TOPIC: WATER CONDITIONING

Water Conditioning is, collectively, the industrialscale process that makes water more acceptable
for an end-use; the process of preparing raw water into the
standard fit to what it is designed for. It may be for drinking, the
industry, or in medicine;
Substances that are ought to be removed,
depending on the end use, include suspended
solids, bacteria, minerals, and hard water ions.
Hard Water:
Contains unacceptable amounts of dissolved
salts of calcium and magnesium; usually present
as bicarbonates, chlorides, sulfates, nitrates
Calcium sulfate CaSO4, Carbonate CO32+, Silicate
(which can also be present in the raw water) form clogging
scales with low thermal conductivity in boilers;
Magnesium silicate, Calcium carbonate CaCO 3
may reduce heat transfer.
Expressed in terms of the dissolved calcium and
magnesium
salts
calculated
as
calcium
carbonate equivalent; expressed in ppm as
CaCO3
2 Classes:
Carbonate
Noncarbonate
Temporary hardness
Permanent hardness
Reduced by heating
Requires chem. Agents
Due to bicarbonates Due
to
sulfates
&
of
calcium
& chlorides of calcium &
magnesium
magnesium

For steam generation in boilers, hard water

creates many problems like (i) scale formation,
(ii) corrosion, (iii) priming and foaming and (iv)
caustic embrittlement.

CaSO4 (high pressure boilers), CaSiO3 or MgSiO3,

Mg(OH)2

Methods for Water Conditioning

I.
ION EXCHANGE
- In water treatment, involves removal of hardness
ions with non-hardness ions
- Uses ion exchange resins
Ion Exchange resin
-Small and microporous bead whose material is
mostly based upon polystyrene-divinylbenzene
(SDVB)
-Organic polymer on which a fixed ion, neutralized
by a counter ion/mobile ion, is permanently
attached. The counter ion being mobile means that it can get
into and out of the resin bead.

Cation-exchange resin bead: fixed ion sulfonates,

mobile ion sodium ion. Anion-exchange resin
bead: fixed ion quaternary ammonium cations as
N+R3, mobile ion Cl-.
With that introduced, we can further define

Ion Exchange
- Reaction in which mobile hydrated ions (counter
ion) of a solid are exchanged, equivalent for
equivalent, for ions of like charge in solution.
- It can take place efficiently if the ion exchange
resin has a higher affinity for the replacement ions
(hardness ions) than the original counter ion.
After Ion exchange is done, the resins undergo

Regeneration:
- Restoration of the ion-exchange resin after
exhaustion; that is, when the limit of its exchange
capacity has been reached.
- Done by passing a corresponding solution through
the inactivated resin bed.
- The softener unit must be temporarily taken out
of service.

History:
1. Thomas Clark patented lime process for
removal of carbonate hardness (1841)
2. Porter soda ash to remove noncarbonated
hardness
2 Kinds:
3. Robert Gans applied zeolites for waterA. A. Cation Exchange
softening in commercial use
- - Occurs when the mobile cation attached to the
negatively charged fixed group on the resin
exchanges for another cation in the solution
Definition of terms:
- Usually of the styrene-divinylbenzene sulfonated synthetic resin
1. Purification removes organic matter,
type, this is stable at high temp., over a wide range of pH, and
microorganisms, and any other undesirable
resistant to oxidizing conditions.
substances for an end-use
-------------------------------------------------------------2. Softening

particularly
removes/reduces
-----------hardness
Treatment:
3. Sludge precipitates that are loose and slimy;
formed by salts that are more soluble in hot 1. 1. Sodium-cation-exchange (RNa+)
Ca2+ and Mg2+ are removed from the hard water as
water (MgCO3, MgSO4, MgCl2, CaCl2)
it exchanges with sodium ions
4. Scale precipitates that are hard; due to the
Process/Reaction:
formation of CaCO3 (low pressure boilers),

In the softener unit, Hard water > Resin Bed > Soft
water

(hard water) (resin)

(*resin)
(soft
water)
(Na-cation-exchanger)
(Ca/Mg-cation
exchanger)

Regeneration:
The bed is washed with a soln of common salt
(NaCl), which removes the Ca and Mg in the form of
their chlorides and simultaneously restores the
cation exchange resin to its sodium state.

(*resin)
(soln in)
(resin) (soln out)
The unit is brought back to service after the by-products and
excess salt are rinsed free.
2. Hydrogen-cation-exchange (RH+)
The exchange resins contain and exchange
hydrogen ions which can remove all cations
(because H+ is lowest in affinity)
Process/Reaction:
In the softener unit, Hard water > Resin Bed > Soft
water
a. Exchanges with bicarbonates:

(hard water)
(sol. CO2)

(resin)

(Na-cation-exchanger)
exchanger)

(*resin)
out)

(soln in)

(resin) (soln

B. Anion Exchange
-Occurs when the mobile anion attached to the
positively charged fixed group on the resin
exchanges for another anion in the solution;
spec. OH-Resins derive their functionality from quaternary
ammonium functional groups.
2 Resin Types:
1. Highly Basic can remove strongly ionized
acids (sulfuric, nitric, hydrochloric), and also,
weakly ionized acids (silicic, carbonic)
2. Weakly Basic can only remove strongly
ionized acids
Reactions:

Process is same with previous exchanges

(with a strongly ionized acid)

(resin)
(untreated water) (*resin)
!!! (as exchanger)
Regeneration:
Highly basic anion exchangers with caustic
soda
Weakly basic , soda ash, ammonium
hydroxide
(based on example of previous reaction)

(*resin)
(soln out)

(soln in)

(resin)

Review:

(*resin)
(Ca/Mg-cation

b. Exchanges with sulfates and chlorides:

(hard water) (resin)

(sulfuric/hydrochloric acid)

It is regenerated with sulfuric acid; most widely

used & most economical

(*resin)

Figure: Resin beads are exhausted. H+ and OH ions

have been released into the water
Ion Exchange technology
Advantages:
Perfect
tool
to
remove
or
exchange
contaminants present in low concentrations. In

(Na-cation-exchanger)
(Ca/Mgcation exchanger)
Acidic water is not desirable so this effluent is either neutralized or
blended with sodium zeolite-treated water.

Regeneration:
Same process with Sodium-cation-exchanger except that

such a case the running time until the resin column is

exhausted can be very long, ranging from a few hours to several
months. When however the concentration of contaminants is
high, say several grams per litre of water, the ion exchange
cycles become exceedingly short and the quantity of
regenerants increases to uneconomical levels.

There is no need to adjust even if the water

hardness varies every time the softener is used

 No sludge formation
Disadvantages:
1. Insoluble impurities or contaminants that
are not ionized cant be removed.

3.

Mixing

and

II.
LIME-SODA PROCESS
It removes Ca and Mg ions as insoluble CaCO 3 and
Mg(OH)2; **whole compound removed, unlike in ion-exchange,
one by one.

Treatment:
1. Lime Ca(OH)2

2. Soda ash Na2CO3

- Only calculated amounts of lime and soda are to be added. Excess

amount of lime & soda causes boiler troubles like caustic
embrittlement.
4.
5.

proportioning of limesoda ash corresponding

to
the
raw water analysis
Pumping of the lime
slurry and soda

Reaction of the reagents

and water, aided by

mixing with or without previous heating ??

6. Coagulation by slow agitation or sludge recirculation
7. Settling/Removal of sludge, and, pumping away of
softened water
8. Washing away of remaining sludge from the tank
bottom and clarifying filters

Advantages: reactions proceed faster,

coagulation
and
precipitation
are
facilitated, and all of the dissolved gases
(e.g. CO2 and air) are driven out.

2 Types:
1. Cold-lime Process
Usually for partial softening of municipal water
& for softening of cooling water

Mg hardness is brought down to almost zero but calcium

hardness remains about 40 ppm.

Process:
a. Calculated quantity of lime and/or soda ash and
water, along with accelerators and coagulators
(to reduce suspended particles) are added to a tank
fitted with a stirrer. **separately
b. After the stirring and softening, the soft water
rises upwards and the sludge settles down.
c. The softened water passes through a filtering
media for further removal of sludge, then, the
filtered water flows out.
Disadvantage: voluminous wet sludge whose
disposal is expensive and troublesome.

**Reducing supersaturation: Recyling fresh/previous sludge back

to the incoming raw water flow results to a more rapid and more
complete reaction, with larger and more easily settled particles in
the newly formed precipitate. This practice also provides costsaving advantages.

2. Hot-lime-soda Process
Almost entirely for conditioning boiler feedwater
Process: Similar with cold lime-soda process,
but, it operates at the boiling point of the water.
Specific:
1. Analysis of raw water
2. Heating of raw water by exhaust steam

III.

PHOSPHATE CONDITIONING
Application: Internal conditioning of boiler
water; conditioning of cooling and process
water
Treatment:
1.
Orthophosphates
and
Complex
phosphates
- precipitate calcium ion reaching the boiler
2. Sodium hexametaphosphate (complex
phosphate) - advantageous where the

boiler water becomes too alkaline. How:

It reduces the alkalinity by reverting to
an acid orthophosphate in the boiler.
Also, it is used for minimizing the
corrosion and pickup of iron by water in
various water systems.

Diagram

IV.
SILICA REMOVAL
Silicate form clogging scales with low thermal
conductivity in boilers; Magnesium silicate may
reduce heat transfer.
Silica is not removed by hydrogen-cation
exchange or sodium-cation exchange; partially
only in lime-soda process.
Treatment:
1. Coagulation and settling (spec. ferric
coagulate) suitable as preliminary steps
especially if the silica concentration in the raw
water is high
2. Dolomitic lime or activated magnesia
V.
DEAERATION
Boiler
corrosion
occurs
by
chemical
or
electrochemical attack of the contents of water,
mainly by dissolved oxygen.
Treatment:
1. Electrode polarization, or organic inhibitors
2. Protective salts covering Fe2+ to interrupt
its reaction with OH- (oxidation of iron)
3. Steam scrubbing - oxygen is removed by
pouring the water down, over a series of
trays contained in a pressurized vessel, and
is scrubbed by steam rising upward; reduce
O2 concentration to about 0.01 ppm.
4. Reducing agents sodium sulfite or
hydrazine hydrate; remove traces of O 2
**(Show rxn)

VI.
DEMINERALIZATION & DESALTING
A. Demineralization
- Removing all the ions in the water; result:
deionized or demineralized water
-

Note: Deionized water must be transported through

stainless steel or glass to keep the pure water from corroding
the transport lines

Process
- Done with hydrogen-cation-exchanger and
anion exchanger (in the hydroxide form)
- The resulting H+ and OH- combine to form
water molecule. Thus the water coming out finally from
the two exchangers is ion free and called
Result: deioinized or demineralized water.

Reaction (Summary):
Hydrogen-cation-exchanger unit

Anion-exchanger unit

Application:
For high-pressure boilers, process and rinse
waters
- Type of system vary according to a. volumes and
compositions of raw water b. effluent-quality
requirements for different uses c. capital and costs
Treatment at different cases:
If silica removal is not required:
1. Hydrogen-cation-exchanger unit
2. Weakly basic anion-exchanger unit
3. Degasifier to remove CO2
If silica removal is required:
1. Hydrogen-cation-exchanger unit
2. Degasifier (usually) to remove CO2 ahead of the
3. Strongly basic anion-exchanger unit
High quality effluent
(Previous steps) followed by polishing units
1. Hydrogen-cation-exchanger unit and SB anionexchanger unit, or
2. Single unit with a mixed bed ionizer of the two

B. Desalting

- Or desalinization; Used to perform partial or

complete demineralization of highly saline waters
(e.g. seawater or brackish waters [water containing
dissolved salts and having very salty taste])
Application:
1. Lowering the saline content suitable for drinking
purposes
2. For use in high pressure boilers/ industrial uses
Treatment:
- Ion-exchange demineralization discussed earlier cant be applied
to the desalting of highly saline waters

1. Electrodialysis

2. Reverse Osmosis

1. Electrodialysis
-This method involves the removal of ions from the
brine solution by applying direct current and
using closely spaced and alternately placed ionsensitive membranes that will allow the passage
of either specific cations or anions.
Process
1) Direct electric current is passed through an
electrodialysis cell where highly saline water
is fed. (Electric field is applied perpendicular to the flow

Note:
-Increased salinity: discarded; Decreased: recirculated
-It does not completely demineralize the water, but reduces
the salinity as to make it suitable for certain uses.

2. Reverse Osmosis
- Osmosis: the flow of solvent from dilute to
concentrated
solution
through
a
semipermeable membrane.
- RO: from concentrated solution to dilute
solution across a semipermeable membrane
by applying hydrostatic pressure in excess
of osmotic pressure.
Membrane material:
1. Cellulose acetate brackish water
2. Polyamides seawater
Process
The used membranes do not allow the solute to
pass, while the solvent is forced through and
collected as a pure solvent.
Diagram

of water.)

2) A. Due to the set-up, anions move towards

the anode, while cations move towards the
cathode.

B. Because of the membranes, cations

pass through cation-exchanger membranes,
and, anions through the anion-exchanger
membranes.

Adv: (i) removal of ionic, non-ionic, colloidal and

high molecular weight solutes from water, (ii) easy
replacement of the semipermeable membrane, (iii)
easy maintenance and economical, as the
membrane lifespan is high
VII.

PURIFICATION (Other methods)

Treatment:
Particles-removal

1. Coagulation and filtration through sand or hard

coal, and, oxidation by aeration remove
organic matter and some microorganisms;
- remove color from the water, remove turbidity

3) As a result, we obtain a salinity decrease in

one space, salinity increase in the next
space, and so on; an alternate streams of
pure water and concentrated salt solution.

(cloudy appearance of water caused by small particles

suspended therein);
*Coagulation / Flocculation
During coagulation, caogulating agent is added to the raw water.
When mixed with the water, this causes the tiny particles of dirt in
the water to stick together or coagulate. Next, groups of dirt
particles stick together to form larger, heavier particles called flocs
which are easier to remove by settling or filtration.
*Diff of precipitation & flocculation: Precipitation means to
transform a water-soluble substance into its insoluble form by
means of a chemical reaction. Adding flocculants and coagulations
aids, the finest suspended compounds or those dissolved in
colloidal form are then transformed into a separable form. This
means that in contrast to precipitation, flocculation is no phase
transition process.
Disinfection

2. Chlorine produces safe and potable water by

disinfecting;

*Disinfection by chlorination can be problematic, in some

(Ref: Fig 3.5 Municipal water treatment
circumstances. Chlorine can react with naturally occurring organic
flowchart from Infilco, Inc.) Steps:
compounds found in the water supply to produce compounds 1. Raw water is aerated to remove iron, odor, & taste.
known as disinfection byproducts (DBPs), which may cause health 2. Softened with lime; Precipitate is coagulated &
hazards.
filtered thereafter.

3. Chloramine made by adding ammonia to 3. Added with chlorine and activated carbon (to
chlorinated water; produces a better-tasting
remove odors and improve flavor)
water; also kills pathogenic organisms
The issue of undesirable byproducts is less serious with
Reducing organic contaminants (mutagenic
chloramine than chlorine. Also, chloramine has a longer
chlorinated organic compounds):
half-life in the distribution system and still maintains
1. Chlorinate the water after filtration and
effective protection against pathogens.
coagulation
2. Dechlorinating
with
sulfites
and
then
4. Ozone also kills pathogenic organisms
Ozone - more cost effective and energy-intensive. It involves ozone
rechlorinating the water with chloramine
being bubbled through the water, breaking down all parasites,
bacteria, and all other harmful organic substances. However, this
method leaves no residual ozone to control

contamination of the water after the process has

been completed.
5. Activated carbon and resins useful in
removing organic compounds
Application: Municipal water treatment
*Requisites of a safe municipal water supply:

Free
from
pathogenic
microorganisms
and
suspended solids
Soft water
Does not have an objectionable taste and odor

Background
Instrumentation
The ion exchange process removes unwanted ions from raw
water by transferring them to a solid material, called an lon
Exchanger, which accepts them while giving back an equivalent
number of desirable species stored on the lon Exchanger
skeleton. The Ion Exchanger has a limited capacity, called its
exchange capacity, for storage of ions on its skeleton. Because
of this, the lon Exchanger eventually becomes saturated with
unwanted ions. It is then washed with a strong regenerating
solution containing the desirable species of ions. These ions
flush out the accumulated undesirable ions, returning the
exchange material to a usable condition. This operation is a
cyclic chemical process, and the complete cycle usually includes
backwash, regeneration, rinsing, and service.