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Chapter 5
5.2 Deposits
Deposits, particularly scale, can form on any water washed equipment surface
especially on boiler tubes as the equilibrium conditions in the water contacting these
surfaces are upset by an external force, such as heat. Each contaminant had an
established solubility in water and will precipitate when it had been exceeded. If
water is in contact with a hot surface and the solubility of the contaminant is lower
at higher temperatures, the precipitate will form on the surface, causing scale. The
most common components of boiler deposits are calcium phosphate, calcium
carbonate, magnesium hydroxide, magnesium silicate, various forms of iron oxide
and alumina.
At the high temperatures found in a boiler, deposits are a serious problem, causing
poor heat transfer and a potential for boiler tube failure. In low pressure boilers with
low heat transfer rates, deposits may build up to a point where they completely
occlude the boiler tube.
In modern intermediate and higher pressure boilers with heat transfer rates in excess
of 1.2 kj/m2/hr, the presence of even extremely thin deposits will cause a serious
elevation in the temperature of the tube metal. The deposits coating retards the flow
of heat from the furnace gases into the boiler water. This heat resistance results in a
rapid*rise in metal temperature to the point at which failure can occur.
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Thickness of Scale
0.5 mm
1 mm
2 mm
4 mm (0.125")
8 mm ( 0.25")
16 mm (0.5)
30 mm ( 1 " )
Table 5.1 shows the increase in fuel consumption due to scales formation
5.3 Corrosion
The second major water related boiler problem is corrosion, the most common
example being the attack ot steel by oxygen. This occurs in water supply systems,
pre-boiler systems, boilers, condensate return lines, and in virtually any portion of the
steam cycle where oxygen is present. Oxygen attack is accelerated by high
temperature and low pH. A less prevalent type of corrosion is alkali attack, which
may occur in high pressure boilers where caustic can concentrate in a local area of
steam bubble formation because of the presence of porous deposits.
Some feed water treatment chemicals, such as chelants, if not properly applied can
corrode feed water piping, control valves and even the boiler internals.
While the elimination of oxygen from boiler feed water is the major step in controlling
boiler corrosion, corrosion can still occur, an example is the direct attack by steam of
the boiler steel surface at elevated temperatures, according to the following
reactions:
4H2O + 3Fe Fe3O4 + 4H2
This attack can occur at steam blanketed boiler surfaces where restricted boiler
water flow causes overheating. It may also occur in superheater tubes subjected to
overheating. Since this corrosion reaction produces hydrogen, a device for analyzing
hydrogen in steam is useful as a corrosion monitor.
The third major problem related to boiler operations is carryover from the boiler into
the steam system. This may be a mechanical effect, such as boiler water spraying
around a broken baffle, it may be caused by the volatility of certain boiler water
salts, such as silica and sodium compounds, or it may be caused by foaming.
Carryover is most often a mechanical problem, and the chemicals found in the
steam are those originally present in the boiler water, plus the volatile components
that distill from the boiler even in the absence of spray.
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2 - Hardness
Water is referred to as being either 'hard' or 'soft'. Hard water contains scaleforming impurities while soft water contains little or none. The difference can easily
be recognized by the effect of water on soap. Much more soap is required to make
lather with hard water than with soft water.
- 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.
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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.
3 - Dissolved solids
These are substances that will dissolve in water. The principal ones are the
carbonates and sulfates of calcium and magnesium, which are scale-forming when
heated. There are other dissolved solids, which is 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.
4 - Dissolved gases
Oxygen and carbon dioxide can be readily dissolved by water. These gases are
aggressive instigators of corrosion.
5- Silica
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Name
Calcium carbonate
Calcium bicarbonate
Symbol
Common name
Effect
CaCO2
Chalk, limestone
Soft scale
Soft scale+CO2
Ca(HCO3)2
Calcium sulphate
CaS04
Calcium chloride
CaCl2
Hard scale
Corrosion
Magnesium carbonate
MgCO3
Magnesrte
Soft scale
Magnesium sulphate
MgSO4
Epsom silts
Corrosion
Magnesium bicarbonate
Sodium chloride
Scale, corrosion
Mg(HCO3)2
NaCl
Common salt
Electrolysis
Sodium carbonate
Na2C03
Alkalinity
Sodium bicarbonate
NaHCO3
Baling soda
Priming, foaming
NaOH
Caustic soda
Alkalinity, embrittlement
Na2SO4
Gluaber salts
Alkalinity
SiO2
Silica
Hard scale
Sodium hydroxide
Sodium sulphate
Silicon dioxide
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Boiler Water Treatment
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 liter (mg/l)
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Softeners are relatively cheap to operate and can produce treated water reliably for
many years. They can be used successfully even in high alkaline (temporary)
hardness areas provided that at least 50% of condensate is returned. Where there is
little or no condensate return, a more sophisticated type of ion exchange is
preferable.
Sometimes a lime/soda softening treatment is employed as a pre-treatment before
Base Exchange. This reduces the load on the resins.
SOFTENER SIZING FORMULA:
C = M T H /R
C = Capacity of softener in cubic feet of resin
M = Makeup water volume per hour in gallons; the volume needed to be softened
(8.34 pounds per gallon)
T = Time in hours desired between regeneration cycles
H = Hardness of water in grains (17.1 ppm per grain hardness)
R = Resin Capacity per cubic foot (this is virtually always 30,000 grains)
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- De-alkalization
Disadvantage of base exchange softening is that there is no reduction in the TDS and
alkalinity. This may be overcome by the prior removal of the alkalinity and this is
usually achieved through the use of a dealkalizer.
There are several types of dealkalizer but the most common variety is shown in
Figure 5.7 It is really a set of three units, a dealkalizer, followed by a degasser and
then a base exchange softener.
Dealkalizers are sometimes called 'split-stream' softening. A dealkalizer would
seldom be used without a base exchange softener, as the solution produced is acidic
and would cause corrosion, and any permanent hardness would pass straight into
the boiler.
A dealkalization plant will remove temporary hardness as shown in Figure 5.8. This
system would generally be employed when a very high percentage of make-up water
is to be used.
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- Demineralisation
This process will remove virtually all the salts. It involves passing the raw water
through both cation and anion exchange resins (Figure 5.9). Sometimes the resins
may be contained in one vessel and this is termed 'mixed bed' demineralisation.
The process removes virtually all the minerals and produces very high quality water
containing almost no dissolved solids. It is used for very high pressure boilers
(Water Tube Boilers) such as those in power stations.
If the raw water has a high amount of suspended solids this will quickly foul the ion
exchange material, drastically increasing operating costs. In these cases, some pretreatment of the raw water such as clarification or filtration may be necessary.
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ultra pure water and boiler feed water. It is also applied in the food sector
(concentration of fruit juice, sugar and coffee), in the galvanic industry
(concentration of wastewater) and in the dairy industry (concentration of milk for
cheese production).
- Desalination with Reverse Osmosis
The desalination unit consists of a number of Reverse Osmosis membranes in several
pressure vessels, which are placed in a certain order. The feed water that is pumped
into the module will be separated into water with a low salt content and water with a
high salt content.
The water with a low salt content is called permeate and the water with a high salt
content is called concentrate or reject. The concentrate flow is regulated by a
pressure vessel, which is placed within the concentrate. The pressure vessel
regulates the percentage of feed water that leaves the module through the
concentrate flow.
Pre-Treatment
Unit
Permeate
High Pressure
Pump
Reject
Membrane Element
Feed
Fig 5.11 Desalination Process
Reverse Osmosis systems are usually designed for a specific permeate flow. To
achieve this flow, a number of membrane elements are required. The number of
membrane elements that is placed within the installation depends upon the designed
flux.
For the desalination of seawater the limiting factor is the maximum feed pressure;
this may not exceeds 69 bars.
Based on the designed flux, the production per unit membrane can be determined:
- Production per element = flux element surface
- Number of elements = permeate flow / production per element
- Number of pressure vessels = number of elements / number of elements
per vessel
- By means of the permeate flow and the required recovery, the feed water
flow is calculated:
Feed water flow = permeate flow / recovery
A certain feed pressure is required, depending on the system design. The flux, the
energy loss in the system and the osmotic pressure determine the feed pressure that
the system requires. The required feed pressure will increase when the membrane
elements are becoming contaminated through the years. A feed pump that enables a
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higher flow than the flow that is theoretically required will than be implicated to keep
the feed pressure continual. A feed pump that increases the feed pressure by 25%
will be satisfactory in practice.
When the system is started up, the initial situation is recorded. All relevant
parameters should be registered and noted in a log. Based on this data the
performance of the installation can be examined and regulated after the system has
been put into action.
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Process
Original water
Cold lime & iron salts
Cold lime-soda
Hot lime-soda
Na2X + anion exchanger
Demineralization
Silica
10
6
7-8
1
1
0.05
Residuals mg/l
Hardness Alkalinity
160
135
Nil
35
65
65
17
40
Nil
20
Nil
1-2
TDS
275
225
210
145
290
1-2
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minimizing blowdown. The higher cost compared to phosphate usually limits the use
of chelates to feed waters having low hardness. There is the risk that breakdown of
the organic molecule at higher temperatures could create a potential problem of
control that could result in corrosion, so chelate programs are usually limited to
boilers operating below 100 bars. The addition of polymers as scale control agents
increases the effectiveness of chelate programs.
It also reduces the corrosion potential by reducing the chelant dosage below
theoretical requirements, so that there is no chelant residual in the boiler water.
Chelates can react with oxygen under boiler water conditions, which can increase the
cost of a chelate program substantially. Overfeed of chelates and concentration
mechanisms in the boiler can lead to severe localized corrosion and subsequent unit
failure.
5.5.2.5 COMPLEXATION/DISPERSION
The newest addition to internal treatment technology is the use of synthetic organic
polymers for complexation and dispersion. This type of program can be used to 100
bars and is economical in all low-hardness feed water systems typical of those
produced by ion exchange. Heat transfer rates are maximized because these
polymers produce the cleanest lube surfaces of any of the available internal
treatment programs. This treatment solubilizes calcium, magnesium, and aluminum,
and maintains silica in solution while avoiding corrosion potential side effects as
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determined by hydrogen levels in the steam. Iron particulates returned from the
condensate system are likewise dispersed for removal via blowdown. A simple
measure of ion transport is used to demonstrate on-line performance of this
program.
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- Agitation increases foaming - The trend is towards smaller boilers for a given
steaming rate.
Smaller boilers have less water surface area, so the rate at which steam is released
per square meter of water area is increased. This means that the agitation at the
surface is greater. It follows then that smaller boilers are more prone to foaming.
- Hardness - Hard water does not foam. However, boiler water is deliberately
softened to prevent scale formation, and this gives it a propensity to foam.
- Colloidal substances -Contamination of boiler water with a colloid in suspension,
for example, milk, causes violent foaming. Note: Colloidal particles are less than
0.0001 mm in diameter, and can pass through a normal filter.
- TDS level - As the boiler water TDS increases, the steam bubbles become more
stable, and are more reluctant to burst and separate.
Corrective action against carryover
The following alternatives are open to the Engineering Manager to minimise
foaming in the boiler:
1- Operation - Smooth boiler operation is important. With a boiler operating under
constant load and within its design parameters, the amount of entrained moisture
carried over with steam may be less than 2%.
If load changes are rapid and of large magnitude, the pressure in the boiler can drop
considerably, initiating extremely turbulent conditions as the contents of the boiler
flash to steam. To make matters worse, the reduction in pressure also means that
the specific volume of the steam is increased, and the foam bubbles are
proportionally larger.
If the plant conditions are such that substantial changes in load are
normal, it may be prudent to consider:
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sludge formation can lead to the boiler water level controls sensing improper levels,
creating a danger to personnel and process alike.
Summary
- The amount of TDS in the boiler water depends on the type of feedwater treatment
that is used. However, for any given feedwater condition control of TDS in the boiler
water is by blowdown. The type of treatment will depend on the source of the
feedwater, its constituents and steam generator requirements.
- The feedwater treatment can include water softeners, demineralizers and/or
polishers to eliminate hardness, silica, other dissolved solids, and suspended solids.
Organic material ingress control equipment may also be provided. A deaerating
heater is also included to minimize the dissolved oxygen. The feedwater treatment
should be compatible with the boiler water treatment and other cycle requirements.
It should be noted that systems which include steam turbines, and superheaters, will
require higher purity feedwater than referenced in this document. In the case of
steam turbines, the manufacturer of the turbine to be used should define the steam
quality requirement needed from the boiler. It should further be noted that steam
quality requirements can differ between the various turbine manufacturers. Thus it is
important that the various equipment manufacturers (boiler, turbine, water
treatment, etc.) be selected, and communicate at an early stage in the project with
the owners representative regarding steam quality and water treatment
requirements, in order to avoid later problems.
- The type of boiler water treatment usually varies with the operating pressure of the
boiler, the quality of the feedwater, and the boiler design. A "caustic phosphate"
treatment is often used with feedwater having high solids, generally in boilers
operating at lower pressures. This treatment provides the chemical conditions
necessary to cope with residual hardness and other scale forming constituents.
- Chelant treatments may be used with operating pressures up to about 1500 psig.
With this treatment it is essential that oxygen in the feedwater be reduced to the
lowest possible levels through mechanical and chemical deaeration. It is also
essential that the boiler be protected from oxygen during any outage periods.
- A "Coordinated Phosphate" treatment may be used at any operating pressure but is
generally used with boilers having high purity feedwater and operating at high
pressures. The phosphate treatment precipitates the hardness compound and also
controls the alkalinity and pH.
- A "Zero Solids" or "All Volatile" treatment does not add any dissolved solids to the
boiler. The pH in the complete cycle is controlled by volatile amines such as
ammonia, morpholine and Cyclohexylamine. The zero solids treatment may be used
at all operating pressures in those boilers having very high purity (low solids)
feedwater. However, this treatment does not provide any corrosion protection of the
boiler whenever the feedwater becomes contaminated. Accordingly, users of this
treatment should be prepared to inject. Phosphate in the boiler water or remove the
boiler from service whenever there are condenser leaks or other contamination.
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Total
Dissolved
Solids
ppm
5000 - 3500
4000 3000
3000 - 2500
Total
Alkalinity
ppm as CaCO
1200 - 900
900 - 700
800 - 600
Suspended
2
Solids max.
ppm
100
25
10
Silica
ppm
1
1
Total
150 - 100
120 100
80 - 50
NOTES:
(1) Maximum values may not be achievable due to plant operating
conditions or feedwater characteristics.
(2) Critically affected by operating conditions and year of boiler
manufacture.
10
8
5
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