Boiler Water Treatment

and case studies

INTRODUCTION
WATER QUALITY

EXTERNAL WATER TREATMENT PROCESSES

Clarification

Deaeration

Precipitation Softening

Demineralizers
INTERNAL WATER TREATMENT PROCESSES

Anti-foam agents
conditioning treatment
Prevention of scale
Prevention of corrosion

Blow down
- CASE STUDY
- SUMMARY AND CONCLUSION

1. INTRODUCTION
Water quality is an important determinant of the
efficient operation of boilers and steam systems.
water
Evaporates

Impurities
become
concentrated

Deposited
on heating
Surfaces (Scale)

Reduces
heat transfer

It has been estimated that for:

every 20 oC increase in flue gas temperature
the boiler efficiency drops by one percentage point.

Boiler water must be treated before

being fed to the system

Lower
Efficiency

WATER QUALITY MUST BE MAINTAINED

If not
treated
properly

Maintain
Quality by
Increased
Blowdown

1. INTRODUCTION
Increase
Wasted
Energy

HOW?

If
treated
properly
Reduced blowdown energy costs.
Increased boiler life,
Problem-free steam supply and
Savings from reduced maintenance
requirements

Water
Treatment
will Pay for
Itself

2. WATER QUALITY
2.1 Water-borne Impurities
Water is a universal solvent and carrier.

It normally contains many impurities taken

from its surroundings.
Whether ground or surface water, it can be
expected to contain the following in
varying amounts:

WATER-BORNE IMPURITIES:

Dissolved and suspended inorganic

compounds
Dissolved and insoluble organic
compounds
Dissolved gases
Microorganisms

1. Dissolved / Suspended inorganic compounds:

carbonates, CO3-nitrates, NO3magnesium, Mg++

Potassium, K+

bicarbonates, HCO3sulfates, SO4

chlorides of calcium
CaCl2
sodium, Na+

(picked up from the earths crust as water

accumulates on the ground)
inorganic suspended materials, such as:

clay, silt, sand, soil, and metal oxides

2. Dissolved / Insoluble organic compounds:

organic acids
insoluble organic matter such as:
leaves,
dead bacteria, and
other biological products and
industrial waste

3. Dissolved gases:

oxygen,
nitrogen,
carbon dioxide,

sulfur dioxide,
methane, and

hydrogen sulfide absorbed from

the atmosphere and sub-surface
sources.

4. Micro-organisms:

bacteria,
algae, and
fungi.

Impurities Affecting Steam

Generation

Suspended
Solids

Dissolved
Inorganic
Compounds

Dissolved
Gases

2.2 Terminology
Acidity: The amount of hydrogen ions (H + )
present in water.
Alkalinity: The term alkalinity refers to the
presence of:
hydroxide (OH-),
carbonate (CO3 - - ), and/or
bicarbonate (HCO3 - ) ions in water.

 pH: Negative logarithm of hydrogen

ion concentration to the base 10
pH = log10 [H+]

Acidic- pH < 7 ( H+ > OH-)

pH: 0- 14

Neutral- pH = 7
Alkaline- pH >7 (OH- > H+)

Cations and Anions: Salts dissolved in water

are completely ionized .

For example, calcium sulfate will be present as

calcium (Ca++) and sulfate (SO4 - - ) ions.
Positive ions are termed as: cations
Negative ions as:
anions.
Common ions of
water impurities
are:

 Hardness:

The term originates from the inability of

certain waters to lather soap due to the presence of
calcium and magnesium compounds which precipitate
soap .
The presence of these compounds in water causes scale
deposits in boilers. Hardness can be termed as:

Temporary (carbonate) due to the presence of

bicarbonates of calcium and magnesium which
can be removed by boiling the water.

Permanent (noncarbonate) caused by

sulfates,
chlorides,

and

nitrates of calcium and magnesium present in

water.

 Suspended Solids:
These are insoluble solids contributing to
the turbidity and coloration of water. Amount
of suspended solids can be measured with
turbidity meters.

TDS (Total Dissolved Solids):

A self-explanatory term referring to the
amount of total dissolved solids present in
water. It is usually estimated by multiplying
the conductivity of water with an appropriate
conversion factor.

 Silica Content:
It is the concentration of silicic acid
H2SiO3 (expressed as SiO2) in raw
water.
It can not be removed by the process of
settling and filtration.
It can only be removed by the ion
exchange process.

2.3 Problems Caused

by Impure Water:

a) Scale deposition
b) Corrosion
in boiler tubes

c) Carryover

2.3.1 Scale and Deposit Formation

The formation of hard scale on the
heating surfaces.
a low
conductivity of:
Scale

has

thermal

11 to 36 mW/cm K
It prevents proper cooling of the
metal surface.
Thermal conductivity

Effect of Thermal Conductivity

Composition of typical hard boiler
scales and conductivities of scales
and metals.

Thermal conductivity of various scales:

Effect of Thermal Conductivity

q= 315000 W/m2
Water side
177 C

Without scale:

Water film
190 C

k for water= 6 mW/cm K

22.2 mm metal

346 C
Gas side

q= 315000 W/m2
Water side

With scale:

Water film

k for water= 6 mW/cm K

177 C

302 C

0.754 mm scale

22.2 mm metal

457C
Gas side

WHY SCALES ARE FORMED?

Scale and related deposits arise if the concentration of salts
exceeds their solubility. Parts of the boiler particularly
susceptible to scale formation are water and furnace tubes,
where heat transfer and water evaporation rates are high. In
boilers, scale and deposit formation are caused by the
following mechanisms:
1. High concentration of dissolved salts. This occurs during
evaporation in the boiler when chemicals with low solubility
precipitate / crystallize out, for example, salts of calcium,
magnesium, and silica, etc.
2. Formation of less soluble salts by chemical reaction, e.g.,
Ca(HCO3 )2 + Heat
CaCO3 + CO2 + H2 O

WATER TREATMENT
WATER TREATMENT

EXTERNAL

Outside the
boiler

INTERNAL

Inside the
Boiler

2. EXTERNAL WATER TREATMENT

Definition:
Treatment of water before entering the boiler.

Important When:
Impurities in water are unacceptably high.
Impurities include:
Suspended solids
Dissolved gases
Dissolved salts
Organic matter
Iron & magnesium oxides & hydroxides

Treatment Processes:

Clarification

Deaeration
Precipitation Softening

Demineralizers

Choice of processes
depends on raw water
characteristics

Fig. Water Treatment Diagram

IMPURITY

Sedimentation for large

solids (required for present- day
water supply quality )

I. Suspended Solids

A) Coagulation & Flocculation

B) Filtration

Clarification

A) Coagulation & Flocculation

Negatively charged particles are suspended in water.

Chemical coagulants added to water to acquire positive

charge
Alum
Aluminum sulphate
Ferrous sulphate

How to administer coagulant?

Dosed in the form of a solution with
5- 10% concentration

Ferric chloride, FeCl3

Precipitate negatively charged suspended particles as

neutralized floc.

 Gentle agitation.
Collects floc into larger aggregates
Settle & removed as sludge

B) Filtration
Suspended particles are removed when water
passes through a bed of granular materials known as
the filter media.
The filter media usually comprise of sand or a
combination of:
sand,
anthracite, or
some other suitable inert material.

Filtration may be carried out under gravity flow or

pressure flow. Pressure filtration is commonly used
in industry.

Classification:

Filters are classified according to the type of

filter media employed such as:
Single medium,
Dual media, or

Multimedia.
Dual and multimedia filters
are more effective and
operate at higher flow rates
than single medium sand
filters

Sand filters operate at:

Flow rates of approximately 5 m3/hr m2
filter area.
Head loss (pressure drop) of 0.3 to 2.7
meters.

Backwash water, which is required to

periodically purge the filter media of
accumulated particles, is 2% to 4% of water
filtered (30- 37 m3/hr).

24

As the build up of retained suspended

particles on the filter media increases, head
loss reaches a predetermined value (usually
0.2 bar), backwash in upward direction is
started,

The backwash flow rate is sufficient to

expand and loosen the bed by at least 10%
of bed volume but not enough to take away
the filter media.

6- 18

Dual and multimedia sand filters:

Additional filtration using granular
activated carbon is sometimes
required to protect ion exchange
beds downstream from:

16
18

traces of chlorine,
9

oxidants, and
dissolved organic matter.

Operation:
Flow rates in the range of 7. 5 to
20 m3/hr m2 filter area
Head loss initially at 0.3 m
increasing to 2.7 m of water.
Backwash needs to be carried
out using approximately 6% of
the water filtered (20- 30 m3/hr).

6- 18

6- 18

Fine sand
Medium sand
Gravel
Graduated

Normal operation

Back wash

1.2 m

For
Backwash

IMPURITY

II. Dissolved Gases

1. Oxygen

Deaeration

2. Carbon Dioxide
Lime soda
precipitation
Degasser with ion
exchange system

Deaerator

DEAERATION:

Dissolved gases in water can cause corrosion of

boiler surfaces.

A deaerator is used to expel dissolved gases,

oxygen in particular, from the water prior to its use.
This also
scavengers.

reduces

the

need

for

oxygen

For boiler feedwater, deaeration by steam heating

is generally used for the following reasons:
1. Steam for heating water is easily available;

2. The condensate from the steam does not contaminate

water;
3. Water is preheated before it is fed to the boiler; and
4. The process is very cost effective.

These deaerators reduce the dissolved oxygen

content to 7 ppb and below.
Even
a
welldesigned feedwater
tank kept above 90
oC by minor steam
purging
will
effectively
reduce
dissolved
oxygen.
Where
a
high
percentage of hot
condensate is being
recovered and the
amount of makeup
comparatively small,
a deaerator may not
be
necessary,
particularly
for
smaller boilers.

For smaller boilers you may not need

a deaerator !!!

Boiler hot well feedwater tank

Solubility of oxygen versus temperature & pressure

100 C

Solubility of oxygen versus temperature

Tray type deaerators:

IMPURITY

III. Dissolved Solids / Hardness

A) Precipitation Softening

B) Demineralizers

Hardness, CO2

TDS / Hardness

1. Ion exchange

2. Membrane processes

2.1 Reverse Osmosis, RO

2.2 Electrodyalysis, ED

Raw Water: Contains neutral salts, e.g.

CaCl2 NaCl Ca(HCO3)2 -

Na 11, Cl 17

A) PRECIPITATION SOFTENING

B) Demineralizers
1. Ion Exchange

Exchange of undesirable ions of dissolved

inorganic salts in the water with a more benign
ion obtained from an insoluble material.
Basic Processes:
Anion

removes ve ions

Cation

removes +ve ions

Types of Ion Exchange Reactions:

STRONG: Converts neutral salts into their corresponding

acids & bases respectively. (Salt Splitting).
WEAK: Does not have this ability.

Vertical Downflow Ion Exchange Unit:

PROCESS STEPS:

1. Reaction Cycle
2. Backwash Cycle
3. Regeneration Cycle
4. Slow Rinse Cycle
5. Fast Rinse Cycle

A) Strong Acid Cation Exchange:

1. Reaction Cycle:

Resin
(R1)

Feedwater
Has Salts (e.g.
CaCl2
Effluent has
HCl and no
Ca
Resin

After
reaction
Ca(R1)2
Salt
Product
Carbonic acid

2. Backwash

Idea:
Loosens Bed.
Removes Suspended

Solids

Backwash: 10- 20 m3/hr for ambient temperature

For hot services 30- 37 m3/hr

3. Regeneration Cycle:

Rate: 4- 8 Bed Volume/ hr

Regenerant
(30% HCl
solution)
Diluted inside to
4- 10% w/w.

Regenerated
Resin

HCl
Bed material
Waste

4. Slow Rinse:

Service:
15- 20 m3/hr

Rate: 4- 8 Bed Volume/ hr

Regenerant is washed out of the resin bed
Quantity of rinse water

Half resin bed

5. Fast Rinse:

Rate: 12 Bed Volume / hr

Washes away the remaining regenerant from the resin bed

Strong acid cation in hydrogen form:

Regenerant HCl

Raw Water

(30% HCl solution)

Diluted inside to 4- 10% w/w.

CaCl2
Semi-treated water

NaCl

Ca(HCO3)2

Softened water (pH: 2.8-3)

HCl, Hydrochloric Acid

To drain:

H2CO3, Carbonic Acid

CaCl2
To next degasser or ion
exchange bed

B) Degasser (Decarbonator for CO2 removal):

Semi Treated Water

Vent (CO2 is removed)

HCl, Hydrochloric Acid

H2CO3, Carbonic Acid
Blower
HCl, Hydrochloric Acid

C) Strong Base Anion Exchange:

From Cation

Pure Water

Resin

Regenerant

Drain

Regenerant: Caustic Soda 50% solution- Diluted inside to

about 4% w/w.

C) Strong Base Anion Exchange Resins, R3:

Regenerant, NaOH
Solution 50%
Sodium Hydroxide

Semi Treated
Water
HCl

Treated water
To drain:
NaCl

Softened water, H2O

(pH: 8.5-9)

Two Stage Strong Acid/ Strong Base

Demineralizer, with Degasser
Regenerant
Hydrochloric Acid

Regenerant
Sodium Hydroxide

VentCO2

NaOH

HCl
Raw Water
CaCl2
NaCl

Strong
Acid
Cation

Blower

Degasser
HCl

Strong
Base
Anion

Treated Water
pH: 8.5- 9

Ca(HCO3)2
Semi-treated water
To drain:

(pH: 2.8-3)

To drain:

CaCl2

HCl, H2CO3 (Carbonic

Acid)

NaCl

What is a Demineralizer?
The removal of all mineral (inorganic) salts dissolved in water.
Degree of removal depends on the process used.

How to Choose a Demineralizer?

1. Two stage: Strong Cation & Strong Anion:
Removes: Dissolved mineral salts/ CO2/ Silica

2. Two stage: Strong Cation & Weak Anion:

Removes: Dissolved mineral salts.
No effect on CO2 & Silica
3. Mixed Bed: (Cation & Anion in a single column)
Removes: Dissolved mineral salts/ CO2/ Silica
Produces very pure water

Selection of an Ion Exchange Process:

Raw
Sodium Two Stage:
Item

Strong/
Weak

Two Stage:
Strong/
Strong

Mixed
Bed

Water

Softening

TDS ppm

350

350

>3

<2

<1

Total
Hardness
ppm

300

<5

__

__

__

Alkalinity
ppm

270

270

__

<2

__

Permanent
Hardness
ppm

30

<5

__

__

__

CO2

10

280

__

__

pH

7.7

7.7

4.5

8.4

7.0

Silica

<0.2

<0.05

Cost Factor

---

10

15

Selection of an Ion Exchange Process:

SAC

WBA

Most economical when:

Silica
CO2
Removal is not essential
In this case, silicate and carbonate anions slip through the
anion exchanger downstream as it is a weak base type

Selection of an Ion Exchange Process:

SAC

WAB

DG

Most economical when:

Silica
Removal is not essential, but CO2 removal is essential

In this case, silicate anions slip through the anion exchanger downstream as
it is a weak base type. The CO3 anions escaping arrest by WBA, form
gaseous carbon dioxide with the H+ protons liberated in the SAC bed. CO2
is eliminated in the degasifier.

Selection of an Ion Exchange Process:

SAC

SBA

Most economical when:

Removal of silica along with other anions, where alkalinity is low.
SAC eliminates all cations associated with other strong and weak acids, and
SBA bed removes all anions with both strong and weak acids, viz silicic
acid.

Selection of an Ion Exchange Process:

SAC

DG

SBA

Most economical when:

Removal of silica along with other anions, where alkalinity is high.
SAC eliminates all cations associated with other strong and weak acids, and
SBA bed removes all anions with both strong and weak acids, viz silicic
acid.

Also, much of the carbonate alkalinity will be eliminated in the degasifier

2 H+

+ CO3--

H2O + CO2 (from SAC bed)

Thereby reducing the load on SBA.

Softening: Softening process does not affect:

1. alkalinity,
2. silica, and
3. dissolved solids content of water;
Demineralizers:
Advantages:
Reduction of scale formation by removal of all
dissolved salts including silica- of particular
importance in high pressure boilers.
TDS reduction reduces boiler blowdown: Savings in
enrgy & chemicals.
Producing high purity water.
Limitations:
Raw water turbidity and the presence of iron and
aluminum can be detrimental for the ion exchanger;
and
Strong oxidizing agents, such as chlorine present in
the raw water will attack the resin.

Advantages:
1. Softened water has low scaling tendency;

2. Operation is simple and reliable; automatic

regeneration is possible at a reasonable
cost;
3.

Regenerant
inexpensive;

is

easy

to

handle

and

4. Softeners are easily available and efficient;

and
5. Variations in water flow rates have, to a
large extent, no effect on treated water
quality.

External Water Treatment Plant

Vent
O2

Vent
CO2

DEARATOR

Raw
water
S
A
N
D

A
N
T
H
R
A
C
IT
E

Filters

C
A
T
I
O
N

DG

A
N
I
O
N

Storage Tank

STORAGE

TO
BOILER

Demineralizer

Waste to drain

3. INTERNAL WATER TREATMENT

EXTERNAL TREATMENT

Boiler feedwater may contain

contaminants that can cause:
Deposits / Corrosion / Carryover.

NEED INTERNAL TREATMENT

Reactions induced within the boiler system to render the water

less harmful to system operation and integrity.
Scale formation is reduced

Converting hardness salts to a

free-flowing sludge

Corrosion is minimized
a) Chemically removing
dissolved oxygen
b) Keeping water alkaline

External treatment cannot replace internal conditioning

completely, but is only used as a supplement when
excessively impure water would result in too high a need for
chemical reactants or products for practical or economical
removal from the boiler.

Internal Treatment Programs

Precipitating
I. Prevention of scale:
a) Control of Hardness

Chelating
Sequestering

b) Maintain sufficient
alkalinity

appropriate chemical
reactions

c) Sludge
conditioning

to keep suspended
particles
and
precipitates formed in a
non adhering state

d) Keep TDS
within limits

II. Prevention of corrosion:

a) In boilers by:
i) Scavenging of oxygen;
ii) Formation of a protective film;
iii) Maintaining sufficient alkalinity.
b) In condensate lines by:
i) Neutralizing carbon dioxide;
ii) Formation of a protective film.

Internal Treatment Programs

Prevention of scale:

a) Control of Hardness
Precipitating
Chelating
Sequestering

Hardness: The term originates from the inability of

certain waters to lather soap due to the presence of
calcium and magnesium compounds which precipitate
soap .
The presence of these compounds in water causes scale
deposits in boilers. Hardness can be termed as:
Temporary

presence of bicarbonates of calcium and magnesium

which can be removed by boiling the water.
Permanent (noncarbonate)
sulfates,
chlorides,
nitrates

3.1 Precipitation Program

Scale formation inside the boiler can be eliminated to a large
extent by maintaining a controlled dosage of either:

1. Carbonate alkalinity or
2. Phosphate alkalinity
in the water to precipitate out the undesired compounds.

3.1.1 Carbonate Cycle

In this form of treatment a controlled reserve of
carbonate alkalinity is continuously maintained in the
boiler water by:

the addition of sodium carbonate (Na2CO3), and

the addition of sodium hydroxide (NaOH)

Both must be present

In this way hardness salts present in the feedwater are

precipitated in the form of sludge:
calcium as: calcium carbonate (CaCO3)
magnesium as:
magnesium hydroxide (Mg(OH)2) or

magnesium silicate (MgSiO3)

ions are present.

when silicate

Sodium
carbonate
Caustic Soda

The carbonate cycle is recommended if the following three

conditions are met:

1. Boiler operating pressure is below 14 barg

2. Feedwater hardness is 70 ppm or more;

3. Total alkalinity is equal to or more than total

hardness

Exhibit 4.1: Breakdown of

sodium carbonate (Na2CO3)
with pressure

At elevated pressures,
carbonates do not exist due to
their breakdown into
hydroxides.
For this reason, a carbonate
program is not suitable for
boilers operating above 14
barg.

Major Drawbacks:
The major drawbacks of this type of treatment are:

1. the large amounts of sludge produced and

2. the large amount of carbon dioxide liberated from
the reactions. ( less if Caustic Soda NaOH is used
and not Soda Ash Na2CO3 ).
The carbonate cycle must be assisted with a suitable polymer
or sludge conditioner to keep the precipitates formed in a
mobile state for their easy removal through blowdown.
These will prevent, for example, the calcium carbonate from
adhering to the heating surfaces and hence baking on as
scale.

(Sodium Phosphates)

If more not
economical
Max. pressure 41 barg.

At higher pressures total hardness of feedwater should not

exceed 10 ppm .

Again the use of a sludge conditioner in a phosphate cycle is

highly desirable in order to keep the precipitates in a
nonadhering state.

Item

Raw
Water

Sodium
Softenin
g

TDS ppm

350

350

>3

<2

<1

Total
Hardness
ppm

300

<5

__

__

__

Alkalinity
ppm

270

270

__

<2

__

Permanent
Hardness
ppm

30

<5

__

__

__

CO2

10

280

__

__

pH

7.7

7.7

4.5

8.4

7.0

<0.2

<0.05

Silica

Two Stage:
Two Stage:
Strong/Wea Strong/Stron
k
g

Mixed
Bed

3.2. Nonprecipitating Program

chelants or
Hardness salts are made soluble with the addition of:
3.2.1 Chelating Program:

sequestrants

Chelating chemicals such as:

Alternatives to Phosphate
EDTA

(Ethylene Diamine Tetracetic Acid),

NTA

(Nitrilo Triacetic Acid) and their salts

They make soluble complexes with the hardness salts and keep them in
solution. The complexes formed are stable at high pressures.

For chelation to work properly:

- the hardness of boiler water should not exceed 1.5 ppm (by economics)
- and pressure of boiler water should not exceed 90 barg.

- If dosed in excess, chelants can corrode boiler internals.

- On the other hand, underdosing can cause scale
formation.
Therefore, the dosage control limits are very narrow for a
successful implementation. In a free chelant program only
a chelant is used in the boiler.

Here iron corrosion may be a problem due to the presence

of the free chelant. To eliminate or reduce this problem , a
blend of chelant plus a polymer is employed which results
in a minimum quantity of free chelant .
This chelant plus polymer program effectively reduces the
chances of iron corrosion.

Alternatively, the chelant may be used with a phosphate to

inhibit virtually any corrosion potential that might exist
with a slight excess of free chelant.

Chelants can be supplemented with scale control polymers

such as acrylates for better results.

Chelating agents are expensive and must be monitored and

controlled with great care although the analytical
procedures for testing their concentrations are difficult.

3.2.2 Sequestering Program (Polymers)

Sequestrants :

render hardness ions ineffective by

forming complexes with them

The method is best suited for feedwater:

Hardness up to 10 ppm
A maximum pressure of 41 barg.
Sequestrants are very effective: 1 ppm of sequestrant can
hold 100 ppm of scalant in solution, and are thus proving
useful and economical.
polymer phosphonates,
Some common
examples are:

polyacrylates, and
polymaliec acid

Internal Treatment Programs

1. Prevention of scale:

b) Maintain sufficient
alkalinity

appropriate chemical
reactions

Proper alkalinity in the boiler water:

Precipitates out hardness

Inhibits acid corrosion.

3.3.2 Alkalinity Control

1. Caustic Soda (Sodium hydroxide)
2. Soda Ash (sodium carbonate)
are the main alkalinity builders in boilers at low pressures. Some
phosphates are also alkaline, and are also employed to maintain
alkalinity in boilers.

The recommended pH of boiler feedwater is 8.5 to 9.2,

but where copper heaters are also present the suggested pH
range is 9.2 to 9.5.

An alkalinity of around 15 ppm is usually preferred in boiler

feedwater for low and moderate pressure boilers.

Coordinated pH/ Phosphate Program

In a coordinated pH/ phosphate program the sodium-tophosphate molar ratio is held at 3: 1 in the boiler,

In a congruent phosphate program the sodium-to-phosphate

molar ratio is maintained between 2.6 and 2.8 (see Exhibit 4.3
for coordinated and congruent control in high pressure boilers).
The aim of coordinated and congruent programs is to eliminate
free caustic alkalinity which, if present, can cause caustic
corrosion at moderate to high pressures.
Sodium hydroxide alkalinity also keeps silica in solution if the
silica-to-caustic ratio does not exceed 0.4. Silica scale is very
hard to remove and also has very high resistance to heat
transfer.

Cordinated and
congruent alkalinity
control programs.

Phosphate/pH coordinated control maintains fixed ratio of sodium to phosphate in

boiler to avoid free alkalinity (lower region ratio below 3.0). By controlled addition of
mono-, di-, and tri-sodium phosphate. Tinted area is region most applicable to lowand moderate-pressure boilers. Higher pressure systems are limited to ratios
between 2 .6 and 2. 8 and 1 to 6 ppm phosphate concentrations.

Internal Treatment Programs

1. Prevention of scale:

c) Sludge
conditioning

to keep suspended
particles
and
precipitates formed in a
adhering state

5.3.1 Sludge Conditioning

This term applies to chemicals that do not let solids in
the boiler to form scale.

They keep the solids in a mobile powdery state for their

easy removal through blowdown.
They distort, disperse and modify the crystals and
hence check the growth of hard scales.
Naturally occurring tannins, lignins, and starches have
long been used as sludge conditioners.
Synthetic polymers of various types, which are much
more effective, are also now in use. They include
polyacrylates, polymethacrylates, polysulfonates, and
organic phosphates

5. INTERNAL WATER TREATMENT

Internal Treatment Programs

1. Prevention of scale:

d) TDS within limits

Total Dissolved Solids (TDS)

Control of TDS is of great significance in a boiler water treatment
program. TDS control limits depend on the operating pressure of the
boiler but the following factors should be kept in mind when
monitoring TDS levels:

1. Low TDS can lead to unnecessary blowdown and

a subsequent waste of energy.

2. Excessive
formation.

dissolved

solids

enhances

scale

3. High TDS levels accelerate corrosion by

increasing water conductivity.
4. Dissolved solids can also contribute to priming
and foaming problems.

2. Prevention of corrosion:
a) In boilers by:
i) Scavenging of oxygen;
ii) Formation of a protective film;
iii) Maintaining sufficient alkalinity.

i) Scavenging of oxygen

i) Scavenging of oxygen
1. Sodium Sulfite
The reaction rate of sodium sulfite is slow.
2Na2SO3 + O2

2Na2S04

(Sodium Sulphate)

Comment:
1 ppm of oxygen stoichiometrically requires 7.88 ppm of 100% sodium
sulfite (Na2S03).

In practice, 1 ppm of oxygen requires 8 ppm of sodium sulfite. The

major disadvantage in its use is that 8 ppm sodium sulfite contributes
9 ppm of sodium sulfate to total dissolved solids in the boiler,
consequently.

Sodium sulfite is recommended for boilers operating:

- pressures below 69 barg, preferably below 41 barg,
- its use is permitted in the food industry.

increasing
blowdown

2. Hydrazine
Hydrazine (N2H4) can economically remove small amounts of dissolved
oxygen. In addition, it reacts to produce nitrogen and water, thereby leaving
the TDS level of the water unaffected:

N2H4 + 02

N2 + H2O

Theoretically 1 ppm of hydrazine is required to react with 1 ppm dissolved

oxygen, but actually 1 .5 to 2 ppm of hydrazine are required per 1 ppm
oxygen. A hydrazine reserve in boiler water is maintained in the range of 0.1 to
0.3 ppm.

Any excess hydrazine decomposes to form ammonia (NH3) according to:

3N2H4

N2 + 4NH3

This decomposition also occurs at 270 C. Ammonia, in the presence of oxygen,

increases corrosion of nonferrous alloys. Use of hydrazine above 270 should be
carefully considered. Hydrazine also reacts with ferric oxide (Fe2O3) to form
a passive magnetite film on the boiler surface, preventing further corrosion:
6Fe2O3 + N2H4

4Fe3O4 + N2 + 2H2O

5. INTERNAL WATER TREATMENT

NOTE:
Hydrazine is toxic (CARCENOGENIC) with a very low flash point
and should be handled with caution as a 15% aqueous solution.

Its use is prohibited in food industry.

Together with sodium sulphite, its application should be carefully
evaluated against the risks, especially in hospitals, etc.

5. INTERNAL WATER TREATMENT

2. Prevention of corrosion:

b) In condensate lines by:

i) neutralizing carbon dioxide;
ii) formation of a protective film.

5.4.2 Treatment for Condensnte Lines

Apart from oxygen corrosion carbon
dioxide corrosion can be a serious
ailment of condensate lines.
The carbon dioxide may be formed by
the decomposition of carbonate or
bicarbonate
alkalinity
at
high
temperature organic matter, use of soda
ash, etc.
Dissolved carbon dioxide in the form of
carbonic acid causes acidic corrosion. By
countering
the
low
pH
with
neutralizing, amines or encouraging
the growth of a nonwettable organic film
on the metal surfaces with filming
amines to prevent contact with the
corrosive condensate, carbonic acidinduced corrosion can be checked.

5.4.2.1 Neutralizing Amines (Unsuitable for food and beverage)

To combat carbon dioxide corrosion, volatile neutralizing amines are
employed to neutralize the waters acidity.
Examples are:
morpholine, cyclohexylanine, diethylaminoethanol,
AMPC (2 amino-2 methyl- 1 proponol).

and

These are employed to maintain a condensate pH in the range 7.8 to

8.5.
All of these amines arc volatile and distill over in steam to dissolve
readily in the condensate. Being alkaline, they neutralize the carbonic
acid present in water and thus overcome low pH values and corrosion.
From the estimates of carbon dioxide produced due to carbonate
breakdow, a dosage of neutralizing amines is calculated to maintain
the proper pH for avoiding corrosion.

3.4.2.2 Filming Amines

These amines, when fed in the boiler, volatilize with
steam and condense to form a monomolecular film in
condensate lines, providing protection from oxygen and
carbon dioxide corrosion.
The treatment level, 1 to 3 ppm of the pure amine, is
independent of carbon dioxide or oxygen concentration.
Octadecylaamine,
hexadecylamine,
and
dioctadecylamine are a typical examples of filming
amines.

3.3.5 Prevention of Carryover, Foaming, and Priming

Priming usually results from:
A sudden reduction in boiler pressure caused by a rapid
increase in the boiler steam load. Bubbles then form
throughout the volume of water, increasing the water
level in the boiler and thereby drenching the separators,
etc.
Priming is similarly caused by an excessively high
water level following a rapid load reduction.
Foaming is the formation of steam-inhibiting surface
bubbles which can lead to the mechanical entrainment of
water droplets (and suspended particles) into the steam.