2.

0 MATERIAL AND METHOD

Water softening is needed due to the hardness occurence and will give adverse effects
to human especially. Hence water softening treatment is required to reduce the impacts
of hardness. There are several type of treatment process for hardness, which involve
membrane separation, lime and soda ash, and ion exchange.
In membrane separation, the membrane to be used in this process is
nanofiltration membrane. Since hardness is large particles, then a coarser and cheaper
membrane can be used in separation of hardness with water. The efficiency of this
technique increases with temperature due to decreasing in viscosity. This membrane
technology is favoured because of its low capital and operational costs. However, it is not
suitable to be used in well or any area which has lower yield of water.
Lime and soda ash is another method used for softening the hardness in water.
This is a simple method as lime, Ca(OH)2 and soda, Na2CO3 are added to the hard water
and the calcium will be precipitated out as Calcium Carbonate, Ca2CO3 and magnesium
will be precipitated out as Magnesium Hydroxide Mg(OH)2. These precipitates were then
removed by coagulation, flocculation, sedimentation and filtration processes.
Another softening method is known as ion exchange. Ion exchange is a water
treatment method where one or more dissolved undesirable contaminant ions are
removed from water by exchange with another other ions of the same or similar electrical
charge and it is reversible. One of the conditions of this method is that both the
contaminants and exchanged substances must be dissolved and have same type of
electrical charge. The typical materials used for ion exchange include resin and zeolite.
This method uses salt to exchange with the hardness minerals as well as regeneration
process.

2.1 Process of Ion Exchange

The type of softening method chosen in this study is ion exchange method by using resin
as the media. Ion exchange basically extensively applied in small water systems and
individual homes apart from industry because of to avoid contaminant of effluent
discharge from industrial areas. Normally, ion exchange for softening includes softening
cycle, backwash cycle, regeneration cycle and rinse cycle.
2.1.1 Softening Cycle

First, raw water is passed through the resin media column where there is already
regeneration done on the resin beads and this is where the ion exchange happened. This
is also known as softening cycle. The softening cycle ends when there is less 5 mg/L of
hardness is detected in the effluent. Almost all softening units have an alarm on the water
meter to indicate when a certain amount of water has passed through the exchange unit.
This is done to ensure the required outlet quality.

2.1.2 Backwash Cycle

Until a point when there is only a few salt ion attached on the resin beads, less hardness
can be removed. This is the stage of “exhausted” stage. When resin beads reach this
stage, backwash and regeneration are required to recover the ability of resin beads to
remove hardness.
In backwash cycle, the resin bed is expanded from its settled and packed
condition and the suspended solids in the resin bed can be washed out. The operator
needs to apply enough backwash water to expand the resin bed by about 50 percent. In
this stage, resin beads also rub against each other so that the accumulated dirts on the
surface of resin beads can be removed.

2.1.3 Regeneration Cycle

The regeneration stage includes brine introduction. The regeneration is usually done by
salt brine. The brine used is usually sodium chloride. Next, brine is introduced into the
resin bed to restore the resin back to sodium form. According to Desilva (2006), a contact
time of 30 minutes in brine introduction is desirable. The brine needs to be in contact with
the resin long enough to allow for complete exchange of hardness ions on the resin with
sodium ions in the brine. It is better to allow more time than to not allow enough. If the
resin is not totally recharged, the next softening run will be short. Equation 2 shows
regeneration of resin bead.

2.1.4 Rinse Cycle

The rinse cycle removes remaining brine from the tank. Normally 10 minutes of rinse flow
equivalent to service flow is sufficient to rinse out excess brine.

Figure 2.1a: Resin Beads

Figure 2.1b: Ion Exchange Treatment Process

2.2 Mechanism of Removal

In the process of passing the raw water into the resin beads column, the hardness in
water, which are calcium ion, Ca2+ and magnesium ions, Mg2+ are exchange with sodium
ion, Na+ or potassium ion, K+ that is temporarily stored in the pores of resin during
regeneration.

Figure 2.2a: Illustration of Ion Exchange

Na+ Ca2+
Ca(HCO3)2 + + 2NaHCO3 (Equation 1)
Na+

Ca2+ Na+
+ NaCl + CaCl2 + NaCl (Equation 2)
Na+

The ion exchange is actually works by selectivity (Michaud, 2011). This means
that ions with lower charge potential will usually be replaced ions which has higher charge
potential. In water softening process, the ions with lower charge potential which are
sodium ion, Na+ or potassium ion, K+ can be readily replaced by the ions with higher
charge potential such as Ca2+ and magnesium ions, Mg2+. Hence, hardness from the
water sources are removed and attached on the resin beads as shown in Equation 1. The
illustration of ion exchange is shown in Figure 2.2a.
In fact, resin bead is just a physical medium that can facilitate ion exchange rather
than a chemical reactant. Based on SAMCO, the resin can be used as ion exchanger
because of its functional groups, which are essentially fixed ions that are permanently
bound within the polymer matrix of the resin. These charged ions will readily bond with
ions of an opposing charge, which are delivered through the application of a counterion.
These counterion will continue to bond with the functional groups until equilibrium is
reached. These can be seen in Figure 2.2b.

Keys:
Na+ = mobile ions (counter-ions)
SO-3 = fixed group
Dark line = polymeric skeleton

Figure 2.2b: Schematic Cation Exchange Resin Bead

2.3 Design of Ion Exchange Column

The design of the ion exchange column is very important so that it can ensure the
adequate performance of the ion exchange. The design criteria include types of bed, flow
rate, water temperature and amount of hardness to be removed.

2.3.1 Types of Bed

Depending on the types of contaminants to be removed, ion exchanger can be divided

into two categories, which are single bed and double bed. Single bed is used for only one
type of resin, which is either cation or anion resin. Hence, it is able to treat only anion or
cation contaminants. For double bed, it is the mixture of cation and anion resin or strong
and weak resin in a single column ion exchanger.

2.3.2 Flow Rate

The first criterion to be considered in design of the softening tank is the service flow rate.
The flow rate is usually determined by maximum demand or average demand. According
to Windsor, if the maximum demand is only a short period, or if there is various operating
flow rate, then the plant can be designed on the average demand to cater the maximum
flow rate and variations in demand. According to Dynamic (2013), the higher the flow rate,
the deeper the softener column of resin is required because this can ensure sufficient
performance of ion exchange.
Besides that, the ion exchange column can be made of plastic, steel and coated
steel. Normally plastic can be used for flow rate around 5 to 10 m³/h while steel is normally
used for even higher flow rates.

2.3.3 Water Temperature

From the Gay-Lussac Law, it stated that as the temperature increases, the pressure will
also increase. Hence, as the temperature of the water decrease, the pressure drop will
increase. When pressure drop increase, the velocity also increase, and the deeper
column is required. This is because if the velocity increases, the contact time of the water
to be stored in the column decreases. Hence, a deeper column is required to ensure
adequate ion exchange.
The increase of pressure drop can also be affected by viscosity of the water. The
higher the temperature, the lower the viscosity of the water. Low viscosity water can
increase the velocity of the water as well as the ion exchange kinetics. In short, the lower
the water temperature, the deeper column is required. The relationship between water
temperature, pressure drop, length of column and viscosity can be seen by Equation 3.

∆P 173 × μ × Vo × Af
= (Equation 3)
L Dp 2

Where,
P = Pressure drop (kPa/m-resin bed)
m = Viscosity of water (Pa.s)
L = Bed depth (m)
V0 = Flow velocity (m/s)
Af = Coefficient (~1.00)
Dp = Diameter of resin bead (m)
2.3.4 Amount of Hardness to Be Removed

If the water intake has high amount of hardness, then a deeper column of resin is
required to ensure adequate ion exchange. However, from Dynamic (2013), if the water
source has high hardness, then the amount of other interfering ions will also be high. As
we know that the mechanism of ion exchange is works with selectivity, hence, some
interfering ion ferrous ion, Fe3+ can affect the softening ability of the column. This is
because ferrous ion has higher molecular weight and it has higher ability to exchange
with sodium or potassium ion compared to calcium ion and magnesium ion.
2.4 Test Conducted

Before design the softening resin column, the level of hardness of the water source
should be determined first so that we can know how depth is the resin column. Besides
that, the hardness of the effluent should also be tested so that the efficiency of the resin
column can be known. There are some tests that can be used for measure the water
hardness. Test for salt in water should also be conducted so that the brine inserted is
comply with the standard.

2.4.1 Titration

Titration is the most common method used for measure the hardness in water. This test
method is usually used for waters that are clear in appearance and free of chemicals that
will complex calcium or magnesium. In this method, calcium and magnesium ions in water
are sequestered by the addition of EDTA, normally disodium ethylenediamine
tetraacetate. The end point of the reaction is detected by means of Chrome Black T4,
which has a red color in the presence of calcium and magnesium and a blue color when
they are sequestered.

2.4.2 Instrument
The presence of hardness in water can also be measured by colorimeter or
spectrophotometer. According to HACH, the limitation of this method is this is only used
for extremely soft water where the concentration is expected to be less than 4 mg/L as
CaCO3. These instruments is suitable to measure exact value of hardness present in the
water.

2.4.3 Test Strip

Test strip can also be used in measuring hardness of water. If the strip is inserted into
water which contains hardness, a colour will be developed on the strip and the colour of
the strip is then matched with the chart. According to HACH, The chart shows colors for
concentrations of 0, 25, 50, 120, 250, and 425 ppm, or 1, 1.5, 3.7, 15, and 25 grain per
gallon (gpg). This strip is only used for several range of hardness. It is not suitable to
measure the exact hardness concentration in the water.
 Figure 2.4.3: HACH Water Hardness Test Strip

2.4.4 Sodium Electrodes

The sodium electrode is a sodium-sensing element that is bonded into an epoxy body.
When the sensing element touches sodium ions in a solution, a potential develops across
the sensing element. The potential is proportional to the level of sodium ions in the sample.
The potential is measured against a constant reference potential with a pH/mV meter or
ISE meter.
Measurement for sodium in water is essential for ion exchange method if sodium
ion is used in the brine solution. From the U.S. Environmental Protection Agency (EPA),
they recommended that the sodium levels in water should not exceed 20 mg/l for
individuals on “no salt diets.” Connecticut’s current “notification level” is 28 mg/l for
individuals on low sodium diets and receiving water from a community water system.
2.5 Factor of Influencing

There are various factors that can influence the efficiency of the ion exchange. They
include selectivity, water conductivity and turbidity, organic chemicals, and bacterial
slimes.
The selectivity can affect the adsorption of ions on the resin. Ions with higher
molecular weight have higher potential to be attracted by resin. For example, interfering
ions such as ferrous ion, Fe3+ has higher molecular weight than calcium ion, Ca2+.
Therefore, iron ion has higher potential to be adsorbed by resin compared to calcium ion.
The other factor is water conductivity. Water conductivity has an effect on the
success ion exchange. Dynamic (2013) stated that the higher the conductivity of the
water, the more interfering ions will attach to the ion exchanger site and hence lead to
failure of softening process.
Besides that, turbidity, organic chemicals, and bacterial slimes resins resulting in
the loss of some of the resin exchange capacity. Hence, it would be better if all the
suspended matter is removed such as by filtration before the softening process.
2.6 Damage of Resin Bead

There are several causes that can damage the resin beads. They are hydraulic shock,
osmotic shock, and chlorine degradation.
Hydraulic shock happens when water flow is suddenly interrupted. Hydraulic
shock is also known as water hammer. When the power of flowing water stops
immediately, it creates a shock wave that transfers back through the plumbing system
and slams into the resin bed. The resin softener acts as a shock absorber in the plumbing
system and takes enormous abuse. As beads become weak from age, the hammering
action of the water cracks them and the resulting pieces backwash out of the resin tank.
The damage of resin bead caused by hydraulic shock is shown in Figure 2.6.1.

Figure 2.6.1: Damage Caused by Hydraulic Shock

Osmotic shock can also cause damage to resin beads. Osmotic shock differs from
hydraulic shock in that osmotic shock is the swelling and contacting of the bead, where
hydraulic shock is the physical destruction of the bead by external water force. Over time,
beads will succumb to osmotic shock and eventually some will crack. As the beads crack,
they break apart and lose mass. The damage of resin bead caused by hydraulic shock is
shown in Figure 2.6.2. This is normally caused by fast rinse. In an immediate fast-rinse
scenario, water enters the bead in large amounts, causing it to swell, crack and possibly
burst. This is the reason for the slow-rinse cycle; rinsing the resin bed slowly helps
prevent this condition.
 Figure 2.6.2: Damage Caused by Osmotic Shock

Another factor of damage of the resin beads is chlorine. The presence of two-
parts-per-million residual chlorine in a water system can cut the life expectancy of a
standard softening resin in half. As chlorine attack the beads, they will swell and take on
moisture. As they swell, pores and channels through the beads close and block access
to the functional groups and then they become mushy as shown in Figure 2.6.3.

Figure 2.6.3: Damage Caused by Chlorine

http://gregknowswater.com/ion-exchange-softener-design-a-gentle-introduction/

file:///C:/Users/user1/Downloads/Brian_Windsor_calculation.pdf

(https://www.des.nh.gov/organization/commissioner/pip/factsheets/dwgb/documents/dw
gb-3-6.pdf).
https://www.des.nh.gov/organization/commissioner/pip/factsheets/dwgb/documents/dw
gb-2-12.pdf
https://www.wqpmag.com/resin-regeneration-fundamentals
http://www.wcponline.com/2011/04/21/ion-exchange-reactions-a-review/
https://www.samcotech.com/ion-exchange-resin-work-process/
https://professionalwatersystems.com/wp-content/uploads/2015/11/Sodium-in-Drinking-
Water.pdf
https://www.hach.com/hardnessguide
http://www.wcponline.com/2010/02/08/its-tough-being-a-resin-bead/