchange
bed. Leakage is caused by incomplete regeneration of the exchanger bed. Ions remaining on
the resin after regeneration can enter into solution during subsequent service cycles.
Stability, Chemical The ability of the ion-exchange resin to retain its capacity in the presence
of chemical oxidants such as chlorine.
Stability, ThermalThe ability of the ion-exchange resin to retain its capacity over extended
periods at elevated temperatures.
Stability, PhysicalThe ability of an ion exchanger to resist breakage caused by physical
manipulation, such as high water flow rates, or by volume changes resulting from osmotic
shock.

Chapter 2: Review of Related Literature

2.1 Ion Exchange

Corpora non agunt nisi fluida sive soluta- substances do not react unless in a liquid or
dissolved state. Most of the the time, in chemistry, this ancient rule holds true. However, there
will always be exceptions. One of which is ion exchange. Its basic principle: a solid reacts with a
solution, in which ions can be exchanged and precipitates can be removed by treating the
solution with a solid ion exchanger (Helfferich, 1995). Ion exchange is defined as the reversible
process of interchanging ions between a solid (ion exchange material) and a liquid in which
there is no change in the structure of the solid(Dow Chemical Company, 1999). Ion exchangers
are commonly used in water treatment and other industries such as in semiconductors and in
nuclear stations (Rohm&Haas, 2008).

Ion exchange naturally occurs and has been used on an industrial basis since 1900s with the
introduction of water softening using natural and later, synthetic zeolites. Sulfonated coal,
developed for industrial water treatment, was the first ion exchange material that was stable at
low pH. The introduction of synthetic organic ion exchange resins in 1935 resulted from the
synthesis of phenolic condensation products containing either sulfonic or amine groups which
could be used for the reversible exchange of cations or anions (Dow Chemical Company, 1999).
Ion exchange (IX) is a reversible adsorption process. The focus ion in the aqueous phase is
transferred to a solid phase and exchanged it with a same charged presaturant ion that diffuses
into solution. Many aqueous contaminants are charged, Ion Exchange is used to remove a
number of contaminants from water which includes bromide, arsenic, cobalt, calcium, dissolved
organic carbon (DOC), nitrate, perchlorates, and uranium. The most commonly used ion in an
anion exchange is Chloride. While the most commonly used ion in a cation exchange is Sodium.
(Maul, Kim, Amini, Zhang, & Boyer, 2014).

Ion exchangers is made of insoluble acids and/or bases which contains salts which are
insoluble as well, and this made them have the ability to exchange either positively charged ions
which are the cation exchanger or negatively charged ones which are the anion exchangers.
Natural substances such as cellulose, proteins, soil particles and living cells exhibit ion
exchange properties which is important in the way the function in nature. (De Franciscis, 1951)
While there is no permanent change in the structure of the solid in the ion exchanger, the
structure of the liquid is rebuilt to have a soft water. Ion exchange is commonly used in water
treatment and provides a separation method for many operations involving other liquids. IX has
special uses in chemical synthesis, agriculture, food processing, mining, medical research, and
other areas and fields involved which are in need of such water without contaminants. Ion
exchange is a good process which has the ability to use and reuse the exchanger for quite a
long time.

2.1.1 Advantages and Disadvantages of Ion Exchanger

The advantages of ion exchange processes are low operation costs, little energy
requirement, cheap regenerant chemicals and well maintained resin beds can last long.
However, limitations during the design stages may represent an impression that ion
exchange methods may have many short comings to be useful in practice. However, that
would not be the case as the advantages mentioned above are very great and can easily
cover any compensation for having some minor shortcomings(De Franciscis, 1951).
2.1.2 Limitations of Ion Exchange
For ion exchange to be effective, difference in affinity between the ion in the resin and
the ions in the hard water must be observed. The resin must have higher affinity
compared to the ion in the resin.

The IX technology is an ideal tool to remove contaminants present in low concentrations.

The running time of the resin column to be exhausted is observed to be very long from
about an hour and extending over a year. When however the concentration of
contaminants is very high, the ion exchange cycles become very short and the quantity
of regenerants increases up until it will be observed that it is not economical to use the
IX. Thus from high concentrations of contaminants, the resin bed will be exhausted in a
faster period of time. In the case of underground water with high salinity or sea water, ion
exchange is not suitable and substitute technologies must be used, such as distillation or
reverse osmosis.
Using activated carbon, molecular sieves and other media can be used to ionise any
contaminant that cant be removed by IX (Rohm&Haas, 2008)
2.2 Ion Exchange Resin
Ion exchange materials for resin beds are insoluble substances containing loosely held ions
which are able to be exchanged with other ions in aqueous solutions which come in contact with
them (De Franciscis, 1951). These are very small plastic beads, with a diameter of about 0.6
mm. These beads are porous and contain invisible water inside the beads, measured as
humidity or moisture content. Most ion-exchange resins are based on a cross-linked
polystyrene or acrylic structure. The synthesis of resins is a two or three-step process consisting
of polymerization, intermediate reactions, and functionalization. The two most commonly used
resins are the polystyrene based with sulphonate group called the cation exchangers and the
other with amine group called the anion exchangers (Miller, Castagna, & Pieper, 2009).

Figure 1 - Examples of ion exchange resins

The resin bed is made of a polymer where individual resin can be found. Every ion in every
resin is considered a part of the polymer structure and has an ion attached to it permanently.
The ion in the resin can be neutralised by a counterion to preserve the neutrality of the resin.
This counterion can be moved in and out of the resin bead. Figure 1 shows schematic cation
and anion exchange resin beads. The dark lines represent the polymer skeleton boundary of the
resin bead, which is porous and contains water. The fixed ions of this cation exchange resin are
sulphonates (SO3) that are attached to the polymer skeleton. (Rohm&Haas, 2008)

Figure 2 - Schematic cation and anion exchange resin beads

Ion exchange resins are more commonly used for water purification than for any other purpose.
In the process of water softening, a cation resin which has an ion of sodium is used to remove
the hard metal ions which can be in the form of calcium or magnesium from the water along with

remnants of iron and manganese, which are often present in the hard water. The stoichiometric
equation for calcium removal in water softening is:
2RNa+ + Ca2+ R2Ca2+ + 2Na+
The alphabet R which is the ion exchange polymer contains sodium ion can exchange its
sodium ions for another ion like calcium and thus it removes the unwanted calcium ions from the
hard water and change it with an equivalent amount of Na:sodium based on the stoichiometry
given. hence, the calcium saturated resin bedding which was the result of the exchange can be
backwashed with brine solution or commonly known as sodium chloride solution, thus
regenerating it back to the sodium form, so the function of the resin in removing unwanted ions
in the hard water can be used for another operation. (Dow Chemical Company, 1999). The
regeneration reaction is considered reversible while the ion exchanger in not permanently
changed unless spent up and reduce its efficiency. In the field, however, resins are usually
regenerated to about two thirds of its total capacity which is a good fraction for another run of
the resin bed (De Franciscis, 1951). Millions of liters of water can be treated per cubic meter of
resin during an ion exchangers years of operation.
2.3 Regerant
Different kinds of organic salts have been studied and used for regenerating different kinds of
ion exchange resins. A regenerant for the resin bed is usually concentrated solution (commonly
2% to 10%) that is capable of reversing the ion exchange equilibrium by the principle of mass
action(Miller et al., 2009). Sodium solution is widely used in full-scale practice and well
documented in the literature. Others such potassium salt for cation exchange and bicarbonate
salt for anion exchange are considered under researched topics because of the limited amount
of previous literature(Maul et al., 2014).
2.4 Regeneration of Ion Exchange Resin Bed

The basic purpose of resin regeneration is to restore the exhausted resin back to its proper ionic
form for service(Desilva, 2014). Regeneration is of great importance because reducing the
regenerant level lowers water quality by allowing a small proportion of the ions which are being
taken up by the resin to slip through without exchange. That passing through of unwanted ions
is called leakage(Woolley, n.d.). Also, this process allows for the reuse of the spent resin bed
therefore contributing to the economic efficiency of the unit operation.
Regeneration can only be performed when the concentration of the regenerant is high, typically
1000 times higher than the concentration in normal water. For instance, salt is used as a brine
with 10 % (about 100 g/L) concentration. The softening resin is regenerated with sodium (Na+)
ions supplied by a salt solution. The regeneration reaction is:
R2Ca + 2 NaCl 2 RNa + CaCl2

In the case of demineralisation, 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
(Rohm&Haas, 2008):
RNa + HCl RH + NaCl

2.5 Chlorine Dioxide

Chlorine dioxide (ClO2), serves as an anti-bacterial agent that reacts with several cellular
constituents, including the cell membrane of microbes. ClO 2 breaks the molecular bonds,
resulting in the breakdown of the organisms by the tearing up of the cell by which taking
electrons from the unwanted organic contaminants through oxidation. Since chlorine dioxide
changes the proteins in the structure of microorganisms present in the cell, the enzyme function
is broken, causing it to kill the bacteria present rapidly. (ChlorDiSys, 1986)

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