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Scaling, Corrosion and Water Treatment on

Steam Generator Systems < 30 bar
By Mr. Ludwig Hoehenberger, TÜV SÜD, Munich, Germany.
Phone: +49 89 5791 1063; Telefax: +49 89 5791 2070; E-Mail: [email protected]

Introduction of Referent
The referent is senior expert with over 40 years experience in Materials Investigation, Failure
Analysis, Water Chemistry and Corrosion in TÜV SÜD Industry Service, Munich, Germany.

1 Basics in Scaling, Corrosion and Water Constituents

1.1 Scaling
Scale in steam generators first must be divided into
- essential necessary dark brown to black, very thin (< 0.1 mm), dense, protective iron oxide
layer (of magnetite), like very thin mill scale, which leads not to increased wall temperature,
- undesired, mostly grey or brownish white, porous scale of water impurities (mostly hardness
scale or silica scale), which leads to more or less elevated wall temperature
- light brown to red brown deposits of porous iron corrosion product (mostly due to the iron
content in boiler feedwater [BFW]) – heavily avoidable – and/or
- local blisters or bark like deposits due to oxygen corrosion during shut down.
All well-designed steam generators and hot water boiler - shell boiler and water tube boiler -
achieve satisfying lifetime only if the boiler steel is able to develop and to maintain the men-
tioned thin protective magnetite (Fe3O4) layer during operation and shut down.
Undesired deposits of water constituents and/or corrosion product increase the wall tempera-
ture of furnaces depending on layer thickness, composition and porosity and may to lead ma-
terial over-heating, subsequent loss in material strength, boiler damages or explosion. Particu-
larly dangerous is silicate scale (Fig. 1) and scale containing oil or fat.

Fig. 1 Thin silicate scale on a fire tube of a shell boiler

led to a severe fire tube deformation due to over heating
1.2 Corrosion
Corrosion is the - mostly electro-chemical - reaction of a metallic material with its environment
that results in a damage of the material or component before its regular lifetime.
The area where a metal corrodes respectively is going into solution in form of metal cations,
like iron (Fe++), is called anode.
The area where the ambient electron conductive medium (electrolyte, mostly water) reacts
with the electrons of the anodic reaction is called cathode. For this reaction e.g. oxygen (O2) is
reduced to hydroxyl (OH–) anions (oxygen corrosion type) or hydrogen (H+) cations from an
acid are reduced to atomic hydrogen (hydrogen corrosion type).
In boilers, the mainly observed corrosion is predominantly the result of different conditions of
the protective magnetite layer (e.g. porous spots and dense layers), defects in the magnetite
layer (e.g. cracks due to different strain) or different aeration conditions of the magnetite layer
(e.g. on top and underneath of deposits, above and below water level lines). It is important to
know that the magnetite protective layer is more brittle than steel and more noble than steel!
The reactions on the most common oxygen corrosion on iron or steel are shown in Fig. 2.

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Fig. 2 Principles of oxygen corrosion

Oxygen corrosion, which leads to local corrosion (pitting), can be frequently observed
- during stand still of boilers (if the pressure is 0 and steam is replaced by air), Figs. 3+4 and
- as atmospheric corrosion on carbon steel.

Fig. 3 Oxygen corrosion on fire tube Fig. 4 Oxygen corrosion on smoke tube
of a horizontal shell boiler of a horizontal shell boiler
Fresh oxygen corrosion appears yellow-brownish, older corrosion and already heated corro-
sion spots brown to dark brown. Corrosion effects are intensified by increasing conductivity.
Other form of corrosion on lower pressure boiler systems is
- acid corrosion due to carbonic acid within steam and condensate lines, see Figs. 5+6,
because corrosion on carbon steel is as higher as lower the pH, and
- erosion corrosion or flow assisted corrosion (FAC) and cavitation, both significantly affected
by flow conditions.

Figs. 5 + 6 Carbonic acid corrosion on condensate return tube (right = enlargement)

FAC may be observed on pumps and pump impellers as well as on water pipes and valves as
the result of a too low pH in combination with too high flow rate, see Fig. 7.
Cavitation is the result of steam bubble formation and their subsequent implosion (distinct au-
dible!), e.g. on top of condensate pipes with condensate/steam mixtures, see Fig. 8 or pumps
operating in hot water. Elevated pressure at pump inlet solves the problem.

Fig. 7 Erosion corrosion on a steam Fig. 8 Cavitation on top side (12:00

block valve used as control valve position) of condensate return pipe

1.3 Water Constituents, Definitions

Natural waters (rain water, river water, well water, domestic water etc.) have, depending of its
origin, very different composition. The most clean natural water is rain water. All other waters
have undissolved (e.g. river water) and more or less dissolved constituents, like hardness,
silica, iron, manganese, organics, oxygen etc.
Following definitions are frequently used to determine waters. Common impurities of waters
and its effects and risks to boiler operation are explained.
1.3.1 Conductivity
The sum of all dissolved (electrical conductive) substances in water can be measured by the
electrical conductivity (standard reference temperature 25 °C).
The conductivity depends on temperature and increases significantly with the temperature,
e.g. 100 µS/cm at 25 °C increases to approx. 440 µS/cm at 100 °C.
SI-Unit / Definition: Siemens (S), S = 1: Ohm (Ω, resistance), 1 S = 1,000,000 µS.
Water became electrical conductive due to dissolved salts, acids (also carbonic acid), lye
(bases) and some organics, see Fig. 9 – but silica doesn’t affect conductivity!

Fig. 9 Specific conductivity at 25 °C of some solutions of acids (1,2), bases (3,4) and salts (5-
10) in water.
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Dissolved in water, the above mentioned substances dissociate into ions with different electri-
cal charge depending of their valence. The ions are divided into cations with positive charge,
like mono-valent sodium ion (Na+), bi-valent calcium ion (Ca++) or tri-valent iron ion (Fe+++) and
anions with negative charge, like mono-valent chloride ion (Cl–), bi-valent sulphate ion (SO4– –)
or tri-valent phosphate ion (PO4– – –).
Also water (H2O) dissociates in traces into one mono-valent hydrogen (H+) cation and one
mono-valent negative hydroxyl ion (OH –), which leads to a very little electrical conductivity.
Purest water shows a conductivity at 25 °C of ca. 0.055 µS/cm corresponding to a specific
resistance of about 18.2 MΩ⋅cm = 18,200,000 Ω⋅cm!

For comparison, in Asia rain water may have a conductivity about 10-20 µS/cm, river water
(unaffected from sea water) 100 - 300 µS/cm and well water or domestic similar values. River
water near the sea and brackish water may have conductivity up to 10,000 - 20,000 µS/cm.
The conductivity of waters affects corrosion activities, as higher the conductivity as higher the
corrosion rate.

1.3.2 pH-Value
The very low dissociation of pure water defines the neutral pH of 7.0, values below pH 7 char-
acterise acidic conditions with increasing acidity down to pH 0 and pH values above 7 that of
basic or alkaline conditions up to pH 14. Attention: Any single pH-step results to a 10 fold con-
centration change! For instance, 0.4 mg/l caustic soda (NaOH) in pure water result to a pH of
9, a content of 4 mg/l NaOH to pH 10, 40 mg/l to pH 11 and 400 mg/l NaOH to a pH of 12 etc.
A caustic alkalinity of 1 mmol/l corresponds to 40 mg/l caustic soda (NaOH).
Moderate alkaline water conditions (pH 9-12) are important to protect iron from corrosion! Acid
or acidic water dissolves the magnetite protective layer and attacks iron/steel.
1.3.3 Hardness
The total hardness of water (mainly calcium and magnesium compounds) must be divided into
carbonate hardness and non-carbonate hardness.
Carbonate hardness (calcium-/magnesium-bi-carbonate) is only soluble in water together with
a specific amount of carbonic acid (carbon dioxide dissolved in water). If this amount of carbon
dioxide is removed due to boiling or reduced by spraying on air or heating, calcium carbonate
(lime stone) will precipitate and forms carbonate scale.
In tropical and sub-tropical countries with heavy rain falls and little lime stone formation, the
carbonate hardness of raw water is relatively low.
Non-carbonate hardness (calcium-/magnesium-chloride, -sulphate, -nitrate etc.) itself is well
soluble in water, only calcium sulphate (gypsum) forms scale if its concentration exceeds
about 2 g/l = 2,000 mg/l. Raw water - particularly river water contaminated with sea water - or
brackish water, shows high non-carbonate hardness because sea water contains - beside very
high sodium chloride content - also much calcium and magnesium chloride.
In presence of silica (silicon acid, silicon oxide) both, carbonate and non-carbonate hardness
are forming scale of calcium-/magnesium-silicate (silicate scale), which reduces heat transfer
extremely.
The most easy, safe and common way to remove hardness is application of a softener. It ex-
changes calcium and magnesium compounds to highly water soluble sodium compounds.

1.3.4 Alkalinity
Alkalinity allows determination of different water constituents, which are important for boiler
operation, by an easy titration method using 0.1 N acid for (positive) + M/P-values and 0.1 N
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base for (negative) – P/M values. Alkalinity is divided into total alkalinity, composite alkalinity
and caustic alkalinity.
The total alkalinity (+ M-alkalinity) indicates bicarbonates (e. g. from carbonate hardness, or
sodium bi-carbonate [reaction product of carbonate hardness in softeners] and includes the
composite alkalinity (+ P-alkalinity) and caustic alkalinity - if any. As far as water shows only
+ M-alkalinity, only bi-carbonates exist (like carbonate hardness or sodium bi-carbonate, which
is typical for raw water).
A negative M-value (– M-value) indicates acidic conditions at a pH below 4.3 and must be ti-
trated with 0.1 N NaOH.
The composite alkalinity (+ P-alkalinity) indicates all alkaline compounds above a pH 8.2 like
sodium carbonate, tri-sodium phosphate and free caustics (e.g. caustic soda) and has re-
placed measurement of caustic alkalinity. Composite alkalinity includes caustic alkalinity!
A negative P-value (– P-value) indicates a pH below 8.2 and weak alkaline and acidic condi-
tions respectively and must be titrated with 0.1 N NaOH.
The caustic alkalinity indicates the content of free caustics only, but needs a special procedure
before titration against P-indicator (Phenolphthalein).

The M-indicator (Methylorange) changes its colour at pH 4.3, the P-indicator (Phenolphthalein)
at pH 8.2, which means in presence of P-alkalinity the water is alkaline! The connection be-
tween +/ – P -value, +/ – M-value and pH and the changes of the indicators can be seen in
Fig. 10.
For shell boiler, the boiler water should be at least tested for composite alkalinity (P-alkalinity)
and total alkalinity (M-alkalinity).

Fig. 10

1.3.5 Silica / Silicate

In tropical and sub-tropical countries with heavy rain falls, raw water has regularly medium to
high concentrations of silica (silicon oxide) and/or silicates (compounds of silica with e.g. cal-
cium, magnesium, aluminium, e. g. alumo-silicates = clay), particularly river after heavy rain
fall. Both, silica and silicates origin from under-ground materials like granite, mica, clay, basalt
etc.; lime stone (calcium carbonate) contains only little silica and has been mostly dissolved by
rain water.
Silica and silicates can be present in dissolved and quasi dissolved (colloidal) form and are not
easy to eliminate or to reduce by water treatment. Mechanical filters and softener are unable
to eliminate e.g. calcium-silicate and silica.
The solubility of silica (silicon oxide) in water increases strongly by temperature and alkalinity.
In neutral or weak alkaline water the solubility is relatively low, which results to formation of
silicon scale.
Silicates are almost insoluble in water, except alkali (Na, K) silicates, which leads to silicate
scale if silica and hardness comes together in absence of phosphate.

1.3.6 Iron, Manganese

Iron and manganese compounds are frequently present in ground water or well water, if their
oxygen content is low. This happens mostly in undergrounds with organic substances like river
sediments - in some cases presence of hydrogen sulphide is likely.
Iron and manganese compounds may lead to scaling in piping systems due to iron ochre. After

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contact with oxygen (air) brown flocks are formed that may cause deposits in softeners and
reduce the activity of softener resin. Iron compounds lead to brown stains on fabrics.
In many cases aeration makes iron compounds removable in mechanical filters. For manga-
nese compounds aeration is often insufficient and stronger oxidation measures are necessary.

1.3.7 Organics
Organics in raw water may origin from nature (e.g. rotted leaves, peat) or human or industrial
sources (e.g. waste water, industrial effluents), also condensate return can be contaminated
through product (e.g. milk, vegetable oil, solvents). Many organics lead to foam formation in
steam generators that affects the steam quality due to carry over of boiler water. Some organ-
ics, like sugar and alcohols decompose to organic acids and lower the pH of the boiler water.
Oil and fat is able to set level control systems out of order, to block side glasses and may form
dangerous scale. Hydro carbons with boiling point below approx. 130 °C regularly do not have
negative effects to boiler.
1.3.8 Gases (Oxygen, Nitrogen, Carbon dioxide etc.)
Oxygen, nitrogen and carbon dioxide is always dissolved in water if it is or was exposed to air.
The solubility of all gases in water depends strongly on temperature, see Fig. 11. Oxygen
leads to oxygen corrosion on carbon or low-alloyed steel if the pH is too low and/or the steel
can not form or maintain a protective layer of magnetite. Nitrogen does not harm boiler opera-
tion. Carbon dioxide lowers the pH-value and leads to acid corrosion on carbon steel.

Fig. 11: Solubility of oxygen and nitrogen in pure water at 1 bar absolute

Oxygen and nitrogen in water is easy to reduce by heating and becomes nearly zero at boiling
conditions! Some chemicals, like sodium sulphite and hydrazine are able to bind oxygen
chemically. Carbon dioxide can be only removed by heating if the water’s pH is below 7-8 or at
pH > 8, if the operation temperature of a thermal deaerator is above 135-140 °C.

2 Water Treatment
Water treatment in this paper means any method to minimise scaling or corrosion in boilers.
It can be done in form of an “Inner water treatment” or “Extern water treatment”.
- Inner boiler water treatment or “chemical treatment” means treatment by exclusively dosing
of chemicals to the boiler feedwater or boiler water with the consequence of sludge forma-
tion within the boiler itself. Presupposition for this kind of water treatment is limited heat
transfer (steam production < 25 kg/m²⋅h), coal or wood firing (not oil!) and sufficient blow
down. The inner side of the boiler must be easy accessible to remove sludge.
This method may be used for small vertical shell boiler only.
- Extern boiler water treatment applies at least softening to bind hardness on the softener
resin and replace hardness by sodium, but can be improved by additional reverse osmosis
(RO) units or e.g. demineralisation. This treatment can be used for any kind of steam boiler
but requires also sufficient blow down to meet the related boiler feedwater and boiler water
requirements. It must be applied for water tube boiler!
The treated water is mostly dosed (conditioned) with some chemicals to adjust e. g. pH or
alkalinity. Thermal deaeration is also an external treatment step.
- Physical water treatment, using e.g. magnets, high frequency fields, high voltage fields etc.
is a not accepted method for boiler feed water or boiler water treatment, because all this
methods do not remove hardness and do not affect silica or silicates!
2.1 Inner boiler water Treatment

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Scaling doe to hardness and silicates can be significantly reduced if sufficient tri-sodium phos-
phate is dosed proportional to the fed hardness and feedwater flow. Carbonate and non-
carbonate hardness react with phosphate and form calcium- and magnesium- phosphate
sludge, which remains mostly in suspended form in the boiler water. During operation, the
sludge must be removed by sufficient blow down. After operation, sediment sludge must be
removed by additional blow down.
Phosphate has a higher affinity to calcium and magnesium than carbonate or silica and avoids
formation of carbonate and silicate scale. In parallel carbonate hardness becomes exchanged
to sodium carbonate, which is alkaline, increases alkalinity and the solubility of silica.
For one cubic meter (m³) water with 1 meq/l hardness, an amount of 120 g tri-sodium phos-
phate (technical grade with 10 mol of crystal water, Na3PO4⋅10 H2O [20 % P2O5]) dissolved in
at least 5 l water is necessary. For instance, to treat 1 m³ feedwater with 3 meq/l = 1,5 mmol/l
= 150 mg/l CaCO3 total hardness an amount of ca. 350 g Na3PO4 ⋅10 H2O is necessary.
Inner boiler water treatment is easy, as far as the total hardness of the raw water is low (less
than 1-1.5 mmol/l), or rain water is used.

2.2 Extern boiler water treatment

2.2.1 Softening
Softening is a simple and safe way to eliminate hardness from a clear water (turbid water must
be treated before e. g. with sand filter) by using filters filled with softener resin (mostly honey-
brown beats with 0.6-1.5 mm diameter made of strong acidic cation exchanger in sodium
form). This resin is able to exchange hardness (calcium and magnesium salts) into sodium
compounds, that are - in comparison to hardness - all highly soluble in water. The resin keeps
the hardness ions and releases sodium ions, that means e.g. calcium bi-carbonate is ex-
changed to sodium bi-carbonate, magnesium chloride to sodium chloride etc. all other con-
stituents were not changed. During operation cycle the hardness is < 0.02 mmol/l = < 2 ppm
CaCO3.
Common softener resins have a hardness capacity of 0.6-0.7 mol/l corresponding to 60-70 g
CaCO3 per litre resin. For instance 50 l sufficient regenerated resin can exchange ca. 3,200 g
CaCO3 or are able to soften approx. 30-32 m³ water with 100 mg/l CaCO3.
If the resin is loaded with hardness and not anymore able for the mentioned ion exchange (it is
exhausted) operation must be stopped. It must be brought back into the required sodium form
by application of an excess of salt (sodium chloride, NaCl) solution (brine), which is called re-
generation. The salt must not have too much insoluble impurities to avoid blockage of the
resin filter bed! Principles about softening and regeneration show Figs. 12 & 13.

Fig. 12:

Fig. 13

Regeneration takes ca. 60 minutes and includes following steps: Back washing (to remove
unsolved particles from the resin bed, but not too fast - otherwise resin is lost!), application of
clear brine for about 30 minutes, rinsing of the brine, final rinsing and testing for hardness.
Necessary equipment for continuous supply of softened water: 2 softener filter (or one and a
storage tank) made of coated steel or glass fibre reinforced polyester, filter internals and resin,
flow meter, water meter, sampling valve for softened water, brine tank with side glass or level
control, injector to dilute brine to about 10 % salt solution and drain valve.

Attention: Softening is the minimal requirement for oil fired steam or hot water boiler with
common heat transfer and for water tube boiler, if there are no further requirements to boiler
operation and steam quality. Optimised quantity of condensate return is very advantageous.
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2.2.2 Reverse Osmosis (RO, Desalination)

Reverse Osmosis is an excellent physical method to reduce the content of all dissolved solids
of water (e.g. total hardness, chlorides and silica) to a minimum that leads to a major reduction
of its conductivity, principle is shown in Fig. 14.
RO is quasi an ultra filtration method that separates bigger water soluble ions from little water
molecules but removes also undissolved matter (e.g. clay, iron oxide), organic substances and
micro organism (e.g. bacteria and germs). The latter noted bigger size matter is able to block
the pores of the polymer membranes of RO modules as well as hardness deposits and col-
loids. Micro organism likes to eat the polymer membranes and may damage the membranes
irreversible. If not domestic water with restricted content of germs is used, the water must be
disinfected with chlorine, hypo-chloride or better with ozone (it reduces also organics) but ex-
cess chlorine or ozone must be removed in an activated carbon filter.
The water for RO units must be really clear, must have only restricted amount of organic mat-
ter and micro organism and must be treated to avoid precipitation of concentrated water con-
stituents in front of the membrane surface, like hardness.
About 70 % of the water to a RO unit can be received as treated water, 30 % must be drained.
An acceptable life time of 3 to 5 years of RO modules can be achieved only, if there is a suffi-
cient, professionally operated water pre-treatment of the water before entering the membrane
module and if the membrane is rinsed, cleaned and disinfected in periodical intervals, particu-
larly for longer shut-down. RO units should operate continuous feeding a storage tank from
where water is taken out on demand.
To avoid precipitation of hardness for smaller RO units (< 20-40 m³/day) upstream of a RO
unit first softening of the raw water is recommended.

The water downstream of RO-units (so called permeate) that is fed with softened water is free
of hardness, shows low conductivity (regularly < 20 µS/cm, mostly due to sodium bicarbonate)
and silica < 0.2 mg/l SiO2!

During thermal deaeration, residual sodium bicarbonate decomposes to alkaline sodium car-
bonate, increases the pH and leads to an excellent weak alkaline BFW for low and medium
pressure boiler.
For pH adjustment in the BW dosing of tri-sodium phosphate is essentially!

RO-units need less control, space for installation, chemicals and are for a water demand
< 20-40 m³/day much cheaper and easier to handle than other treatment methods, but once
again the water pre-treatment must be done professionally.
Permeate is recommended if the conductivity of the raw water or boiler feedwater is high and if
better steam quality is required, e.g. for food production, cosmetic or pharmacy industry.
Optimised quantity of condensate return is very advantageous.

Fig. 14
Principles of Osmosis and
Reverse Osmosis (RO).

Fig. 15
Partly unrolled cross flow membrane
module

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2.2.3 Deaeration
Thermal deaeration is the simplest way to minimise the content of dissolved gases in water
like oxygen, nitrogen and carbon dioxide, because their solubility in water depends strongly on
the temperature and becomes zero at boiling conditions, see Fig. 11.
Common are tray deaerator, sketch see Fig.16 operating at over-pressure of 0.3-1 bar. They
heat the BFW to temperatures > 100 °C and reduce oxygen to the limits < 0.02 mg/l as far as
the deaerator has a sufficient number (at least 4-5) of trays, like vertical deaerator. Horizontal
deaerator with 2-3 trays reduces the oxygen content only to about 0.1-0.3 mg/l.
For smaller plant at least partial thermal deaeration at temperatures between 50 and 80°C is
recommended, which can be easy achieved with sufficient hot condensate return and indirect
heating with blow-down water using a tube coil within the storage tank. Remaining oxygen can
be eliminated by dosing of an oxygen scavenger like sodium sulphite.

Fig. 16

3 Boiler Types and Water Requirements

3.1 Boiler Types
The boiler types are divided into
- Shell boiler with boiler water around the fire box respectively flame tube as well as around
the smoke tubes and flue gas within the tubes and
- Water tube boiler with boiler water within the tubes, and flue gas around the tubes.
The water tubes are connected to a steam drum to separate water and steam (drum boiler).
Vertical Shell or Package Boiler are mainly coal fired one-pass steam generator with fire box
and some horizontal smoke tubes, operate at a pressure up to 10 bars and have steam capac-
ity less than 2,000 kg/hr. Their specific steam production is regularly < 25 kg/m²·hr. Only on
that type of boiler inner water treatment is acceptable!
Horizontal Shell boiler are mainly gas or oil fired, see Fig. 17, three-pass steam generator with
one or two fire tubes as first pass and smoke tubes for second and third pass. The design re-
stricts the operation pressures to ca. 30 bars and steam capacity to about 25 t/h. They are
equipped mostly with economiser but rarely with super-heater. They were delivered as pack-
age on a frame and supply steam to small and medium scale plants, but occasionally also to
large-scale plants as auxiliary boiler for start up. If they are heated by solid fuel (coal, wood
etc.) they may have in front of the fire tube a compartment with water tubes.

Fig.17:

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The smoke tubes are fitted into the front and rear tube-sheet with a gap between tube and
tube-sheet and welded at the flue gas side only, which leads to heated gaps at these spots
and to localised concentration of boiler water constituents within the gaps.

Water-tube boiler are mostly gas/oil/coal fired steam generators with natural or assisted circu-
lation for pressures up to 180 bar and a steam production in industrial plants up to approx.
500 t/hr equipped with super-heater, de-super-heater and feedwater pre-heaters.
Quick start up boiler are mainly small gas or oil fired water tube boiler with natural or forced
circulation that produce saturated steam in less than 30 minutes but with higher BW content in
steam than other boiler.

3.2 Definition of Water Types

Raw water is any water before water treatment took place, like domestic water, well water,
river water, rain water etc.
Filtered water is water after a mechanical filtration to remove undissolved matter.
Softened water is water or pre-treated water downstream a softener using strong acidic cation
exchanger in sodium form and salt (sodium chloride) as regenerant. The water is free of hard-
ness (< 1 ppm CaCO3 or < 0.01 mmol/l) but silica and conductivity is unchanged.
Decarbonised water is treated water downstream a lime hydrate decarbonisation after filtration
or decarbonised water downstream a weak acidic cation exchanger. Both waters must be sof-
tened if used as make-up water. The water is distinct lower in carbonate hardness and con-
ductivity but silica is unchanged if ion exchanger is used. Hot lime decarbonisation may re-
duce silica for 10-30 %.
Desalinated water is water from Reverse Osmosis units (permeate), that must be softened as
make-up water for boiler if the water before the RO unit is not softened. The water shows at
least a direct conductivity at 25 °C < 30 µS/cm (mostly < 10 µS/cm) and silica content < 0.5
mg/l (ppm) SiO2.
Make-up water is treated water used as substitute for the loss of condensate in the system.
Condensate return is clean condensate return from consumers. It should not be mixed with
make-up water before thermal deaeration. Possible contamination with impurities from pro-
duction requires adequate online quality control and e. g. condensate treatment.
Condensate is valuable because it is clean water (with low conductivity and without hardness
and silica) it is hot and contains energy. A condensate return of e.g. 50 % reduces the feedwa-
ter conductivity for about 50 %!
Boiler Feedwater (BFW) is the treated, conditioned and deaerated water fed to the steam gen-
erator. It is mostly a mixture of condensate return and make-up water. For pH adjustment and
oxygen scavenging mostly “conditioning” chemicals are added.
Boiler water (BW) is the water circulating within the boiler. It consists of concentrated BFW.

3.3 Boiler Feedwater and Boiler Water Requirements

3.3.1 Presuppositions
Water Requirements of the Boiler Manufacturer is warranty related!
Check the boiler feedwater and boiler water requirements of the boiler manufacturer referring
to boiler pressure and design and compare it with the quality of the existing or planed water
treatment plant and the realistic feedwater quality - including condensate return. Is it with the
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existing water treatment possible to meet the requirements under economical conditions?
Steam Purity and Steam Requirements is warranty related!
Check the boiler manufacturer’s guarantee of the steam produced and compare it with the
requirements or demand for processing. The BW content in steam should not exceed 0,1 -
0.2 %. As far as the steam is used for indirect heating only, up to 0.5 % BW content in steam
is acceptable. The BW content in steam must be guarantied by the boiler manufacturer!

3.3.2 Water Requirements

International standards:
There are Standards from America (e.g. from ASME), Europe (EN 12 953-10 for Shell Boiler,
EN 12 952-12 for Water Tube Boiler), Japan etc. as well as national standards.
The requirements do not differ very much, but refer basically to modern boiler - vertical shell
boilers are not included in international standards.
The water requirements refer to steam generator & hot water boiler made of low-alloyed or
carbon steel that are heated by combustion of one or more fuels or by hot gases.
Most Standards describe safety related minimum requirements and apply to components be-
tween the feedwater inlet and the steam outlet.

Applicable Feedwater and Boiler Water Requirements are shown in the following for:

3.3.2.1 Vertical Shell (Package) Boiler

With operation pressure > 0.5-10 bar(g) and ≤ 1,5 t/hr steam production
Preliminary Remarks:
These water requirements refer to steam generators that are heated by combustion of manu-
ally fed solid fuel. The boilers must have a specific steam production < 25 kg/m²⋅hr and must
be equipped with at least one sufficient blow-down drain.
For boiler with specific steam production ≥ 25 kg/m²⋅hr, pressure >10 bar and/or steam pro-
duction > 1.5 t/hr as well as for boiler being heated by combustion of liquid fuel or gas, the
water requirements for “Shell Boiler” must be applied.

Water Treatment:
In general softening of the make-up water or boiler feedwater should be standard to avoid
scaling and sludge formation within the boiler.
If there is no make-up or boiler feedwater treatment with a softener, at least “Inner Boiler Wa-
ter Treatment” (IBWT) through dosing of suitable chemicals in sufficient amount must be ap-
plied.
Sufficient intermittent blow-down and rinsing of show glasses as well as external level control-
lers/indicators etc. is essentially, at least once per day, with IBWT every 8 hrs.

Requirements:
The following values show safety related minimum requirements for both softened boiler feed-
water and not softened feedwater that becomes treated within the boiler itself (“Inner Boiler
Water Treatment” (IBWT) to minimise corrosion and deposition.

Boiler Feedwater (BFW) Softened with IBWT

∗ Total Hardness (Ca + Mg) a ppm CaCO3 < 10 < 150

∗ pH value at 25 °C ⎯ (7.5) 8 - 9.5 7.0 - 9.5
∗ Composite Alkalinity (P-value) ppm CaCO3 2.5 - 25 0 - 25

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Oxygen b mg/l < 0.5 <5

Boiler Water (BW) From softened BFW with IBWT

Undissolved matter c almost clear < 5 ml / 100 ml

∗ pH value at 25 °C ⎯ 11 - 12.3 11 - 12.0
∗ Composite Alkalinity (P-value) ppm CaCO3 100 - 1500 100 - 500
∗ Total Hardness (Ca + Mg) a ppm CaCO3 < 10 < 50
∗ Direct Conductivity at 25 °C µS/cm < 5000 < 3000
∗ Phosphate (PO4) a mg/l 10 - 20 10 - 40
∗ Most important values; mg/l is equal to ppm.

Notes
a
Water samples must be clear filtered to get correct values!
b
Oxygen content is reduced physically if water is heated at ambient pressure up to:
- 85 °C the oxygen content is reduced to approx. 2 mg/l
- 95 °C the oxygen content is reduced to approx. 0.5 mg/l.
At lower temperatures the oxygen content can be reduced through dosing of oxygen
scavenger e. g. sodium sulphite.
c
Undissolved matter as sediment sludge after settling time of 1 hr.

Test of chemical composition

The noted parameters shall be checked periodically. The frequency of testing shall be speci-
fied in the boiler operating instructions. For feedwater and boiler water at least weekly tests of
the most important values (∗) pH value or alkalinity, hardness, conductivity, phosphate and
undissolved matter for IBWT operation are recommended.

3.3.2.2 Horizontal Shell (Package) Boiler and Water tube Boiler

With operation pressure > 0.5-30 bar(g)
Preliminary Remarks:
These water requirements refer to steam generator & hot water boiler > 110 °C that are
heated by combustion of fuels or by hot gases. Shell boiler fired with solid fuel may have in
front of the fire tube an external furnace possibly cooled with water tubes.
These requirements apply to components between the feedwater inlet and the steam outlet
but do not cover the quality of steam produced and/or economical reasons etc.
For certain purposes, it will be appropriate to adapt the chemical requirements in order to op-
timise e. g. the steam purity (for super-heater operation) and plant reliability.
Water Treatment and Conditioning
Water Treatment: At least softening of the make-up water, boiler feedwater or circulating hot
water has to be standard to avoid scaling and sludge formation; make-up water of higher qual-
ity may be necessary in particular cases.
Conditioning: The specific geometry of common shell boilers with heated gaps/crevices at
joints between welded and/or rolled flue gas tubes and tube sheets or reverse chambers re-
spectively requires particular conditioning of the feedwater and boiler water with phosphate.

Requirements:
The noted safety related minimum requirements for the boiler feedwater, boiler water or circu-
lating hot water are set to reduce the risk of corrosion, sludge formation or deposition within

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the boiler. The values stated shall apply to continuous operation. During start-up, some values
may deviate for a restricted period of time and to a limited extent to be specified by the boiler
manufacturer.
A Steam Generator
A 1 Boiler Feedwater (BFW)
For boiler with operation pressure bar(g) > 0.5 - 15 > 15 - 30
∗ Total Hardness (Ca + Mg) a
ppm CaCO3 <2 <1
∗ pH value at 25 °C ⎯ (7.5) 8 - 9.5 8.5 - 9.5
∗ Oxygen b mg/l < 0.1 < 0.02

A 2.1 Boiler Water (BW) Using BFW with direct Conductivity > 30 µS/cm
Boiler with operation pressure bar(g) > 0.5 - 15 > 15 - 30
∗ Direct Conductivity at 25 °C c µS/cm < 4 000 < 2 000
∗ pH value at 25 °C ⎯ 10.5 - 12.0 10.5 - 11.8
∗ Composite Alkalinity (P-value) c ppm CaCO3 100 - 900 100 - 600
∗ Total Hardness (Ca + Mg) a ppm CaCO3 < 10 <3
∗ Phosphate (PO4) a, d mg/l 10 - 30 10 - 30
∗ Silica (SiO2) mg/l < 120 < 100

A 2.2 Boiler Water (BW) Using BFW with direct Conductivity ≤ 30 µS/cm
Boiler with operation pressure bar(g) > 0.5 - 15 > 15 - 30
∗ Direct Conductivity at 25 °C µS/cm < 2 000 < 1 000
∗ pH value at 25 °C ⎯ 10.5 - 11.5 10.5 - 11.3
∗ Composite Alkalinity (P-value) ppm CaCO3 25 - 250 10 - 100
∗ Total Hardness (Ca + Mg) a ppm CaCO3 <3 <1
∗ Phosphate (PO4) a, d mg/l 10 - 30 10 - 20
∗ Silica (SiO2) mg/l < 100 < 80

B Hot Water Boiler

B 1 Feedwater and Make-up Water
∗ Total Hardness (Ca + Mg) a ppm CaCO3 <5
∗ pH value at 25 °C ⎯ > 7.0
B 2 Circulating Hot Water with temperature >110 °C
∗ Direct Conductivity at 25 °C µS/cm < 1 000
∗ Total Hardness (Ca + Mg) a ppm CaCO3 <5
∗ pH value at 25 °C ⎯ 9.5 -11.5
∗ Composite Alkalinity (P-value) ppm CaCO3 25 – 250
Notes
a
Not really clear water samples must be filtered clear to get correct values!
b
Oxygen content can be reduced physically almost to < 0.05 mg/l if water is heated to boiling
temperatures, preferable using thermal deaerator. At lower temperatures the oxygen content
can be reduced through dosing of an oxygen scavenger e. g. sodium sulphite.
c
With super-heater operation consider 50 % of the noted upper value as maximum value.

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d
Tri-sodium phosphate dosing must be applied for shell boiler, if BFW with direct conductivity
≤ 30 µS/cm is used, but it is also recommended for BFW > 30 µS/cm!
∗ most important values; mg/l is equal to ppm in water.

Test of chemical composition

The noted parameters shall be checked continuously or periodically. The frequency of testing
shall be specified in the boiler operating instructions. For steam boiler at least daily, and for
hot water boiler weekly tests of the most important values (∗) pH value or alkalinity, hardness,
conductivity, oxygen or excess of oxygen scavenger, silica and phosphate are recommended.

4 General Comments and Recommendations

The mentioned BFW and BW requirements can be kept easier and more economical if there is
sufficient condensate return – collect as much as possible! As noted, regularly the condensate
is pure hot water with e.g. temperature > 80 °C that contains in this case an energy about 340
kJ/kg that corresponds, regarding the heat value, to about 10 kg coal per m³ condensate and
considering the boiler’s efficiency to 30-40 kg coal saving – already not considered the lower
blow down rate.
Condensate with temperature > 100 °C, like condensate from ironing, releases steam that
leads to high loss of energy! The steam can be cooled and condensed with spraying cool sof-
tened make-up into the steam flow of the vent of the condensate tank or installation of a cool-
ing coil made of stainless steel.
The energy of 1 kg released steam is about 3,100 kJ, which is almost 10 times more than that
of condensate of 80 °C and leads to 250-350 kg coal saving per 1000 kg steam!
Pumps for hot water must be connected in short distance to the hot water tank and must have
a wide diameter at their inlet part (incl. block valve, best ball valve) to avoid pressure drop and
cavitation at the pump. Hot water can be safely pumped if there is a little pressure at the inlet
side of the pump, which can be easy achieved if the water level of a hot water tank is about 2-
3 m above the pump inlet.
During boiler operation and steam production, the dissolved and undissolved water constitu-
ents become concentrated and must be kept within the limits of the BW requirements by dis-
continuous or continuous blow-down, that means some hot boiler water is taken out of the
boiler and drained. This hot blow-down water contains energy, e.g. boiler water of 5 bar pres-
sure 670 kJ/kg. A discontinuous blow-down makes it difficult to take the energy back because
of the high flow rate in short time of some seconds. A continuous blow-down device takes a
low flow rate of BW continuously out, which can be used to heat up BFW indirectly using a coil
made of carbon steel. Discontinuous blow-down is economical with boiler > 10 bar and > 2 t/hr
steam production.

5 Inorganic and Organic “Anti-Scalants“ and “Dispersants“

These chemicals can be applied in shell and drum boilers to minimize scaling. Specific organic
anti-scalants can be dosed also as preventive measure to clean a boiler from some thin scale
during operation.
Inorganic anti-scalants like Tri-sodium / Tri-potassium phosphate, also used as alkalising
chemicals, are applicable in boilers up to 180 bars. They react with hardness (Ca-, Mg-
compounds) to hydroxyl apatite that remains mostly in suspension and avoids scale of lime-
stone, gypsum and aluminium-silicate. Due to stronger affinity of phosphate to hardness than
to silica, silicate scale can be significantly reduced in presence of phosphate.
Organic anti-scalants are mostly a mixture of poly-carbonic (poly-acrylic) acids or amides, as
well as organo-phosphonates. Many products show a weak complex forming behaviour and

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keep Ca- /Mg-compounds in solution but are not too aggressive to iron oxides like chelants
and applicable for boiler pressure < 120 bars.
Chelants are strong complex forming agents like EDTA, NTA and keep hardness and metal
ions in solution. Too high concentrations attack the protective iron oxide layer and are not rec-
ommended in low pressure industrial boiler.
6 Preservation
Preservation means basically any method to avoid corrosion - mostly oxygen corrosion - on
the waterside of boilers, parts of it or auxiliary components made of low-alloyed steel during
shutdown and stand-by, but also during storage and transportation.
A sufficient and commonly present protective layer of iron oxides on the waterside of boilers
(being in operation before shut down for at least 1 month) is able to protect low-alloyed steel in
presence of humidity or moisture and air for restricted time only.
If softened water or permeate is used, the time without preservation is restricted to approx. 1
week, but with frequent shut-down times much shorter!
Exceeding times or frequent shut-down times requires preservation methods by either
- Wet preservation (in absence of air) e.g. by replacing of air by nitrogen or complete kept
filling of the boiler with at least alkaline water, better containing oxygen scavenger, or
- Dry preservation (in absence of moisture) by drying with desiccants, e.g. silica gel or
regenerative circulating dryers.

Wet preservation is recommended particularly for shorter downtime by e.g.:

- Completely filled boiler (and kept filled up to vent!) with alkaline boiler water (pH about 10)
for some days or excess of oxygen scavenger and pH 10-11 for some weeks to few month.
For short shut down, let the boiler cool down to approx. 1 bar and fill it with BFW up to the
vent. Keep the boiler filled and check it every 2 days.
- Keeping steam pressure from other boiler in operation and maintain a steam blanket. That
leads to condensate formation at the steam/water interface, lowers the BW pH and needs
drainage to keep the water level in the boiler. Risky if the steam is not oxygen free!
- Application of inert gas (nitrogen) with partly filled or empty but wet boiler for some weeks
to few months. Keep and check nitrogen over pressure of 10-20 mbar. Vent the boiler suffi-
ciently before somebody is entering the boiler to avoid suffocation.

Dry preservation is recommended for longer downtime (some months) by either

- Desiccants e. g. silica gel (but avoid direct contact to steel!) or caustic lime (CaO) or
- Application of re-circulating dryer in case of preservation of bigger volume tanks.
Preservation on the flue gas side of boilers may be necessary too, particularly on coal and oil
fired boilers.

7 Sampling of Boiler Feedwater and Boiler Water / On Line Control

Sampling pipes should be made of stainless steel (at least of TP 321 or 316), be as short as
possible and in a diameter of approximately 10 x 1.0 – 1.5 mm or 12 x 2 mm.
Hot samples should be cooled down to ca. 25 -30 °C with a flow of at least 25 kg/hr. The
cooler coil should be made from stainless steel. Cooler are urgently recommended for boiler
with pressure > 10 bar and for oxygen measurement in BFW.
All sampling devices should have a straight blow out line before entering the cooler or the
measuring equipment.

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7.1 Sampling of Water

No special design necessary, but a representative average (bulk) sample must be available.
Sampling device for oxygen measurement must be gas tight by welding or particular high pres-
sure fittings and valves!
Sampling points are recommended after any treatment step and chemical dosing point, which
leads to a possible change of the water quality and are a must for BFW and BW, for instance:
- Raw water and water after pre-treatment (flocculation, filtration, de-chlorination).
- Treated water after softening or RO plant
- Raw condensate and/or from condensate tank,
- BFW after deaeration and chemical dosing - optimal at boiler inlet
- BW from continuous blow down (min. 100 l/hr) close to the drum or directly from the boiler
opposite the feedwater inlet.

7.2 Chemical Control of Plant Circuits

Manually controlled must be at least Boiler Feedwater (BFW) and Boiler Water (BW) once per
day for the following safety related parameters:
Total and composite alkalinity (P- an M-value) or pH
Total hardness
Conductivity
Phosphate / Anti-scalants - if dosed
Silica 2 x per week
On-Line controlled should be conductivity of BW because it can be used as signal for auto-
matic blow down. The conductivity measurement should be temperature corrected to standard
reference temperature of 25 °C.
Measurement of hardness in make-up water and condensate return should be done on de-
mand. Oxygen can be measured with “Karmina Chemets” in BFW.

8 Boiler Pre-Treatment and Chemical Cleaning of Boilers

8.1 Procedures for Boiler Cleaning
8.1.1 Alkaline boil out
Before alkaline boil out, new boiler, especially water tube boiler must be mechanically cleaned
and rinsed with BFW or softened water - best alkalised to a pH around 9.5 with volatile chemi-
cals - to remove solids until the drained water is almost clear! Rinse and check every drain for
possible blockage.
New boiler should undergo at least an alkaline boil out to remove oily and fatty matter as well
loose oxides and dust, commonly using tri-sodium phosphate, caustic soda, a mixture of both
or other alkaline chemicals like dispersants well dissolved in water (boil out solution up to a pH
of approx. 10 -10.5) at elevated temperature up to approx. 70 % of the normal operation pres-
sure. During boil out any contamination of steam lines to consumer must be definitely avoided.
For boiler with heated crevices e. g. between tubes and tube-sheet, like shell boiler or process
gas cooler the exclusively use of caustic soda is prohibited (may initiate caustic stress corro-
sion cracking, SCC) and tri-sodium phosphate recommended. Before operation the boil out
solution must be drained and the boiler must be rinsed sufficiently through all drains to remove
further solids and to dilute the boil out chemicals to conditions (pH, conductivity) close to that
of the incoming rinsing water.

8.1.2 Chemical Cleaning during shutdown

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Acid Cleaning (Pickling)

Before any acid cleaning an alkaline boil out is necessary to get a “hydrophilic” (easy to wet)
surface. Acid cleaning is recommended for new boiler in case of significantly corroded sur-
faces and for boiler with local heat flux > 250 kW/m², particularly if there are many welds in the
area with high heat flux. On boilers already being in service, acid cleaning is necessary if inor-
ganic scale is thicker than acceptable (depending on heat flux and composition > 0.1 to 1
mm). It is usually carried out with inhibited inorganic (preferable hydrofluoric or hydrochloric
acid) or inhibited organic acids (citric acid, glycolic acid, formic acid etc.). Silicate scale can be
dissolved only with hydrofluoric acid, which must be done by experts!
Inhibitors for acid cleaning are organic compounds that reduce corrosion to metallic surfaces
drastically in specific media. They reduce the rate of the anodic processes of metal dissolution
by the formation of an “organic protective film” on the exposed metal. Mill scale and other
scale is not protected and will be dissolved as supposed.
Inhibitors must be adapted to the type of acid, the metal in service and to temperature. The
inhibitor concentration and maximal application temperature (mostly not exceeding 60-80°C)
must be kept within its correct range following supplier’s application recommendation for opti-
mal corrosion protection.
For any chemical cleaning the limits of the application conditions for the combination - solvent,
e.g. acid, inhibitor, temperature and application time - must be kept exactly to avoid excessive
material attack. The loss of base metal must not exceed 20 g/m² (= 2.5 µm loss of wall thick-
ness) during application. A representative steel sample with different thick mill scale layers
should be merged into the solvent to check the cleaning progress during application.
The cleaning process must be controlled by measuring at least acid and metal concentration.
For test cases an average sample of the applied solvent of at least 10 litres (e. g. 1-2 l from
any batch) of the cleaning solution should be taken and kept to repeat corrosion tests.
For austenitic stainless steel, hydrochloric acid is not permitted! Ferritic stainless steel shows
against some acids higher corrosion rate than mild steel!
Any acid cleaning should be finished with a passivation step to form a thin homogeneous ox-
ide layer; cleaned boiler shall go into operation as soon as possible
Chemical Cleaning with other Chemicals
Chelants like EDTA or NTA where applied regularly in alkaline solution but should be rarely
used for cleaning because of inhomogeneous cleaning and environment effects. They need
application temperatures > 80 -100 °C, which is frequently adjusted by direct firing with a risk
of heterogeneous temperature distribution, different cleaning effect and corrosion rate.

8.1.3 Chemical Cleaning during operation

Cleaning during operation (see also chapter 5) is possible as far as the scale thickness do not
exceed 0.3 mm (localised max. 0.5 mm), thicker scale may peel off and may affect the boiler
water circulation. Easy removable is scale consisting > 50 % of calcium and magnesium com-
pounds without fat or oil. Application of aggressive chelants like EDTA or ETA is possible but
difficult to handle and affects the environment.
Recently biological degradable organic anti-scalants and dispersants have been developed
with lower complex forming strength than EDTA or NTA, which can be used for cleaning dur-
ing operation. Producer of such weaker complex forming agents are international chemical
treatment companies such as Betz, Drew, Grace-Dearborn, Kurita or Ondeo (Nalco). These
chemicals should be used temporarily - may be one month per year - to remove thin scale
preventively. As far as a boiler was operated according to the BFW and BW requirements,
chemical cleaning is not necessary within less than 5 years. Frequent cleaning activities indi-
cate clearly lack in BFW and BW treatment or insufficient preservation during stand still.
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