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Block 3 The Boiler House Water Treatment, Storage and Blowdown for Steam Boilers Module 3.

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SC-GCM-29 CM Issue 1 © Copyright 2005 Spirax-Sarco Limited

Module 3.9
Water Treatment, Storage and
Blowdown for Steam Boilers

The Steam and Condensate Loop 3.9.1


Block 3 The Boiler House Water Treatment, Storage and Blowdown for Steam Boilers Module 3.9

Water Treatment, Storage and


Blowdown for Steam Boilers
Before boiler blowdown can be discussed and understood it is necessary to establish a definition
of water along with its impurities and associated terms such as hardness, pH etc.
Water is the most important raw material on earth. It is essential to life, it is used for transportation,
and it stores energy. It is also called the ‘universal solvent’.
Pure water (H20) is tasteless, odourless, and colourless in its pure state; however, pure water is
very uncommon. All natural waters contain various types and amounts of impurities.
Good drinking water does not necessarily make good boiler feedwater. The minerals in drinking
water are readily absorbed by the human body, and essential to our well being. Boilers, however,
are less able to cope, and these same minerals will cause damage in a steam boiler if allowed to
remain.
Of the world’s water stock, 97% is found in the oceans, and a significant part of that is trapped
in the polar glaciers - only 0.65% is available for domestic and industrial use.
This small proportion would soon be consumed if it were not for the water cycle (see Figure 3.9.1).
After evaporation, the water turns into clouds, which are partly condensed during their journey
and then fall to earth as rain. However, it is wrong to assume that rainwater is pure; during its fall
to earth it will pick up impurities such as carbonic acid, nitrogen and, in industrial areas, sulphur
dioxide.
Charged with these ingredients, the water percolates through the upper layers of the earth to the
water table, or flows over the surface of the earth dissolving and collecting additional impurities.
These impurities may form deposits on heat transfer surfaces that may:
o Cause metal corrosion.
o Reduce heat transfer rates, leading to overheating and loss of mechanical strength.
Table 3.9.1 shows the technical and commonly used names of the impurities, their chemical
symbols, and their effects.

Atmospheric moisture

Precipitation Evaporation
Evaporation and transportation from oceans
from surface water bodies, land Consumptive
surface and vegetation use

Well

Water
table Percolation Streams flow to oceans
Total surface and
ground water flow
to oceans

Ocean

Fresh Saline
ground water Interface ground water
Fig. 3.9.1 Typical water cycle

3.9.2 The Steam and Condensate Loop


Block 3 The Boiler House Water Treatment, Storage and Blowdown for Steam Boilers Module 3.9

Table 3.9.1 Impurities in water


Name Symbol Common name Effect
Calcium carbonate CaCO3 Chalk, limestone Soft scale
Calcium bicarbonate Ca(HCO3)2 Soft scale + CO2
Calcium sulphate CaSO4 Gypsum, plaster of paris Hard scale
Calcium chloride CaCI2 Corrosion
Magnesium carbonate MgCO3 Magnesite Soft scale
Magnesium sulphate MgSO4 Epsom salts Corrosion
Magnesium bicarbonate Mg(HCO3)2 Scale, corrosion
Sodium chloride NaCI Common salt Electrolysis
Sodium carbonate Na2CO3 Washing soda or soda Alkalinity
Sodium bicarbonate NaHCO3 Baking soda Priming, foaming
Sodium hydroxide NaOH Caustic soda Alkalinity, embrittlement
Sodium sulphate Na2SO4 Glauber salts Alkalinity
Silicon dioxide SiO2 Silica Hard scale

Raw water quality and regional variations


Water quality can vary tremendously from one region to another depending on the sources of
water, local minerals (see Figure 3.9.2). Table 3.9.2 gives some typical figures for different areas
in a relatively small country like the UK.

Soft to moderately soft


Newcastle upon Tyne
Slightly hard to moderately hard

Hard to very hard

York
Leeds
Manchester
Lincoln

Norwich
Birmingham

Cardiff
Bristol London

Brighton

Southampton
Fig. 3.9.2 Regional variations in water quality

Table 3.9.2 Water variation within the UK - All impurities expressed in mg /l calcium carbonate equivalents
Alkaline Non-alkaline Total
Area hardness hardness Total Non-hardness dissolved
(temporary) (permanent) hardness salts solids (TDS)
Leeds 12 10 22 24 46
York 156 92 248 62 310
Birmingham 28 72 100 130 230
London 180 192 372 50 422

The Steam and Condensate Loop 3.9.3


Block 3 The Boiler House Water Treatment, Storage and Blowdown for Steam Boilers Module 3.9

The common impurities in raw water can be classified as follows:


o Dissolved solids - These are substances that will dissolve in water.
The principal ones are the carbonates and sulphates of calcium and magnesium, which are
scale -forming when heated.
There are other dissolved solids, which are non-scale forming.
In practice, any salts forming scale within the boiler should be chemically altered so that they
produce suspended solids, or sludge rather than scale.
o Suspended solids - These are substances that exist in water as suspended particles.
They are usually mineral, or organic in origin.
These substances are not generally a problem as they can be filtered out.
o Dissolved gases - Oxygen and carbon dioxide can be readily dissolved by water.
These gases are aggressive instigators of corrosion.
o Scum forming substances - These are mineral impurities that foam or scum.
One example is soda in the form of a carbonate, chloride, or sulphate.
The amount of impurities present is extremely small and they are usually expressed in any
water analysis in the form of parts per million (ppm), by weight or alternatively in milligrams per
litre (mg /l).
The following sections within this Module describe the characteristics of water.

Hardness
Water is referred to as being either ‘hard’ or ‘soft’. Hard water contains scale-forming impurities
while soft water contains little or none. The difference can easily be recognised by the effect of
water on soap. Much more soap is required to make a lather with hard water than with soft
water.
Hardness is caused by the presence of the mineral salts of calcium and magnesium and it is these
same minerals that encourage the formation of scale.
There are two common classifications of hardness:
o Alkaline hardness (also known as temporary hardness) - Calcium and magnesium
bicarbonates are responsible for alkaline hardness. The salts dissolve in water to form an alkaline
solution. When heat is applied, they decompose to release carbon dioxide and soft scale or
sludge.
The term ‘temporary hardness’ is sometimes used, because the hardness is removed by boiling.
This effect can often be seen as scale on the inside of an electric kettle.
See Figures 3.9.3 and 3.9.4 - the latter representing the situation within the boiler.

Carbon dioxide combines with water to form carbonic acid:

CO2 H20 H2C03


Carbon dioxide Water Carbonic acid

Limestone (calcium carbonate) is dissolved by carbonic acid to form calcium bicarbonate:

H2C03 CaCO3 Ca(HCO3)2


Carbonic acid Calcium carbonate Calcium bicarbonate

Fig. 3.9.3 Alkaline or temporary hardness

3.9.4 The Steam and Condensate Loop


Block 3 The Boiler House Water Treatment, Storage and Blowdown for Steam Boilers Module 3.9

Carbon dioxide combines with steam to form carbonic acid:


Ca(HCO3)2 CaCO3 CO2
H20
Calcium Heat Calcium Carbon
water
bicarbonate carbonate dioxide

Similarly, magnesite (magnesium carbonate) is dissolved by carbonic acid to form magnesium bicarbonate:
Mg(HCO3)2 MgCO3 CO2
H20
Magnesium Heat Magnesium Carbon
water
bicarbonate carbonate dioxide

Fig. 3.9.4 Non-alkaline or permanent hardness (scale + carbonic acid)

o Non-alkaline hardness and carbonates (also known as permanent hardness) - This is also
due to the presence of the salts of calcium and magnesium but in the form of sulphates and
chlorides. These precipitate out of solution, due to their reduced solubility as the temperature
rises, and form hard scale, which is difficult to remove.
In addition, the presence of silica in boiler water can also lead to hard scale, which can react
with calcium and magnesium salts to form silicates which can severely inhibit heat transfer
across the fire tubes and cause them to overheat.

Total hardness
Total hardness is not to be classified as a type of hardness, but as the sum of concentrations of
calcium and magnesium ions present when these are both expressed as CaC03. If the water is
alkaline, a proportion of this hardness, equal in magnitude to the total alkalinity and also expressed
as CaC03, is considered as alkaline hardness, and the remainder as non-alkaline hardness.
(See Figure 3.9.5)

Non-alkaline hardness Alkaline hardness Total


(permanent) (temporary) hardness

Fig. 3.9.5 Total hardness

Non-scale forming salts


Non-hardness salts, such as sodium salts are also present, and are far more soluble than the salts
of calcium or magnesium and will not generally form scale on the surfaces of a boiler, as shown
in Figure 3.9.6.

2NaHCO3 Na2CO3 CO2


H20
Sodium Heat Sodium Carbon
water
bicarbonate carbonate dioxide

Na2CO3 2NaOH
H20 C02
Sodium Heat Sodium
water Carbon dioxie
carbonate hydroxide

Adding the total hardness + non-hardness salts gives:


Total Non hardness Total dissolved solids
hardness salts (TDS)

Fig. 3.9.6 The effects of heat

The Steam and Condensate Loop 3.9.5


Block 3 The Boiler House Water Treatment, Storage and Blowdown for Steam Boilers Module 3.9

Comparative units
When salts dissolve in water they form electrically charged particles called ions.
The metallic parts (calcium, sodium, magnesium) can be identified as cations because they are
attracted to the cathode and carry positive electrical charges.
Anions are non-metallic and carry negative charges - bicarbonates, carbonate, chloride, sulphate,
are attracted to the anode.
Each impurity is generally expressed as a chemically equivalent amount of calcium carbonate,
which has a molecular weight of 100.
pH value
Another term to be considered is the pH value; this is not an impurity or constituent but merely
a numerical value representing the potential hydrogen content of water - which is a measure of
the acidic or alkaline nature of the water. Water, H2O, has two types of ions - hydrogen ions (H+)
and hydroxyl ions (OH-).
If the hydrogen ions are predominant, the solution will be acidic with a pH value between 0 and
6. If the hydroxyl ions are predominant, the solution will be alkaline, with a pH value between 8
and 14. If there are an equal number of both hydroxyl and hydrogen ions, then the solution will
be neutral, with a pH value of 7.
Acids and alkalis have the effect of increasing the conductivity of water above that of a neutral
sample. For example, a sample of water with a pH value of 12 will have a higher conductivity
than a sample that has a pH value of 7.
Table 3.9.3 shows the pH chart and Figure 3.9.7 illustrates the pH values already mentioned
both numerically and in relation to everyday substances.
Table 3.9.3 The pH scale
pH Hydrogen ion concentration Hydroxyl ion concentration
Nature
value H+ H-
0 100 10-14 Acid
7 10-7 10-7 Neutral
14 10-14 100 Alkaline

3.9.6 The Steam and Condensate Loop


Block 3 The Boiler House Water Treatment, Storage and Blowdown for Steam Boilers Module 3.9

pH value
0 0.1 Hydrochloric acid (3.6% HCI)
0.3 Sulphuric acid (4.9% H2SO4)

1 1.1 Hydrochloric acid (0.36% HCI)


1.2 Sulphuric acid (0.49% H2SO4)
2.0 Hydrochloric acid (0.036% HCI)
2 2.1 Sulphuric acid (0.049% H2SO4)
Lemon juice 2.3 2.4 Acetic acid (6% CH3COOH)
Wine 2.8 to 3.8 2.9 Acetic acid (0.6% CH3COOH)
Vinegar 3.1 3
Fruit juice 3.5 to 4.0 3.4 Acetic acid (0.06% CH3COOH)

Marshy water 4.0 4

Beer 4.0 to 5.0 5


5.2 Boric acid (0.2% H3BO3)

6
Milk 6.3 to 6.6

Water, chemically pure 7.0 7

8
Sea water 8.3 8.4 Sodium bi. carb. solution (0.42% NaHCO3)

9
9.2 Borax solution (1.9% Na2B407)

10

10.6 Ammonia solution (0.017% NH3)


11 11.1 Ammonia solution (0.17% NH3)
11.6 Ammonia solution (1.7% NH3)
12 12.0 Potassium hydroxide solution (0.056% KOH)
Lime-water, saturated 12.3

13 13.0 Potassium hydroxide solution (0.56% KOH)


13.0 Sodium hydroxide solution (0.4% NaOH)

14 14.0 Potassium hydroxide solution (5.6% KOH)


Fig. 3.9.7 pH chart 14.0 Sodium hydroxide solution (4% NaOH)

The Steam and Condensate Loop 3.9.7


Block 3 The Boiler House Water Treatment, Storage and Blowdown for Steam Boilers Module 3.9

Questions
1. Temporary hardness salts are reduced by:
a| Raising the water temperature ¨
b| Lowering the water temperature ¨
c| Raising the pH value ¨
d| Letting the water settle ¨

2. What is the effect of CO2 in a steam system?


a| The formation of scale ¨
b| The formation of sludge ¨
c| Corrosion ¨
d| Acidity ¨

3. Which of the following forms soft scale or sludge?


a| Magnesium sulphate ¨
b| Sodium carbonate ¨
c| Sodium bicarbonate ¨
d| Calcium bicarbonate ¨

4. Which of the following are principal dissolved solids that are scale forming?
a| Carbonates and sulphates of sodium ¨
b| Calcium bicarbonate ¨
c| Carbonates and sulphates of magnesium ¨
d| Bicarbonate of sodium and magnesium ¨

5. What is the effect of temperature on calcium and magnesium sulphates?


a| They separate out as soft scale and sludge ¨
b| They precipitate out of solution and form hard scale ¨
c| Foaming and carryover occurs ¨
d| The TDS is increased ¨

6. What is the treatment for scale forming salts in boiler feedwater?


a| They are chemically treated to modify the pH ¨
b| The feedwater tank is raised to at least 85°C ¨
c| They are chemically treated to produce suspended solids ¨
d| They are removed by filtration means ¨

Answers
1: a, 2: c, 3: d, 4: c, 5: b, 6: c

3.9.8 The Steam and Condensate Loop