INTRODUCTION

What is a Boiler?

A boiler is a class of vessel used to transform water under pressure into steam by
application of heat

In the boiler furnace, the chemical energy in the fuel is converted into heat

The function of the boiler is to efficiently transfer heat to the contained water

The volume of water increases up to 1600 times as it boils. This is sufficient to

cause explosion

WARNING

Boiler is dangerous and must be handled with care

WHY TREAT BOILER WATER?

Complete pure water is not achievable

Impurities in boiler water include dissolved solids, dissolved gases and suspended
matter

THE MAJOR PROBLEMS ASSOCIATED WITH BOILER FEED WATER

Scaling/deposition

Corrosion – oxygen attack, caustic corrosion

Boiler water carryover

Wasted fuel due to scale may be approximately 2-5%

NOTE: Water tube boilers experience heat flux rates as high as 250,000Btu/hr./ft 2

COMMON IMPURITIES IN RAW WATER

Dissolved solids – These are substances that will dissolve in water, carbonate and
sulphates of calcium and magnesium, which are scale forming when heated)

There are other dissolved solids which are non-scale forming

Suspended solids – These are substances that exist in water as suspended particles.
They are usually minerals or organic in origin. These are not a problem as they can
be filtered.

Dissolved gases – Oxygen and carbon dioxide can be readily dissolved in water.
These gases are aggressive instigators of corrosion.
Scum forming substances – These are mineral impurities that foam and scum, e.g.
soda in form of carbonate, chloride and sulphate

Hardness – Hard water contains scale forming impurities while soft water contains
little or none

There are two types of hardness

Alkaline harness (also known as temporary hardness) Calcium and Magnesium

carbonates are responsible for this type of hardness

These salts dissolve in water to form an alkaline solution. When heat is applied, they
decompose to release carbon dioxide and soft scale or sludge. Their hardness is
removable by boiling

Non-alkaline harness and carbonates (also known as permanent hardness) calcium

and Magnesium but in the form of sulphate and chlorides. These precipitate out of
solution due to their reduced solubility as temperature rises and form hard scales
which are difficult to remove

The presence of silica can also lead to hard scale, which can react with calcium and
magnesium scales to form silicates, which can severely inhibit heat transfer and
cause overheating

Total hardness is the sum of concentrations of calcium and Magnesium ions present
when these are expressed as CaCO3

pH – A numerical value representing a potential hydrogen content of water –which is

a measure of the acidic or alkaline nature of the water

 Conductivity – The symbol of conductance is G.

The unit of conductance is Siemens, named after the 19 th century German

engineer and industrialist Ernst Werner Von Siemens. It used to be called the
mho, which is just Ohms written backwards
v i
R= , G=
i v

i
σ=
p
1 mho/cm = 100s/m

 Alkalinity is a measure of the capacity of water to neutralize acids. Alkalinity of

water is due primarily to the presence of Bicarbonate, carbonate and hydroxide
ions. Salts of weak acids such as Borates may also contribute
 Carbonate alkalinity is a measure of the carbonate and bicarbonate ions in a
solution
 OXYGEN CORROSION PREVENTION IN STEAM GENERATION SYSTEM

 Oxygen in addition of being dissolved in feed water may enter a steam

generator combined with corrosion products such as ferric oxide (Fe2O3), copper
oxide (CuO) etc.
 Oxidized Iron for example is not removed by deaeration and may cause
corrosion in high heat transfer areas of the steam generation

4Fe2O3 + Fe  3Fe3O4

Iron is taken from the coil metal as Fe2O3 is reduced to magnetic Iron oxide
(Fe3O4)

 Hydrazine can minimize this type of attack by reacting with and reducing these
oxidized corrosion products.

N2H4 + 6Fe2O3  4Fe3O4 + N2 + 2H2O

Oxygen is then directly removed by the magnetic Iron oxide formed as shown

4Fe3O4 + O2  Fe2O3

 In practice high initial dosage of hydrazine are needed before a residual is

established. This tends to confirm that Hydrazine is used up by first reacting with
oxidized corrosion products.
 The starting dosage for Hydrazine is usually absent twice the amount needed to
react with oxygen.
 Carbonate alkalinity in the steam generator can hydrolyze under the action of
heat and liberate carbon dioxide which will be carried along with the steam to
form a corrosive carbonic acid product with the condensate in process heat
exchanger or condensate piping.
 Ammonia has been successfully employed for neutralization of carbon dioxide
and elevation of pH. It is anticipated that not more than 0.2 to 0.3 ppm of
ammonia will be required to maintain the desired pH range

SCALE

 The primary cause of scale formation is the fact that the solubility of the scale-
forming salts decreases with an increase in temperature
 The higher the operating temperature (and pressure) in a steam generator the
more insoluble the incrusting salts become.
 The chief mechanism of scale formation is due to the crystallization of scale
forming salts from the solution, locally supersaturated
 Crystallization of scale results directly on the heating surface even when the
solubility of the scale forming salts has not been exceeded in the steam
generator water.
 At boiling temperatures, calcium and Magnesium bicarbonates decompose to
their respective carbonates and carbon dioxide being produced in the reaction
 The solubility of most calcium and magnesium salts decrease with increase in
temperature. These salts are collectively termed “Hardness” Magnesium
sulphate is the exception, but it usually reacts in steam generator water to form
less soluble Magnesium salts
 Calcium sulphate, at higher temperatures decrease in solubility and tends to
deposit out in the hotter parts of the steam generator where scale can cause the
most damage.
 In general all hardness salts are potential scale formers, since they deposit out
of solution as water is heated.
 The solubility of sodium increases as water is heated and does not normally
cause steam generator deposits. Should a higher deposit of sodium be found in a
steam generator deposit, it indicates an unusual condition such as where water
is evaporated to virtual dryness.
 Scale may form other items such as silica or products from silica may deposit out
as calcium silicate and prove to be quite troublesome in steam generator
operation.
 Maintenance of high alkalinity concentration in steam generator water is an aid
in control of this problem, however only limited silica concentrations can be
controlled.
 Soluble iron entering a steam generator with the feed water will be precipitated
by a steam generator water pH of 10 or more and consequently this pH range is
generally maintained in a high pressure steam generator.
 The different types of scale formed, all possess a low degree of heat
conductivity. The presence of scale is therefore equivalent to spreading a thin
film of insulation across the path of heat travel from the hot gases to the steam
generator water. This heat insulating material will retard heat transfer and cause
a loss of steam generator efficiency.
 Even more important than the effect of scale in causing heat loss, however is the
effect of scale causing the overheating of boiler metal and subsequent tube
failure

TREATMENT

Treatment to prevent steam generator scale is needed in every scale. Even though
the feed water hardness is less than 1ppm, treatment is usually required.

One ppm of feed water hardness (or Iron) slipping through a softener adds up to
about 200kg of potential scale a year, in a steam generator making 50,000lbs/hr
(20,000kg/hr).
Treatment involves:

 Controlling hardness precipitation – reaction should occur in the cooler area of

the steam generator drum at or near the feed water entrance. The hardness
 should come out of solution and be suspended in the water rather than
depositing out directly on steam generator metal
 Conditioning steam generator water suspended solids or sludge.
 The sludge must be properly treated before passing to the hot steam generator
area to keep it from sticking to the tubes.
 The excess sludge must be removed by blowdown. This is done by intermittent
blowdown at the low point in the steam release area in the steam generator
drum.

STEAM CONTAMINATION

Steam contamination may occur when steam generator reacts in any one of the
following ways: Foams, Primes or during carryover

FOAMING

 Foaming is the condition resulting from the formation of bubbles on the surface
of the steam generator water

The foam produced may entirely fill the steam space of it may be of relatively
minor depth. In either case, this foaming condition causes appreciable
entrainment of water with the steam. It should be pointed out that demisting
pad and other mechanical equipment are used to prevent the release of wet
steam to the system. Regardless of mechanical provision, steam generator
water should be maintained as pure as possible to contain foaming

PRIMING

 Priming is a more violent and spasmodic action resulting in the throwing of slugs
of steam generator water over with the steam
 This condition can exist because of high water level, broken baffling, a sudden
drastic increase in steam load and a sudden or severe contamination of steam
generator water.
 Very often a combination of several of these conditions contributes to priming.

CARRYOVER

 Carryover is the term applied to the continuous entrainment of relatively small

quantity of steam generator water solids with the steam
 The term carryover is also used to cover the general conditions more exactly
divided into foaming, priming and carryover.
 When steam generator water solids are carried over in the steam (such as silica)
deposits will occur in non-return and stop valves, super heaters, steam piping
and turbines.
 Such deposits can promote failure of super heater tubes and loss in turbine
efficiency

SILICA CARRYOVER

 One of the most common types of carryover is silica carryover

 The key to minimizing silica carryover is to maintain silica content of the steam
generator below 3.5ppm when at an operating pressure of 105.5kgcm -2
(1,500psig)
 The dissolved silica in the steam production under normal operating conditions
would be not more than 0.02ppm.
 With a steam silica content of 0.02ppm or less as determined empirically by
turbine experts and utilities operators, appreciable turbine deposits would not
occur
NOTE: this content is a practical maximum limit

COORDINATED PHOSPHATE TREATMENT

 In the phosphate treatment, a small quantity of caustic is added to the steam

generator to maintain it in an alkaline state, but avoiding the presence of
excessive free hydroxide
 At 5% solution of di/tri-sodium phosphate is injected intermittently or
continuously into the steam generator drum as required to maintain a small
phosphate residual of 10-20ppm
 The primary purpose of phosphate addition to the water is to precipitate the
hardness constituents under the proper pH conditions of between 9.5 and 10.0
 The coordinated phosphate treatment is not generally used in steam generators
operating above 112.5kgcm-2

COORDINATED PHOSPHATE CURVE

 Above is a coordinated phosphate control for control in the moderately high

pressure steam generators operation should be on or below the curve to prevent
free caustic in the steam generator
 If operating above the curve as traces of impurities enter the cycle with the
make-up water, the phosphate will be precipitated producing free hydroxide. The
free hydroxide can be controlled by adding di-sodium phosphate
 Generally, free hydroxide should be maintained within 0 – 1ppm

SOLID ACCUMULATION

 If suspended solids (sludge) and dissolved solids are allowed to accumulate

because of low blowdown rate, the possibility of sludge deposits and carryover in
the steam is enhanced
 During start up periods, suspended Iron might be high in relation to total solids
and blowdown might be partly or entirely based on Iron concentration
 High suspended Iron in steam generator water can produce serious deposit
problems
 The importance of frequent intermittent high rate blowdown during both the
initial and subsequent startups should be emphasized to ensure as complete a
removal of solids as possible in a minimum period of time
 If the steam generator water is visibly dirty at the blowdown after heating is
started, the blowdown frequency should be about twice an hour for a duration of
one to two minutes at each blowdown point
 When the water appearance is about normal, samples should be analyzed for
total dissolved solids, Iron and silica
 There will be frequent periods of two or three hours duration, such as during
regeneration of the demineralizer unit, that a slight increase of solids will be
present in the steam generator feed water.
 This slight increase of solids may be compensated for by phosphate injection
and slightly increased blowdown

PHOSPHATE HIDEOUT

 Phosphate hideout is not usually encountered in the operation 105-kgcm-2

steam generators, but will probably be evident to some degree.
 It is the term used to express the phenomenon of the partial disappearance of
phosphate in the steam generator water upon increase in load and its
reappearance upon load reduction
 The term is used where the hideout is greater than 5ppm change between high
load and low load
 High pressure steam generator operation, phosphate residual levels are
maintained at a low level range to avoid appreciable phosphate hideout
 A precise blowdown schedule cannot be arrived at by water analysis alone
 Inspection of system components for deposits and laboratory analysis of
sampled deposits after a period of operation, and any remedial measures taken
are required before attempting finalization of blowdown practice
 Intermittent blowdown is not efficient at maintaining a consistent level of solids
in the steam generator, so a continuous blowdown connection should be
provided to minimize solid fluctuation in the steam generator water and to
provide a more accurate control of the rate
 This blowdown connection is usually located on the steam drum near the
discharge from the generating tubes and away from the feed water inlet
 An internal collector pipe is usually supplied for this nozzle
 Until the steam generator water purity approaches normal, the steam generator
pressure should be limited to approximately 35.2kgcm -2 with minimum steam
load
 As steam generator water purity approaches normal the blow down frequency
can be reduced accordingly and pressure can be gradually increased
 Blowdown from furnace tubes should be stopped
 Analysis of steam generator water samples should be made rather frequently
since relatively wide fluctuations could conceivably occur in the quality of the
water
 Before hot gases are started to elements of steam generator system not yet in
service, they should be thoroughly blown down to be sure they are free of any
solid accumulation
 The blowdown will also preheat those elements for operation.
NOTE: Once they are in service as a general rule, no heat receiving tube bundle
should be blown down
 It is also essential that the steam generator be properly secured during short
term out of service periods which could result from equipment malfunction or by
startup delays
 During these periods, the steam generator drum should be immediately
blanketed with Nitrogen and a positive pressure of Nitrogen maintained until
such time that the steam generator system is readied for steam production
 In addition small residual of O2 scavenger should be maintained

CONCLUSION

 The expected steam quality of 50ppb is achieved by using a high purity feed
water, an effective feed water treatment program, and by good control of the
steam generator water composition in a well-designed system with proper and
efficient operation supported by accurate sample analyses