Water Softening and

Demineralization
Pengolahan Air dan Limbah Industri
DTK 2019

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Contents
• HARDNESS
1. How does water become hard?
2. What are the objections to hard water?
3. How is hardness expressed?
4. What degree of hardness is considered objectionable?
5. How is hardness removed?
• LIME-SODA ASH SOFTENING
1. What are the chemical reactions that happen with lime addition?
2. What are the chemical reactions with soda ash?
3. What are the types of lime-soda ash processes?
• Conventional lime-soda ash treatment
• Excess lime treatment
• Split treatment
• Design Considerations
• Sludge Removal

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Contents
4. How are the lime dosages determined?
• Calculations of Chemical Dosages
• Recarbonation
• Process Description
• ION EXCHANGER
• ZEOLITE SOFTENING
• Chemistry of the Ion-Exchange Reaction
• Advantages of the Ion-Exchange Process
• Operation of units
• Operating problems
• DEMINERALISATION

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

HARDNESS
Water softening

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Hardness

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

How does water become hard?
• Water becomes hard by being in contact with soluble,
divalent, metallic cations (positive ions having a valence
of 2).
• The two main cations that cause water hardness are
calcium (Ca) and magnesium (Mg).
• Calcium is dissolved in water as it passes over and through
limestone deposits.
• Magnesium is dissolved as water passes over and through
dolomite and other magnesium bearing formations.
• Because groundwater is in contact with these geologic
formations for a longer period of time than surface
water, groundwater is usually harder than surface
water.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

What are the objections to hard
water?
• Calcium and magnesium precipitate soap:
• Forming a curd which causes “bathtub ring” and dingy
laundry (yellowing, graying, loss of brightness, and
reduced life of washable fabrics), and
• Feels unpleasant on the skin (red, itchy, or dry skin).

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

What are the objections to hard
water?
• Hard water forms scale, usually calcium carbonate, which
causes a variety of problems.
• Left to dry on the surface of glassware, silverware, and plumbing
fixtures (shower doors, faucets and sink tops), hard water leaves
unsightly scale, called water spots.
• Scale that forms on the inside of water pipes eventually reduces the
water pipes’ carrying capacity.
• Scale that forms within appliances, pumps, valves, and water
meters causes wear on moving parts.
• When hard water is heated, scale forms much faster. This creates an
insulation problem inside boilers, water heaters, and hot-water
lines and increases heating costs.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

How is hardness expressed?
• Calcium carbonate is one of the more common
causes of hardness, total hardness is usually
reported in terms of calcium carbonate
concentration (mg/L as CaCO3), using either of two
methods:
a. Calcium and magnesium hardness.
b. Carbonate and non-carbonate hardness.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

How is hardness expressed?
• Hardness caused by calcium is called calcium hardness,
regardless of the salts associated with it. Likewise, hardness
caused by magnesium is called magnesium hardness. Since
calcium and magnesium are normally the only significant
minerals that cause hardness, it is generally assumed that:

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

How is hardness expressed?
• Carbonate hardness is primarily caused by the carbonate
and bicarbonate salts of calcium and magnesium.
• Non-carbonate hardness is a measure of calcium and
magnesium salts other than carbonate and bicarbonate
salts, such as calcium sulfate, CaSO4, or magnesium
chloride, MgCl2.
• Total hardness is expressed as the sum of the carbonate
hardness and non-carbonate hardness.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

What degree of hardness is
considered objectionable?

It has often been proposed that ideally water should have a total
hardness of 75 to 85 mg/l (as CaCO3) and a magnesium hardness
of not more than 40 mg/l as CaCO3 to minimize magnesium
hydroxide scaling at elevated temperatures

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

How is hardness removed?
• “Softening” is the term which refers to the process
of hardness removal.
• The two basic methods of softening public water
supplies are chemical precipitation and ion
exchange.
• Other methods can also be used to soften water,
such as electrodialysis, distillation, freezing, and
reverse osmosis. (Expensive!)

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

LIME-SODA ASH
SOFTENING
Water softening

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Lime-Soda Ash Softening
• Chemical precipitation is one of the more common
methods used to soften water.
• The chemicals normally used are:
• Lime (calcium hydroxide, Ca(OH)2). Lime is used to
remove the chemicals that cause the carbonate
hardness.
• Soda ash (sodium carbonate, Na2CO3). Soda ash is used
to remove the chemicals that cause the non-carbonate
hardness.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

 What are the chemical reactions
that happen with lime addition?

CO2 does not contribute to the hardness, but it reacts with the lime, and therefore
uses up some lime before the lime can start removing the hardness.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

What are the chemical reactions
with soda ash?

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

What are the types of lime-soda
ash processes?
• Conventional lime-soda ash treatment
• Excess lime treatment
• Split treatment

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Conventional lime-soda ash
treatment
• When the content of the water has little
magnesium hardness only the calcium ions need to
be removed.
• This is termed conventional lime-soda treatment.
• Only enough lime and soda ash are added to the
water to raise its pH to between 10.3 and 10.6.
• The calcium hardness will then be removed from
the water, but little if any magnesium hardness will
be removed.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Excess lime treatment
• When the magnesium hardness of water is more
than about 40 mg/l (expressed as CaCO3),
magnesium hydroxide scale will deposit in
household hot-water heaters operated at normal
temperatures of 140 to 150° F.
• To reduce this magnesium hardness, more lime
than is used in the conventional process must be
added to the water.
• The extra lime will raise the pH above 10.6 so that
the magnesium hydroxide will precipitate out of the
water.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Split treatment
• When the water contains high amounts of magnesium,
a process called split treatment may be used.
• Approximately 80 percent of the water is treated with
an excess of lime to remove the magnesium at a pH
above 11, after which it is blended with 20 percent of
the source water.
• When the water is mixed with the water that does not
undergo softening, the carbon dioxide and bicarbonate
in that water tend to recarbonate the final blend. The
split treatment process reduces the amount of
chemical needed to remove the hardness from the
water by about 20 to 25 percent, a significant saving.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri
 Design Considerations
• In lime soda-ash
softening plants, the
softening process may be
carried out by a sequence
of rapid mix, flocculation,
and sedimentation or in a
solids-contactor softener.
• In the solids contactor the
rapid mix, flocculation,
and sedimentation occur
in a single unit.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

How are the lime dosages
determined?
• There are two methods for calculating approximate
lime and soda ash dosages:
• the conventional-dosage method and
• the conversion factor method
• Lime is used to remove carbonate harness, and both
lime and soda ash are used to remove non-carbonate
hardness.
• If the total hardness is less than or equal to the total
alkalinity, then there is no non-carbonate hardness, only
carbonate hardness.
• If the total hardness is greater than the total alkalinity, then
the noncarbonate hardness equals the difference between
the total hardness and the total alkalinity, and the carbonate
hardness equals the total alkalinity..

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

How are the lime dosages
determined?
• If total hardness is equal to or less than (<) total
alkalinity, then:

Lime Dosage = the carbon dioxide concentration [CO2]

+ the total hardness concentration [Total Hardness]
+ the magnesium concentration [Mg]
+ [Excess]

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Alkalinity
• Alkalinity is the capacity of water to neutralize
acids. This is determined by the content of
carbonate, bicarbonate and hydroxide.
• Alkalinity is expressed in milligrams per liter of
calcium carbonate.
• Alkalinity is a measure of how much acid can be
added to a liquid without causing any significant
change in pH.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Alkalinity
• There are two procedures used to measure alkalinity.
• Both procedures involve adding a weak solution of acid,
usually sulfuric acid, to a water sample until the pH
decreases to 8.3 and then adding more of the acid
solution to the water sample until the pH decreases to
4.5.
• One method uses a pH meter while the other uses
reagents of Phenolphthalein, which changes color at pH
8.3, and Methyl Orange, which changes color at pH 4.5,
to determine how much acid is needed to decrease the
pH of the water sample to those levels.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

 Alkalinity
• The procedures mentioned above will enable you to find the
Phenolphthalein alkalinity (P) and the Total alkalinity (T).

where N = Normality of the acid (this will be given) and 50,000

is a conversion factor used to express in terms of mg/l of
CaCO3.

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Alkalinity
• Example 0.02N sulfuric acid is used to titrate 110 ml of
water. 3.3 ml of titrant is needed to reach the
phenolphthalein point (pH = 8.3), and 13.2 ml is needed to
reach the methyl orange point (pH = 4.5). What are the total
and phenolphthalein alkalinities?
• Answer:

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• The relationship between the various alkalinity constituents-
-bicarbonate(HCO3), carbonate(CO3), hydroxide(OH) -, and
total alkalinity(T)--is shown in the following table. It gives an
indication of how the P alkalinity relates to the total or (M +
P) alkalinity and how this relationship determines the type
of carbonate present.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

 Relationship between pH and alkalinity constituents
(HCO3-, CO32- and OH- )

When the pH is less than 8.3, all alkalinity is in the bicarbonate form and is commonly referred to
as natural alkalinity. When the pH is above 8.3, the alkalinity may consist of bicarbonate,
carbonate, and hydroxide. As the pH increases the alkalinity progressively shifts to carbonate and
hydroxide forms.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Alkalinity
A laboratory test of a water to be softened shows the
following results for alkalinity:
P alkalinity = 0 mg/l
T alkalinity = 200 mg/l
Refer to the table above for the type of alkalinity that is
present in the water.
The P alkalinity is equal to 0, so the total alkalinity is
equal to the bicarbonate alkalinity.
Bicarbonate Alkalinity = Total Alkalinity
= 200 mg/l
The first row also indicates that since P = 0, the
carbonate and hydroxide alkalinity also equal 0.
Carbonate alkalinity = 0
Hydroxide alkalinity = 0

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Alkalinity
Another water sample shows the following results for alkalinity:
P alkalinity = 20 mg/l
T alkalinity = 50 mg/l

The P alkalinity is less than 1/2 T. This means that the alkalinity is
made up of bicarbonate and carbonate alkalinity in the following
amounts:
Bicarbonate = T - 2P = 50 mg/l - (2 x 20) mg/l = 50 mg/l - 40 mg/l
= 10 mg/l
Carbonate Alkalinity = 2 P = 2 x 20 mg/l
= 40 mg/l
Hydroxide = 0 mg/l

The results of the alkalinity test would also indicate that the pH of
the water is greater than 8.3, since P alkalinity cannot be present
when the pH is less than 8.3.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Calculations of Chemical Dosages
• The quicklime dosage can be calculated with the
following formula:

A = Carbon Dioxide in source water

B = Bicarbonate alkalinity removed
C = Hydroxide alkalinity in softener effluent
D = Magnesium removed in softening

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DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri
Calculations of Chemical Dosages
• When treating a water that contains non-carbonate
hardness, the use of soda ash is required. The
amount of soda ash needed can be estimated by
using the following formula:

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Calculations of Chemical Dosages
• After softening, the pH of the water is generally above 10. If
left at this elevated pH, the water will plate the filter sand
and cause problems in the distribution system. Carbon
dioxide, through what is called recarbonation, is added to
lower the pH. The amount of carbon dioxide (CO2) required
can be estimated by using the following formula:

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Conversion Method

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Example
• The following test results were provided by the
laboratory:
• CO2 concentration 25 mg/l as CO2
• HCO3 (bicarbonate) concentration 205 mg/l as CaCO3
• Mg (magnesium) concentration 9 mg/l as Mg
• non-carbonate hardness concentration 95 mg/l as CaCO3
• Assuming no excess lime is added, find the correct
dosages in milligrams per liter for lime (containing
90% pure CaO) and soda ash (containing 99% pure
Na2CO3) required to remove all hardness.

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Example

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Example

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Recarbonation
• Depending on the amount of lime or chemical needed
to reduce the amount of calcium or magnesium in the
water, the treated water will generally have a pH
greater than 10.
• It is necessary to lower the pH to stabilize the water
and prevent the deposition of hard carbonate scale on
filter sand and distribution piping.
• Recarbonation is the most common process used to
reduce the pH. This procedure involves the addition of
carbon dioxide to the water after the softening.
Generally, enough carbon dioxide is added to reduce
the pH of the water to less than 8.7.

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Recarbonation
• When low magnesium water is softened, no excess lime
needs to be is added. After softening, the water becomes
supersaturated with calcium carbonate and has a pH
between 10.0 and 10.6. When carbon dioxide is added, the
excess calcium carbonate is converted back to permanent
hardness or calcium bicarbonate by the following formula:
Ca2+ (calcium ion) + CO32- (carbonate ion) + CO2 (carbon
dioxide) + H2O (water)
= 2HCO3- (bicarbonate ions)

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Recarbonation
• When high magnesium water is softened, excess lime needs to be
added to raise the pH above 11, so that magnesium hydroxide
precipitates out. After this treatment, enough carbon dioxide
must be added to neutralize the excess hydroxide ions as well as
convert the carbonate ions to bicarbonate ions. The first stage of
this reaction reduces the pH to between 10.0 and 10.5. In this
range, calcium carbonate is formed and magnesium hydroxide
that did not precipitate, or did not settle out, is converted to
magnesium carbonate.

Ca2+ (calcium ion) + 2 OH- (hydroxyl ions) + CO2 (carbon dioxide) <----
> CaCO3 (calcium carbonate) + H2O (water)

Mg2+ magnesium ion) + 2 0H- (hydroxyl ions) + CO2 (carbon dioxide)

<----> MgCO3 (magnesium carbonate) + H20 (water)

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Recarbonation
• Additional carbon dioxide needs to be added to lower the
pH to between 8.4 and 8.6. When that is done, the
previously formed calcium carbonate redissolves and the
carbonate ions are converted to bicarbonate ions as shown
below:

CaCO3 (calcium carbonate) + H20 (water) + CO2 (carbon

dioxide) <----> Ca2+ (calcium ion) + 2HCO3- (bicarbonate ions)

Mg2+ (magnesium ion) + CO32+ (carbonate ion) + CO2 (carbon

dioxide) + H20 (water) <----> Mg2+ (magnesium ion) + 2 HCO3-
(bicarbonate ions)

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Process Description
• Two types of recarbonation processes are used:
• Single-stage recarbonation
• Two-stage softening

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Single-stage recarbonation
• For treatment of low-magnesium water, where excess-lime
addition is not required, single-stage recarbonation is used.
• The water is mixed with lime or soda ash in the rapid-mix basin,
resulting in a pH of 10.2 to 10.5. If non-carbonate hardness
removal is required, soda ash will also be added at this step.
• After rapid mixing, the resulting slurry is mixed gently for a period
of 30 to 50 minutes to allow the solids to flocculate.
• After flocculation, the water is allowed to flow into a
sedimentation basin where the solids will be removed by
sedimentation.
• Following sedimentation the clear water flows to the
recarbonation basin where carbon dioxide is added to reduce the
pH to between 8.3 and 8.6.
• Any particles remaining in suspension after recarbonation are
removed by filtration.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Two-stage softening
• Two-stage softening is sometimes used to recarbonate
high magnesium water that has to be treated with
excess lime. In this process, excess lime is added in the
first stage to raise the pH to 11.0 or higher for
magnesium removal.
• Following first stage treatment, carbon dioxide is added
to reduce the pH to between 10.0 and 10.5, the best
value for removal of calcium carbonate.
• If non-carbonate hardness removal is required, soda
ash will be added at this point.
• After second stage treatment, the water flows to a
secondary recarbonation tank, where the pH is reduced
to between 8.3 and 8.6.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

ION EXCHANGE
Water softening

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

ION EXCHANGE
• Ion exchange is an adsorption phenomenon where the
mechanism of adsorption is electrostatic. Electrostatic
forces hold ions to charged functional groups on the surface
of the ion exchange resin. The adsorbed ions replace ions
that are on the resin surface on a 1:1 charge basis. For
example:

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Applications of ion exchange in
water & wastewater
• Ca, Mg (hardness removal) exchange with Na or H.
• Fe, Mn removal from groundwater.
• Recovery of valuable waste products Ag, Au, U
• Demineralization (exchange all cations for H all anions for
OH)
• Removal of NO3, NH4, PO4 (nutrient removal).

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Ion Exchangers (types)

• Natural: Proteins, Soils, Lignin, Coal, Metal oxides,

Aluminosilicates (zeolites) (NaOAl2O3.4SiO2).
• Synthetic zeolite gels and most common -polymeric resins
(macroreticular, large pores).

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Polymeric resins

Divinylbenzene:

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Ion Exchanger Resin

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Resin classification
• Resins are classified based on the type of functional group
they contain and their % of cross-linkages
• Cationic Exchangers:
• Strongly acidic – functional groups derived from strong acids e.g.,
R-SO3H (sulfonic).
• Weakly acidic – functional groups derived from weak acids, e.g.,
R-COOH (carboxylic).
• Anionic Exchangers:
• Strongly basic – functional groups derived from quaternary
ammonia compounds, R-N-OH.
• Weakly basic - functional groups derived from primary and
secondary amines, R-NH3OH or R-R’-NH2OH.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Simplified Ion Exchange Process

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

ION EXCHANGE
SOFTENING
Water softening

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Ion Exchange Softening
• The ion-exchange method of water softening has
been used extensively in smaller water systems and
individual homes.
• It is based on the ability of the ion-exchange resin,
zeolite, to exchange one ion from the water being
treated for another ion that is in the resin.
• Zeolite resin exchanges sodium ions for ions
causing hardness in the water, such as calcium and
magnesium. Sodium is one component of softening
salt, with chlorine being the other.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Chemistry of the Ion-Exchange
Reaction

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Hardness unit
• The measurements used to express water hardness in the ion-
exchange process differ from the units that are normally used in
the lime-soda softening process. Hardness in the ion-exchange
process is expressed as grains per gallon rather than mg/l of
calcium carbonate. The following conversions show the
relationship between mg/l and grains per gallon:

1 grain 17.12 mg/l 1 grain 0.143 lbs per 1000 gallon 7000 grains 1 lb
per gal

• An example of this relationship: if a water contains 10 grains of

hardness, what would the hardness be expressed as in mg/l?

10 grains x 17.12 mg/l / grain = 171.2 mg/l of hardness

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Advantages of the Ion-Exchange
Process
• Compared with lime-soda ash softening, ion-
exchange softening has certain advantages, the
main ones being its compactness and its low cost.
• The chemicals used are safer for the operator to
handle and the operation of the zeolite-softening
process is much easier. It can be almost totally
automated.
• The resins have the ability to remove all of the
hardness from the water

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

The ion-exchange process
components
• Ion exchange material
• Ion-exchange units
• Salt storage
• Brine-feeding equipment
• Devices for blending

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Ion exchange material
• There are a number of materials, including some
types of soils, that can act as cation exchangers for
softening.
• A natural green sand called glauconite has very
good exchange capabilities, and it was once widely
used.
• Synthetic zeolites, known as polystyrene resins, are
the ones most commonly used now. Their cost is
reasonable, and it is easy to control the quality of
the resin. They also have much higher ion-exchange
capacities than the natural material.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Example
• If water to be treated contains 10 grains per gallon of
hardness, how many gallons of water would the resin
remove? The tank holds 500 cubic feet of resin with the
capability of removing 45,000 grains per gallon per
cubic foot.

• Gallons = cubic feet x grains per cubic foot

grains per gallon
= 500 cubic feet x 45,000 grains/cubic foot
10 grains per gallon
= 22,500,000 grains
10 grains/gallon
= 2,250,000 gallons before regeneration

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Ion-exchange units
• The units containing the resin resemble pressure filters.
• The units are normally of the downflow type, so the
media also acts as a filter. The size and volume of the
units are dictated by the hardness of the water and the
volume of treated water needed to be produced
between each regeneration cycle.
• The resin is supported by an underdrain system that
removes the treated water and distributes the brine
evenly during the regeneration process. The minimum
depth of the resin should be no less than 24 inches
above the underdrain.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri
Salt storage
• The salt is stored as a brine, ready to be used for
the regeneration of the resin.
• The amount of salt needed ranges from 0.25 to
0.45 pounds for every 1,000 grains of hardness
removed.
• The tank should be coated with a salt-resistant
material to prevent corrosion of the tank walls.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Brine-feeding equipment
• Concentrated brine contains approximately 25
percent salt.
• The brine should be diluted to about 10 percent
before it is added to the tank during regeneration.
• It is generally injected with the use of a venturi or
by the use of a metering pump.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Devices for blending
• A properly operated ion-exchange unit produces a
water with zero hardness but with high corrosivity.
• Since a total hardness of 85 to 100 mg/l is the most
desirable, the effluent from the ion-exchange unit
is generally blended with source water to raise the
hardness in the finished water.
• Blending is normally accomplished by metering
both the effluent from the softener and the raw
water added. Meters are installed in both lines so
that the operator can adjust and monitor the
blend.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

OPERATION OF UNITS
The basic steps in the operation of an ion-exchange
softening unit are:
1. the softening cycle,
2. backwash,
3. regeneration,
4. slow rinse, and
5. fast rinse.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri
Softening Cycle
• The softening cycle involves the feeding of water
into the unit until hardness appears in the effluent
from the unit.
• The cycle ends when 1 to 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.
• Loading rates for synthetic resins are in the area of
10 to 15 gpm/square foot of media surface area.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Backwash Cycle
• Once the hardness breaks through, the softener unit needs to be
regenerated.
• In down-flow units the resin must first be backwashed to loosen
the resin since it becomes compacted by the weight of the water,
and to remove any material that has been filtered out of the
water by the resin.
• The backwash rate is normally 6 to 8 gpm/square foot of zeolite
bed area. The operator needs to apply enough backwash water to
expand the resin bed by about 50 percent.
• The backwash water is usually discharged to a box containing
orifice plates that establish and measure the flow rate.
• Distributors at the top of the unit provide for uniform water
distribution and uniform wash-water collection. Underdrains help
the uniform distribution of the backwash water on the bottom of
the resin.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Regeneration
• To regenerate an ion-exchange unit, concentrated brine
is pumped to the unit from the storage basin.
• The brine is diluted through the injector to a solution
containing about 10 percent salt before it is passed
through the resin.
• The time required for regeneration is about 20 to 35
minutes. The flow rate of brine through the resin is
measured in gallons per minute per cubic foot of
media.
• The brine needs to be in contact with the resin long
enough to allow for complete exchange of the hardness
ions in the resin with sodium ions in the brine.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Rinse Cycle
• The regeneration cycle must be followed by a rinse
cycle to remove the remaining brine from the tank.
• The total amount of rinse water needed is 20 to 35
gallons per cubic foot of resin.
• The rinse is started at a slow rate--2 gpm/square
foot of surface area--and continued until the
chloride concentration of the effluent, which
should be monitored frequently, is quite low.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Disposal of brine
• The total volume of the brine that is used during a
regeneration cycle, together with the rinse water
that follows, varies from 1.5 to 7 percent of the
amount of water softened by the unit.
• The chloride concentration in this wastewater could
be as high as 35,000 to 45,000 mg/l.
• This amount of chlorides will upset a wastewater
treatment plant, so the brine usually will have to be
disposed of by lagooning.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

OPERATING PROBLEMS
Problem areas in operation included:
• breakdown of the resin,
• iron fouling,
• presence of suspended material in the source water, and
• unstable water

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Resin Breakdown
• The synthetic resins will normally last 15 to 20
years, but certain conditions can cause the resin to
breakdown sooner.
• Oxidation by chlorine is probably the most common
cause of resin breakdown.
• When chlorine is used to oxidize iron in the water,
the chlorine should be removed before the ion
exchange unit.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Iron Fouling
• Iron in the source water will seriously affect the ability
of the resin to remove the hardness ions.
• Ferrous iron can be oxidized during the softening and
precipitate out as iron oxide on the resin.
• No amount of brine will remove the iron fouling.
• If the iron oxide is formed before the exchange unit, it
can be filtered out by the resin and removed during the
backwashing of the unit.
• Normally if the iron concentration in the source water
is high, iron removal is provided ahead of the exchange
unit to prevent fouling of the unit.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Suspended material
• Turbidity, organic chemicals, and bacterial slimes
seriously affect the resin by coating it, resulting in
the loss of some of the resin’s exchange capacity.
• The best solution to this problem is the removal of
the suspended matter by the normal water
treatment methods of coagulation, sedimentation,
and filtration before the softening process.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Unstable water
• Any water that has been softened by the ion-
exchange process will be corrosive and will have to
be stabilized to prevent corrosion from taking place
in the distribution system.
• The way to accomplish this is by adding phosphates
or other chemicals to reduce the corrosivity of the
water.

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

DEMINERALIZATION
Water softening & demineralization

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Demineralisation
• Virtually all the dissolved matter in natural water supplies is
in the form of charged ions. Complete deionization (i.e.
demineralisation) can be achieved by using two resins.
Demineralization:

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Demineralisation

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

The Demineralisation Ion
Exchange Operating Cycle
• The demineralisation plant with down flow service
and downflow regeneration (Co-flow regeneration)
operating cycle is as follows:
• Demineralisation service flow/resin exhaustion
• Resin bed backwashing
• Resin regeneration Regeneration cycle
• Resin rinsing

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

 Resin Selectivity – SAC & SBA
• Strong acid cation (SAC) exchanger
o Na most weakly held by cation resin
o Na first to breakthrough the resin bed
• Strong base anion (SBA) exchanger
o SiO2 / HCO3 most weakly held by
anion resin
o SiO2 / HCO3 therefore the first to
break through the resin bed
o SiO2 / HCO3 breakthrough often
occurs when a SAC/SBA plant exhausts

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri
Alternatives to SAC  SBA
• Alternative plant layouts and alternative resins for
improved economics of treating a range of feed
water compositions.
• Examples are:
• Add a Degasser before the SBA unit
• Use Weak Acid Cation resin (WAC) before SAC resin
• Use Weak Base Anion (WBA) resin before SBA resin

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Degassing

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Degasser

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Degasser
• Relies on equilibrium between CO2, HCO3, and pH
• Used to reduce alkalinity in decationised water by stripping
carbon dioxide using air
• Takes load off Anion column. Lower operating cost
• Does little work if the raw water alkalinity is low

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Resin bed backwashing
• Flow to expand resin bed typically 40 - 60%
• Required to:
• De-compact resin bed
• Remove suspended solids and resin fines
• Reclassify the resin bed
• Prevents:
• High bed pressure drop
• Resin bead breakage
• Reduced service flow
• Assists:
• Efficiency of demineralisation & regeneration process

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Regeneration
• Regeneration is the treatment of the resin bed
(chemical) to replace impure cations and anions.
• The spent regenerant containing the undesirable
ions is then discarded to the plant wastewater
system.

Regeneration:

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

Regeneration
• HCl – Hydrochloric Acid
• Can be used at high concentration (e.g. 5% w/v) during
regeneration even on hard water
• Offers higher resin capacity for given regen level (gacid/lResin)
• Good for iron removal
• Needs fume control
• Greater storage volume required
• More expensive OPEX and CAPEX
• H2SO4 – Sulphuric Acid
• Difficult regeneration with high TH / TC ratio
• Heat of dilution with high bulk concentration
• Lower efficiency
• Cheaper OPEX and CAPEX

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri
DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri
Resin Rinsing
• Required to remove regenerant & eluted contaminants
from the resin beds.
• Slow/Displacement rinse
• Downflow of 3BV water at 5BV/h (typical) or dilution water
flow.
• Continuation of the chemical regeneration
• Fast Rinse
• Ideally rinse to drain (min 1-2 BV)
• Recirculation of water round cation and anion resins to save
water
• Co flow plant will recycle to below achievable outlet quality
• Flowrate as feed water flowrate until treated water quality
achieved

DEPARTEMEN TEKNIK KIMIA FT UGM Pengolahan Air & Limbah Industri