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Hardness
Alkalinity
pH
TDS
Silica
Suspended solids
Dissolved oxygen
If there is a difference exists between operating value and target value, then
decreasing or increasing blow down and adjusting chemical dosages will be done
1. Hardness
Total hardness is the combined concentration
of dissolved calcium and magnesium salts.
Alkaline or temporary hardness is caused by
bicarbonates, carbonates or hydroxides.
Bicarbonates which predominate in most
natural waters are easily broken down when
the temperature is raised.
Non-alkaline or permanent hardness is caused
mainly by chlorides, sulphates and nitrates.
Water hardness is the most common
contributor to boiler scaling
Water Hardness
classification
Water
hardness
classification
Soft
Moderate
Hard
Very Hard
mg/L or ppm
as CaCO3
0-60
61-120
121-180
> 180
2. Alkalinity
The extent to which a solution is alkaline
(i.e. has a pH value greater than 7)
It is a measure of its hydroxide (caustic),
carbonate and bicarbonate and hydroxides
content. Expressed in terms of calcium
carbonate content.
These bases break down to form carbon dioxide
in steam, which is a major factor in the corrosion
of condensate lines.
High Alkalinity also contributes to foaming and
carryover in boilers.
3. pH
is a measure of a solution's acidity
In water, small numbers of water molecules (H2O) will
disassociate into hydrogen ions (H+) and hydroxide ions
(OH-).
Other compounds entering the water may react with these,
leaving an imbalance in the numbers of hydrogen and
hydroxide ions.
When more hydrogen ions react, more hydroxide ions are
left in solution and the water is basic; when more
hydroxide ions react, more hydrogen ions are left and the
water is acidic.
Measure of pH
pH is measured on a logarithmic scale between 1
and 14 with 1 being extremely acid, 7 neutral, and
14 extremely basic. The more extreme the pH, the
more likely corrosion problems are to occur
Because it is a logarithmic scale there is a ten fold
increase in acidity for a change of one unit of pH,
e.g. 5 is 100 times more acid than 7 on the pH
scale
4.TotalDissolvedSolids(TDS)
Thetotaldissolvedsolids(TDS)inwaterconsist
ofinorganicsaltsanddissolvedmaterials.
Innaturalwaters,saltsarechemicalcompounds
comprisedof
Anions()suchascarbonates,chlorides,sulphates,and
nitrates(primarilyingroundwater),and
Cations(+)suchaspotassium(K),magnesium(Mg),
calcium(Ca),andsodium(Na).
Measure of TDS
It is a measure of the total amount of solids in
solution. Expressed as parts per million (ppm).
Generally estimated on-site by measuring
electrical conductivity. If the boiler water
conductivity is measured in-situ, then allowance
should be made for temperature and pH effects
as the hot, highly alkaline nature of boiler water
would give a falsely high reading. A substantial
part of TDS is due to alkalinity.
If the design values for TDS are exceeded, carryover from the boiler will increase leading to a
bad steam quality.
5. Silica
Silica is found as dissolved silicate
and in a suspended complex form.
It can combine with other compounds
to give scales that are strongly
insulating and difficult to remove and
cause high resistance to heat transfer
Nephelometric
Turbidity Units
7. Dissolved gases
Oxygen and carbon dioxide are the most
important.
Dissolved oxygen (DO) is an important factor
in determining the corrosiveness of water.
The solubility of oxygen in water depends on
temperature and pressure.
Dissolved carbon dioxide gives carbonic acid.
Even this weak acid can lower the pH to values
where the water becomes highly corrosive.
The type of boiler, pressure and heat flux
dictate the boiler water chemistry that can be
used to achieve the required steam purity and
efficiency.
Nature
Soluble
Ionic
Impurities
- Cations: Calcium, Magnesium, Sodium
Ammonium, Iron, Manganese etc.
Anions:
2.
Insoluble
-Nonionic
Bicarbonates,
Carbonates,
Nitrates, Chlorides, Dissolve-silica,
etc.
Suspended
matter,
Turbidity,
Silt,
Colloidal-silica.
Gaseous
4.
Others
Corrosion
Localized attack on metal can result in a forced
shutdown.
Because boiler systems are constructed primarily of
carbon steel and the heat transfer medium is water, the
potential for corrosion is high.
The relative rate of corrosion of steel varies with boiler
water pH and the level of dissolved oxygen.
Good water treatment aims to keep the pH within the
safe range of pH 8.2 - 12.5 while addition of oxygen
scavengers prevents iron being oxidised to ferric
oxide or rust.
pH Vs Corrosion
CORROSION
due to
DISSOLVED OXYGEN (DO)
4Fe + 3O2
Steel + Dissolved
Oxygen
2FeO3
Iron Oxide (Rust)
Corrosion
due to
Dissolved Carbon-dioxide
(i)
Fe + CO2 + H2O
Iron + Carbon-dioxide + Water
(ii)
4FeCO3+O2 + 10H2O
Iron Carborate + Oxygen + Water
Carbon-dioxide
(iii)
4Fe(OH)3
Iron Hydroxide
FeCO 3 + H2
Iron Carbonate +Hydrogen
4Fe(OH) 3 + 4H2O+CO2
Iron Hydroxide+Water +
2Fe 2O3
+ 6 H2O
Mg(OH)2 + 2HCL
2. Cacl2 + 2H2O
Ca(OH)2 + 2HCL
3. Mg(NO3)2 + 2H2O
Mg(OH)2 + 2HNO3
4. Ca(NO3)2 + 2H2O
Ca(OH)2 + 2HNO3
5. MgSO4 + 2 NaCL
MgCL2 + Na2SO4
Corrosion in boiler
Corrosion
in boiler
systems
can
quickly
result in
tube
failure
and plant
shutdown
Caustic Attack
If too much alkali is added or allowed to
concentrate, it can cause corrosion of the boiler
metal.
The attack may involve local dissolution of the
metal, usually on high heat transfer surfaces
which have become fouled, or cracking of the
metal.
Caustic cracking of stressed steel can occur
when the concentration of caustic is greater than
50,000 mg/L
Leads to sudden rupture and explosion of boilers.
Scaling
Scaling in the boiler occurs when the solubility of
a compound is exceeded. either through
chemical reaction, increased concentration or
higher temperatures.
Example: calcium and magnesium salts
dissolved in the feedwater become less soluble
as the feedwater is heated and eventually
precipitate out. Hardness contributes
significantly to scaling, particularly when water
is heated.
CaCO3
+ H2O + CO2
Mg (HCO3)2
Na2CO3 + H20
2NaOH + CO2
Scaling
Boiler scale and deposits form when
impurities precipitate on hot boiler tubes.
This hard shell is called scale
and is often found on the
outside of the fire tubes
Deposit-Related
problem
Deposits (Scale) in boilers cause
two major problems. i.e. fouling of
heat transfer surfaces and
restriction of water flow.
SOLUTIONS :
Removal of hardness salts by external
treatment.
Scale prevention by using internal
inhibitors.
Steam Contamination
Steam purity refers to the contamination of
the steam by solids, non-aqueous liquids or
volatile compounds.
It is not the same as steam quality, which is
concerned with the amount of moisture
from partial condensation in the steam
SOLUTIONS:
Antifoams can be used to prevent foaming
Control boiler water TDS to avoid carry-over.
Foaming
Carryover
Carryover is water leaving the boiler
with the steam.
normal
buble
carry over
buble
Priming
As the water level is raised the
volume of the steam space is
decreased, the speed of the steam
across the surface is increased
drawing foam and water droplets
towards the steam outlet.
A sudden increase in steam demand
can cause a slug of boiler water to
enter the steam outlet.
This is known as priming.
Operation of the boiler below its
design pressure will also produce a
similar effect.
Insoluble
Settling
Types of
treatment
Soluble
Clarification
Filtration
Gaseous
De-aeration
for oxygen
in De aerator
Activated carbon in
pressure filter
for chlorine.
Softening
Dealkaliser
Demineralization
Reverse Osmosis
EXTERNAL WATER
TREATMENT
Good external water treatment saves
significant amounts of energy.
Removing hardness will avoid scale.
Reducing feedwater TDS will reduce
blowdown and thus save energy.
Removing alkalinity, dissolved oxygen and
carbon dioxide will reduce the risk of
corrosion.
Lower oxygen levels in the feedwater
mean lower chemical costs.
External treatment
(involves complete or partial removal of
impurity).
Technology
1.Base
exchange
softening
Purpose
Using ion exchange to convert
calcium and magnesium salts that
would cause scale into sodium salts
which do not precipitate, i.e.
removal of hardness.
4.Reverse
osmosis
5.De-
1. Base exchange
softening
Water softeners
The water softeners "Ion
Exchange" process to
convert the hard water
ions of calcium and
magnesium to sodium
ions.
The resultant water is
less than 4 ppm total
hardness
Capacity upto 5-50m3/hr
2. Dealkalisation
Dealkalisation reduces TDS by removing alkaline salts.
Generally used to treat the feedwater for low and
medium pressure boilers and when a very high percentage of
make-up water is to be used.
In a weak acid cation exchanger. the less strongly alkaline
impurities - carbonate and bicarbonate ions are replaced
by positively charged hydrogen ions. The carbonic acid
that is produced is removed in a degassing tower.
If pH is acceptable and hardness has been reduced
sufficiently, the degassed water can be used directly.
If not; pH adjustment and base exchange softening are
necessary.
Dealkalizer
3. Demineralisation
Demineralisation
Demineralisation
Demineralisation
Passage of the water through the cation
exchanger produces a solution of dilute acids,
which are exchanged by hydroxide in the anion
exchanger to give water.
If carbonates and bicarbonates are present in the
water, removal of carbonic acid in an intermediate
degassing tower will reduce the requirement for
hydroxide exchange in the anion bed.
The cation and anion exchangers are regenerated
with mineral acid and sodium hydroxide
respectively.
used for high pressure, high heat flux and oncethrough boilers.
4. Reverse
Osmosis
5. Deaeration
Used to remove
dissolved oxygen
from feed water,
either by thermal,
chemical or
mechanical means.
Oxygen is driven off
as the temperature
increases.
Free carbon dioxide is also removed in the deaerator. thus reducing carbonic acid level (H2CO3).
Lower oxygen levels in the feed water reduce the
subsequent amount of oxygen scavengers needed
Choice of external
treatment Methods
The factors affecting the selection of
technology :
Economics of Water
treatment
The capital and operating costs for external
water treatment vary according to the plant
type and duty.
raw water analysis
treated water specification
chemical and effluent charges
temperature
flow rate
energy consumption
maintenance costs.
Effectiveness in
Removing Impurities
INTERNAL WATER
TREATMENT
Selection of the most appropriate treatment regime for a
particular boiler system saves both energy and money.
Careful control of boiler water chemistry saves money
through reduced consumption of energy, water and
treatment chemicals.
Controlled dosage saves energy and avoids wasting
expensive treatment chemicals.
Preventing scale formation, minimising silicate and other
deposits, eliminating dissolved oxygen, neutralising
dissolved carbon dioxide and minimising concentration
effects all lead to more efficient boiler operation.
Internal treatment
Preventing Scale
Formation
Scale prevention is based upon
controlled precipitation of hardness
as a fine; mobile sludge that can
be removed during bottom
blowdown
Achieved by the application of the
carbonate or phosphate cycle
(depending on system pressure).
Carbonate Cycle
The formation of calcium sulphate scale, which is difficult
to remove was historically prevented by using a controlled
reserve of carbonate and hydroxide ions in the boiler
water. It is suitable for boilers operating up to about 10
bar.
Above this pressure, thermal breakdown of carbonate
prevents adequate reserves being maintained.
In the carbonate cycle. any hardness entering the boiler
precipitates as calcium carbonate or magnesium
hydroxide. The natural alkalinity of the feedwater may be
sufficient to cause precipitation; if not. carbonate or
hydroxide are added to make up the deficit.
Other additives - tannins, lignins, starches and a wide
variety of synthetic polymers - can be used to improve the
mobility of the precipitates and thus enhance their
removal by bottom blowdown.
Phosphate Cycle
Since carbonate breakdown increases with temperature,
the phosphate cycle was developed for use at higher
pressures. Phosphate is used to precipitate any calcium
present. For magnesium, the preferred precipitant is
hydroxide alkalinity, which yields magnesium hydroxide
This method of scale prevention involves a controlled
reserve of soluble phosphate and maintenance of caustic
alkalinity at a specific pH in the boiler water to
precipitate hardness as a mobile sludge. The phosphate
is normally added as trisodium phosphate, which also
adds alkalinity. However, if a reduction in alkalinity is
required. salts such as disodium phosphate or
monosodium phosphate can be used as these are acidic.
Phosphate salts are normally dosed directly into the
boiler to avoid precipitation in feed lines.
Other Deposits
Preventing silicate deposits
Keeping the silica in solution by
maintaining the appropriate silica:
caustic alkalinity ratio.
Oxygen removal
Adding oxygen scavengers.
Avoiding carry-over
Use of antifoams to prevent foam
production
Boiler Water
Silica
(ppm SiO2)
Total
Alkalinity**
(ppm CaCO3)
Specific
Conductance
(micromhos/cm)
(unneutralized)
Iron
(ppm Fe)
Copper
(ppm Cu)
Total
Hardness
(ppm CaCO3)
0-300
0.100
0.050
0.300
150
700*
7000
301-450
0.050
0.025
0.300
90
600*
6000
451-600
0.030
0.020
0.200
40
500*
5000
601-750
0.025
0.020
0.200
30
400*
4000
751-900
0.020
0.015
0.100
20
300*
3000
901-1000
0.020
0.015
0.050
200*
2000
1001-1500
0.010
0.010
0.0
0***
150
1501-2000
0.010
0.010
0.0
0***
100
Total solids
(ppm)
Alkalinity
(ppm)
Suspended
solids (ppm)
Silica* (ppm)
0-300
3500
700
300
125
301-450
3000
600
250
90
451-600
2500
500
150
50
601-750
2000
400
100
35
751-900
1500
300
60
20
901-1000
1250
250
40
1001-1500
1000
200
20
2.5
1501-2000
750
150
10
Over 2000
500
100
0.5
DEARAT
OR/F.W.
BOILER
DRUM
Sat/S.H
STEAM
EFFECTS IF INCREASES
EFFECTS IF
DECREASES
pH
8.8-9.2
9.8-10.2
8-9
Caustic enbritlement
T.H.
Nil
Nil
Nil
Scale Formation
---
V/cm
<0.5
<200
<0.3
Indications of impurities
---
SiO2
<0.02
<5.0
<0.02
PO4
Nil
5-20
Nil
T.D.S.
Nil
50-100
Nil
N2H4
0.01-0.02
Nil
Nil
Ammonium Salts
D.O.
<0.007
Nil
Nil
Corrosion
Better
Iron
<0.01
Nil
Nil
Scale Formation
Better
Cl2
Nil
Nil
Nil
Corrosion,Hydrogen damage
Better
Nil
Nil
Nil
Better
Causes corrosion
Better
Corrosion
Better
Corrosion
Internal Water
Treatment for Idle
Boilers
Boilers are sometimes left standing idle and
cold for maintenance, operational or other
reasons. In such circumstances, there is a
risk of corrosion occumng. Any corrosion is
likely to be localised as pitting or water line
attack.
A boiler can he kept full of water or with a
nitrogen blanket for up to three months. If
there is a risk of freezing the boiler should
be kept dry.
Wet Storage
Raise the water level to eliminate air
spaces.
Increase oxygen scavenger levels to 20 - 25
times the normal dose.
Adjust the pH to 11.
If a non-drainable superheater is present:
fill with demineralised water;
add a volatile oxygen scavenger and alkali to
give the same values as for the boiler section;
take precautions to avoid ingress of boiler water.
Dry Storage
Drain the boiler , eliminating water pools.
Dry the internal surfaces by blowins warm, dry air
through all the waterways.
Store the boiler with heaters and manhole doors open
for ventilation.
For closed storage, place a desiccant and possibly a
vapour phase inhibitor inside the boiler before it is
sealed.
Consider using nitrogen blanketing to prevent ingress
of moist air.
Check chemical levels and desiccant regularly. Top up
or change as necessary.
Take adequate precautions to prevent corrosion of the
fireside.
40/600
60/900
8/1200
8.5 to 9.5
8.5 to 9.5
8.5 to9.5
8.5 to 9.5
0.5
nil
pH
0.05
0.02
0.01
0.01
0.05
0.05
0.02
0.02
1.0
0.1
0.1
Oil
Nil
Nil
Nil
Nil
Medium Pressure
20/300
40/600
60/900
8/1200
pH
10.5 to 11.5
10 to 11
9.8 to10.5
9.8 to 10.2
700
500
300
Mg/1 (Max)
3
300
150
60
30
50 to 100
30 to 70
20 to 50
10 to 45
Less than
half the
caustic
alkalinity
20
10
30 to 50
20 to 40
0.05 to0.3
0.05 to 0.1
3000
2000
1200
700
200
50
Case study
BOILER FEED WATER ANALYSIS
Description
Parameter
Recommended
Actual
Recommended
Actual
8.5 - 9.5
9.0 - 9.5
10.5 - 11.5
12.0
TDS
350
400 - 500
3500
3200 5000
Total hardness
< 10
5 - 40
P - Alkalinity
50
40
350
1100 1500
M - Alkalinity
100
250 - 300
1200
1600 1800
pH