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TAKORADI THERMAL POWER STATION

HRSG BOILER CHEMISTRY TRAINING

For
Operators and Maintenance Staff
www.vra.com 1.0 INTRODUCTION
1.1 Brief description of the HRSG
• The HRSG is an assembly of tubes arranged in the path of
waste heat, with water running through the tubes (see
figure 1 below). At TTPS the source of the waste heat is
the hot exhaust from the Gas Turbines.

• Generally, the two main kinds of HRSGs are:

a. Drum HRSGs and
b. Once-Through HRSGs
www.vra.com 1.0 INTRODUCTION
1.1 Brief description of the HRSG
a. Drum HRSGs
• Drum HRSGs have feed-water drums that feed the HP
evaporator tubes with water. The water circulates through the
different sections of HP evaporator tubes, drawing heat from
the hot exhaust, producing steam in the process.

• NB: Depending on the design, the HRSG may have one or two
more drums (boiler drums) that enable boiler water
recirculation and the production of steam in the drum.
www.vra.com 1.0 INTRODUCTION
1.1 Brief description of the HRSG
a. Drum HRSGs cont’d
• Steam from the boiler drum is drawn through the superheater
tubes located at a hottest section of the HRSG. The steam
draws more heat hot exhaust and becomes superheated
steam which goes to run the steam turbine.
www.vra.com 1.0 INTRODUCTION
1.1 Brief description of the HRSG
b. Once-Through HRSGs

• Once-through HRSGs have a feed-water drum but no boiler

drums. The feed-water drum supplies the tubes with water,
which flows through the various sections of the tubes till the
water becomes superheated steam (without recirculation of
boiler water in any drum).
www.vra.com 1.0 INTRODUCTION
1.1 Brief description of the HRSG

• The superheated steam is used to run the turbine and then

the exhausted steam is condensed in the condenser.

• The condensate is pumped to the de-aerator to remove

carbon dioxide, oxygen and other non-condensable gases.

• The de-aerated water then goes into the feed-water drum to

begin the cycle of steam production again.
Figure 1: HRSG Schematic Diagram

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www.vra.com 1.0 INTRODUCTION
1.2 The HRSG’s Purpose and Chemistry
• The purpose of the HRSGs is to exploit the energy in the waste heat
from the Gas Turbine exhaust to produce good quality steam to run
the steam turbine

• In the presence of water and oxygen, iron will corrode. This is of

concern because the drums and tubes are made of iron and water
flows through these tubes. Impurities found in water will form
deposits in the boiler drums and tubes. These deposits can also
enhance corrosion in the drums and tubes. Some of these
impurities can also be carried along with the steam into the steam
turbine and deposit on the blades which is difficult to remove.
www.vra.com 1.0 INTRODUCTION
1.2 The HRSG’s Purpose and Chemistry
• Chemical conditioning and monitoring of the HRSG water and
steam quality is necessary to prevent corrosion, scale and
deposit formation.

• The chemical conditions maintained in the HRSG during

operation, that ensure the continuous production of good
quality steam, satisfactory protection of the HRSG and Steam
Turbine from corrosion, scale formation and deposition of
undesired material is known as the Boiler Chemistry.
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2.0 HRSG BOILER CHEMISTRY AND CONTROL

The objectives of Boiler Chemistry Control are to prevent

• Corrosion in the HRSG and Steam Turbine
• Scale formation in the HRSG
• Deposits formation in the HRSG and Steam Turbine
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.1 Corrosion in the HRSG and Steam Turbine

2.1.1 Corrosion
Corrosion is the oxidation of metal iron in the presence of water
and oxygen, to form oxides and hydrated oxides of iron. Under
normal conditions, hydrated Fe3+ oxide, Fe2O3 . H2O called
haematite is formed, which is commonly known as rust. Once
corrosion begins, it is self sustaining and difficult to control.
Fe + ½ O2 + H2O  Fe(OH)2
2Fe(OH)2  Fe2O3 . H2O (rust)
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.1 Corrosion in the HRSG and Steam Turbine

2.1.1 Corrosion
The HRSG drums, tubes, steam pipes and steam turbine
components are all made of iron and hence susceptible to
corrosion. There is therefore the need to put in place measures
to prevent corrosion to prolong the life of the HRSG and Steam
Turbine.
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.1 Corrosion in the HRSG and Steam Turbine
2.1.2 Corrosion control
Corrosion is also facilitated in an acidic environment and
inhibited in an alkaline environment. The iron components and
water are essential for steam production but oxygen and acidic
pH are not. Therefore corrosion can be controlled by,
• Removing oxygen and
• Maintaining alkaline pH
in the HRSG water and steam.
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.1 Corrosion in the HRSG and Steam Turbine

2.1.2 Corrosion Control

Removing oxygen and maintaining an alkaline pH in the HRSG
water and steam controls corrosion by promoting another kind
of oxidation reaction which forms the oxide (Fe3O4) called
magnetite.
3Fe + 4H2O ==> Fe3O4 + 4H2
Magnetite forms a firm layer on the surface of the drums and
tubes, preventing further oxidation of the underlying metal and
hence forms a protective layer against further oxidation.
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.1 Corrosion in the HRSG and Steam Turbine
2.1.2 Corrosion Control – Maintaining Alkaline pH
Alkaline pH is maintained by dosing alkaline chemicals into
the feed-water and boiler drums.

pH measured at the operating temperature on a surface is

significantly lower than that measured under room
temperature conditions as shown in figure 2 below.

The relationship between at-temperature pH and corrosion is

shown in figure 3 below.
2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.1 Corrosion in the HRSG and Steam Turbine
Fig 2. Change of pH with temperature

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2.0 HRSG BOILER CHEMISTRY AND CONTROL

Fig 3. Effect of pH on general corrosion of carbon steel

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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.1 Corrosion in the HRSG and Steam Turbine
2.1.2 Corrosion Control – Oxygen Removal
Oxygen is removed from the HRSG by the two methods listed
below:

(1) Mechanical oxygen removal

(2) Chemical oxygen removal

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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.1 Corrosion in the HRSG and Steam Turbine
2.1.2 Corrosion Control – Oxygen Removal

(1) Mechanical oxygen removal:

In the de-aerator, feed-water falls on baffle plates, breaking
up into small droplets and with the aid of elevated
temperatures, the non-condensable gases (eg. carbon
dioxide, oxygen) are liberated. Small amounts of oxygen
however, remain in the feed-water as dissolved oxygen,
which can only be removed by chemical means.
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.1 Corrosion in the HRSG and Steam Turbine
2.1.2 Corrosion Control – Oxygen Removal
(2) Chemical oxygen removal:
Oxygen scavenging chemicals are dosed into the feed-water
to react with dissolved oxygen in the feed-water to form
gaseous products, which are removed from the HRSG.
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.1 Corrosion in the HRSG and Steam Turbine

2.1.2 Corrosion Prevention – Oxygen Removal

• It is important to ensure that after oxygen removal, the HRSG
is tight enough to prevent air ingress into the HRSG.
• The most likely/common sources of air ingress are leakages on
the suction side of pumps and the breathing action of tanks.
• See fig 4 for effect of low oxygen and high pH on corrosion.
 2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.1 Corrosion in the HRSG and Steam Turbine
Fig 4. Effect of oxygen and pH on general corrosion of carbon steel

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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.1 Corrosion in the HRSG and Steam Turbine

2.1.2 Corrosion Control – Passivation

Passivation of iron is the formation of a protective metal oxide
layer on the surface that prevents further oxidation of the metal
surface. Formation of magnetite by oxygen removal and
maintaining alkaline pH is one way to achieve passivation.
Magnetite is also formed when some oxygen scavengers like
Hydrazine and carbohydrazide react with haematite. Therefore
the use of these oxygen scavengers also facilitates passivation.
6 Fe2O3 + N2H4  Fe3O4 +N2 +H2O
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.2 Scale formation in the HRSG

2.2.1 Scale Formation

• Scale is formed in the HRSG due to the presence of the scale
forming ions Calcium (Ca) and Magnesium (Mg) in the water.
Scale forming ions exhibit retrograde solubility properties,
that is they are less soluble in water with increasing
temperature. As a result they tend to deposit on hot surfaces
in layers, building up with time and resulting in decreased
heat transfer, rendering the HRSG inefficient.
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.2 Scale formation in the HRSG

2.2.2 Prevention of Scale Formation

• Avoiding contamination of feed-water
• Dosing anti-scaling chemicals
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.2 Scale formation in the HRSG
2.2.2 Prevention of Scale Formation - Avoiding Feedwater Contamination
• Feed-water contamination is primarily prevented by using de-mineralized
water for feed-water and make-up water in the HRSG. However,
occasionally the quality of demin water used may be poor and may
contain mineral ions including scale forming ions. It must be ensured that
demin water used is always of good quality.
• Another source of contaminants is condenser tube leakage. Seawater is
used in the condenser to cool the exhausted steam. If there is a leakage in
the condenser tubes that carry the seawater, the condensate will be
directly contaminated with seawater. Seawater contains many mineral
ions including scale forming ions in high concentrations. Condensate
quality must be monitored continuously and corrective action taken as
soon as condenser tube leakage is detected.
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.2 Scale formation in the HRSG
2.2.2 Prevention of Scale Formation - Avoiding Feedwater Contamination

Although measures are taken to avoid ingress of scale forming ions,

contamination may still occur. To deal with such situations, phosphate
is dosed into the boiler water. A residual amount above the threshold
required to exceed the Ksp (solubility product) of the Calcium and
Magnesium Phosphate salts, is maintained in the water. Calcium and
Magnesium form sparingly soluble salts with Phosphate. Therefore any
Calcium or Magnesium ions that enter the water are immediately
precipitated in the presence of phosphate without giving them the
chance to form scale. These precipitates can be removed from the
water by blown-down.
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.3 Deposit Formation in the HRSG and Steam Turbine

Deposit formation in the HRSG and Steam Turbine are a result of:
• Dissolved salts content in the HRSG water and
• Silica content in the HRSG water
Deposits due to dissolved salts content occur mainly in the HRSG
but also occur in the Steam Turbine when water droplets are
carried along with the steam.
Deposits due to silica content in the HRSG on the other hand
occur in the Steam Turbine.
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.3 Deposit Formation in the HRSG and Steam Turbine
2.3.1 Deposit formation from dissolved salts
• Dissolved salts precipitate out of solution and leave behind
deposits of the salts when they become too concentrated in
water or when the water evaporates. In the boiler drum and
tubes, where water continuously evaporates to form steam,
there is a risk of deposit formation on the walls of the drum
and the walls of the tubes (especially in areas of high heat
flux) if the dissolved salt content in the water is high.
Dissolved solids in water droplets that are carried along with
the steam into the steam turbine, will eventually form deposit
on the turbine blades.
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.3 Deposit Formation in the HRSG and Steam Turbine
2.3.2 Silica Deposits
Silica is volatile in steam at high pressure. The volatility of silica is
related to the amount of silica in the water, the pH of the water
and the operating pressure (see figure 5). If silica in the boiler
drum water is higher than 10ppm, there is the risk of silica
becoming gaseous and being carried along with the steam into
the steam turbine. Once the pressures reduce in the steam
turbine, the silica loses its gaseous nature and deposits on the
turbine blades. A build up of silica deposits on the blades
reduces the efficiency of the steam turbine. Silica deposits are
hard and difficult to remove, requiring long downtime.
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.3 Deposit Formation in the HRSG and Steam Turbine

2.3.3 Preventing Deposit Formation

Deposit formation in the HRSG can be prevented/controlled by
• Minimizing entry of contaminants into the HRSG
• Maintaining Low Levels of Contaminants in the HRSG
• Preventing carryover into the steam turbine.
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.3 Deposit Formation in the HRSG and Steam Turbine

2.3.3 Preventing Deposit Formation

Deposit formation in the HRSG can be prevented/controlled by
• Minimizing entry of contaminants into the HRSG
• Maintaining Low Levels of Contaminants in the HRSG
• Preventing carryover into the steam turbine.
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.3 Deposit Formation in the HRSG and Steam Turbine
2.3.3 Preventing Deposit Formation – Minimizing Contaminant entry
into the HRSG

• Feed-water Contamination: The feed-water is the main source of

contaminants entering the HRSG. The first step required to prevent
contamination in the HRSG is to use de-mineralized water.
However, occasionally the quality of demin water used may be
poor and may contain mineral ions and silica. If this source of
contamination persist, contaminants will build up in the boiler
drum and increase the risk of deposit formation. It must be
ensured that demin water used is always of good quality.
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.3 Deposit Formation in the HRSG and Steam Turbine
2.3.3 Preventing Deposit Formation – Minimizing Contaminant entry
into the HRSG cont’d
• Condenser Tube Leakage: Another source of contaminants is
condenser tube leakage. Seawater is used in the condenser to cool
the exhausted steam. If there is a leakage in the condenser tubes
that carry the seawater, the condensate will be directly
contaminated with seawater. Seawater contains many mineral ions
including scale forming ions in high concentrations. Condensate
quality must be monitored continuously and corrective action
taken as soon as condenser tube leakage is detected.
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.3 Deposit Formation in the HRSG and Steam Turbine
2.3.3 Preventing Deposit Formation – Minimizing Contaminant Entry
into the HRSG cont’d
• Chemical Dosing : Chemicals dosed into the HRSG are of the
industrial grade and may contain contaminants in small
amounts. It is important to procure chemicals from a reliable
source and also conduct quality analyses on the chemicals to
avoid using chemicals with high amounts of contaminants.
Also, water used to prepare dosing chemicals should be good
quality demin water. The use of contaminated demin water or
ordinary water will introduce contaminants into the HRSG.
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.3 Deposit Formation in the HRSG and Steam Turbine
2.3.3 Preventing Deposit Formation – Maintaining Low Levels
of Contaminants in the HRSG
• Use of Volatile Chemicals: Volatile chemicals do not leave
behind any deposits as they are carried along with the steam
into the condenser and removed in the de-aerator. As much
as possible, treatment chemicals used must be volatile if the
required chemical condition can be achieved.
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.3 Deposit Formation in the HRSG and Steam Turbine
2.3.3 Preventing Deposit Formation – Maintaining Low Levels
of Contaminants in the HRSG cont’d
• Carryout Blow-down to remove contaminants: Blow-down is
the gradual draining of the contents of the boiler drum whiles
simultaneously re-filling with fresh feed-water. It is a way of
removing contaminants from the HRSG. Dissolved salts,
suspended solids and silica contaminants are removed
gradually during blow-down to reduce the level of
contaminants in the boiler drum.
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.3 Deposit Formation in the HRSG and Steam Turbine

2.3.3 Preventing Deposit Formation – Maintaining Low Levels of

Contaminants in the HRSG cont’d

• Use of Condensate Polishers: Some plants install a condensate

polisher. This is a mixed bed resin vessel which removes
contaminants that are carried over with the steam into the
condensate or condensate contaminants from condenser tube
leakage.
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.3 Deposit Formation in the HRSG and Steam Turbine

2.3.3 Preventing Deposit Formation – Preventing Carryover into

the Steam Turbine.
Carryover is the transportation of solid, liquid and vaporous
contaminants from the boiler drum, along with the steam into
the steam turbine. This can occur in the following two ways:
• Mechanical carryover
• Vaporous carryover
Both means of carryover have to be avoided to prevent
transporting contaminants into the steam turbine.
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.3 Deposit Formation in the HRSG and Steam Turbine
2.3.3.1 Preventing Carryover – Avoiding Mechanical Carryover
• In mechanical carryover, water droplets containing suspended
solids, dissolved salts and silica are carried along with steam
into the steam turbine. Demisters are installed in the upper
section of the boiler drum close to the steam outlet to trap
water droplets and prevent them from being carried along
with the steam. As the trapped droplets increase, they fall
back into the water phase. It is essential to ensure that the
demisters are in place and functioning well by inspecting the
drum when the opportunity arises.
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.3 Deposit Formation in the HRSG and Steam Turbine
2.3.3.1 Preventing Carryover – Avoiding Mechanical Carryover cont’d

• Operating at higher than recommended drum levels, can

increase the risk of mechanical carryover. It is essential that
the HRSG operated within the recommended boiler water
level limits.
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2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.3 Deposit Formation in the HRSG and Steam Turbine
2.3.3.1 Preventing Carryover – Avoiding Vaporous Carryover
Silica is volatile in steam at high pressures. The volatility of silica
depends on the amount in the water phase and the pH of the
water (see figure 5). To avoid vaporous carryover, it is essential
to keep the silica level below the threshold limit taking into
consideration the pH of the water. The only way to do this to
• Use good quality demin water with no silica
• Monitor the silica level in the water and steam and Blow-
down to maintain low silica in both boiler water and steam.
 2.0 HRSG BOILER CHEMISTRY AND CONTROL
2.3.3.1 Preventing Carryover – Avoiding Vaporous Carryover
Fig 5. Effect of pressure and pH on silica volatility

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3.0 HRSG CHEMICAL CONDITIONING
3.1 Feed-water Treatment

Feedwater treatment involves the dosing of the following kinds of

chemicals :
a. A volatile pH alkalizing agent and
b. Oxygen scavenger
www.vra.com 3.0 HRSG CHEMICAL CONDITIONING
3.1 Feed-water Treatment
a. Dosing volatile pH alkalizing agent
• The objective of dosing the volatile alkalizing agent is to raise the pH
of the water in the feed-water drum and tubes and the pH of steam.
This helps to protect the feed-water drum, tubes, steam pipes and
the steam turbine from corrosion. Although steam is not produced in
the feedwater drum, the feedwater is pumped into the boiler drum
where the water is turned into steam and the volatile chemical
moves along with the steam into the steam turbine. After steam
condensation, volatile alkalizing agent, which is non-condensable
chemical is removed in the de-aerator. This chemical therefore needs
to be dosed continuously to maintain the desired pH.
www.vra.com 3.0 HRSG CHEMICAL CONDITIONING
3.1 Feed-water Treatment

b. Oxygen scavenger dosing

• The objective of dosing the oxygen scavenger into the feedwater is to
chemically remove dissolved oxygen from the HRSG after mechanical
de-aeration. This chemical is constantly used up in reacting with
dissolved oxygen and therefore the need for continuous dosing,
whiles the HRSG is in operation.
www.vra.com 3.0 HRSG CHEMICAL CONDITIONING
3.2 Feed-water Treatment Chemicals

a. Volatile alkalizing agents

• Ammonia
• This is a commonly used alkalizing agent for HRSG pH control.
Ammonia however has a very high distribution ratio, which means
that it is very volatile and does not stay in the water phase for long.
It therefore does not provide enough protection in the condensate
system against corrosion. Especially in the case where carbon
dioxide is produced in the action and decomposition of organic
oxygen scavengers.
 www.vra.com 3.0 HRSG CHEMICAL CONDITIONING
3.2 Feed-water Treatment Chemicals
a. Volatile alkalizing agents cont’d
• Neutralizing Amines:
• Neutralizing amines hydrolyze in water to generate the necessary hydroxide
ions required to neutralize carbon dioxide. Neutralizing amines are surface-
active and will remove corrosion products that are present in the condensate
system and boiler. When amine treatment is first started in a system that
contains old deposits from corrosion by-products, these deposits may slough
off (shed off) and contaminate the condensate.
• Therefore when using neutralizing amines, it is essential to blend two or three
based on their ratios to give sufficient protection of the steam and
condensate system.
• Depending on the distribution ratio, some amines will stay in the vapor phase
longer in a system than others and could leave certain areas unprotected. One
type of neutralizing amine will not offer sufficient protection to an entire
system. Therefore, two or more neutralizing amines are used in combination
to protect the total system.
• Examples of Neutralizing Amines are Cyclohexylamine and morpholine
www.vra.com 3.0 HRSG CHEMICAL CONDITIONING
3.2 Feed-water Treatment Chemicals

a. Volatile alkalizing agents cont’d

• Filming Amines: Filming amines function by forming a protective barrier
against both oxygen and carbon dioxide attack. These amines form films
directly with the steam and condensate line metal and develop a barrier
to prevent contact of the corrosive steam and condensate with the piping.
Filming amines are also highly surface-active and will remove corrosion
products that are present in the condensate system and boiler. Care must
be taken not to dose in excess as this will cause the rapid removal of
deposits. This will result in the excessive accumulation of corrosion
products in the boiler and condensate system, causing blockage of traps
and valves in the condensate system
• Examples are Octadecylamine and Soya amine
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3.2 Feed-water Treatment Chemicals
a. Volatile alkalizing agents cont’d

Distribution Ratios for Neutralized Amines

Amine Distribution Ratio

Morpholine 0.4
Diethylaminoethanol 1.7
Dimethylisopropanolamine 1.7
Cyclohexylamine 4.0
Ammonia 10.0
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3.2 Feed-water Treatment Chemicals

b. Oxygen Scavengers
A suitable oxygen scavenging chemical should be able to
effectively react with dissolved oxygen in the feed-water to form
products that will not have an overall negative impact on the
chemical condition of the water and steam.
The commonly used oxygen scavengers in the industry are listed
in Table 2 below and briefly discussed after Table 2.
 3.0 HRSG CHEMICAL CONDITIONING
3.1 Feed-water Treatment
Table 2: Oxygen Scavengers
Name Volatily as Metal Passivator Contributes Solids Toxicity Theoretical
VLDR Dosage
(per part O2)

Catalyzed non- N Y 7.9

Sulfite volatile
Catalyzed 0.08 Y N suspected 1
Hydrazine carcinogen

Carbohydrazide volatile Y N 1.4

Erythorbate non Y N G.R.A.S. 11

volatile
Methylethylket volatile Y N 5.4
oxime
Hydroquinone volatile Y N 6.9
DEHA 1.26 Y N relatively 1.2
non-toxic 52
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3.0 HRSG CHEMICAL CONDITIONING
3.3 Boiler water Treatment
Boiler-water treatment involves the dosing of sodium phosphates which
performs the dual function of corrosion prevention and scale inhibition.
Sodium polyphosphates hydrolyze in water to give Sodium hydroxide and
sodium hydrogen phosphates.
Na3PO4 + H2O  NaOH + Na2HPO4 - Alkaline
Na2HPO4 + H2O  NaOH + NaH2PO4 - Neutral
NaH2PO4 + H2O  NaOH + H3PO4 - Acidic

The sodium hydroxide raises the pH of the water whiles the sodium
phosphates inhibits scale formation.
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3.0 HRSG CHEMICAL CONDITIONING
3.3 Boiler water Treatment
• In drum boilers, steam generated in the boiler drum continuously exits to
the steam turbine. The boiler drum is also continuously replenished with
feed-water to replace the exiting steam. Therefore a water phase and
steam phase constantly exists in the Boiler drum during operation. The pH
conditioner that is dosed in the feed-water of high pressure boilers are
volatile and evaporate with the steam in the boiler drum. This leaves the
water phase of the boiler drum with a pH which is lower than that
required for sufficient protection against corrosion. This therefore brings
about the need to dose a chemical to raise the pH to the required alkaline
range for protection against corrosion. Caustic soda and sodium
phosphate are the chemicals that serve this purpose. Sodium phosphate
has an additional benefit of introducing phosphate ions to combat scale
formation. This will be explained further in later slides.
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3.0 HRSG CHEMICAL CONDITIONING
3.3 Boiler water Treatment
• The process of steam generation in the HRSG is a continuous cycle. As
water is converted into steam in the boiler drum, dissolved salts and other
non-volatile contaminants remain in the water. Contaminant that enter
the HRSG will accumulate in the boiler drum water phase. Scale forming
contaminants that accumulate in the water phase will increase the risk of
scale formation in the HRSG boiler drum and tubes.

• As mentioned earlier, in addition to raising the pH, sodium phosphate is

dosed into the boiler drum to introduce phosphate ions into the boiler
water. The phosphate salts of the scale forming ions (Calcium and
Magnesium) are sparingly soluble because of their very low solubility
product (Ksp). By maintaining a residual amount of phosphate ions in the
water, the phosphate salts of the scale forming ions readily precipitate out
of solution, which can be removed by blow-down, hence eliminating the
danger of scale formation.
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3.0 HRSG CHEMICAL CONDITIONING
3.3 Boiler water Treatment

• Contaminants that enter the HRSG , will cause the dissolved salts also to
accumulate in the boiler drum water phase, increasing the risk of deposit
formation in the HRSG drums and tubes and even in the steam turbine
through carryover. To avoid this risk of deposit formation, there is the
need for periodic blow-down when the amount of dissolved salts increase
beyond the desired limit, as indicated by the TDS or conductivity.
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3.0 HRSG CHEMICAL CONDITIONING
3.3 Boiler water Treatment

Types of Chemical Treatment Regimes

• Caustic Treatment (CT): Caustic soda, a solid alkalization agent, useful in

raising pH of boiler water. However, free hydroxide led to caustic attack on
the tubes and drum causing caustic embrittlement, caustic gouging and
contributing to hydrogen damage.

• Phosphate Treatment (PT): Trisodium phosphate, used alone or in

conjunction with caustic soda, was a major improvement in boiler water
treatment as Trisodium phosphate hydrolyses to form caustic and is also a
scale inhibitor. However, did not eliminate the risk of producing free
hydroxide in excess of that associated with trisodium phosphate.
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3.0 HRSG CHEMICAL CONDITIONING
3.3 Boiler water Treatment
Types of Chemical Treatment Regimes cont’d
• Co-ordinated Phosphate Treatment (CPT) : Also called (captive alkalinity)
was introduced to deal with problem of free caustic. This regime placed a
limit on pH with respect to phosphate concentration. Na:PO4 = 3.0; the
stoichiometric ratio of Na and PO4 in trisodium phosphate to prevent free
caustic. However due to difficulty in control, problems with ratio going as
low as below 2.0 and creating acidic environment leading to corrosion
problems and also phosphate hideout problems.

• Congruent Phosphate Treatment (CPT): Modification of co-ordinated CPT,

which set the ratio Na:PO4 = 2.6 – 2.8 to prevent creating acidic
environment and yet maintaining sufficient alkaline condition to protect
corrosion. However, there were still problems with phosphate hideout in
high pressure boilers. Risking under-deposit corrosion and low pH
problems.
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3.0 HRSG CHEMICAL CONDITIONING
3.3 Boiler water Treatment
Types of Chemical Treatment Regimes cont’d

• Equilibrium Phosphate Treatment (EPT): Introduced to prevent phosphate

levels from rising too high and creating caustic related corrosion problems
and phosphate hideout. Worked on the principle of the maximum
phosphate concentration that a particular boiler can tolerate to prevent
hideout.

• All volatile treatment (AVT) : Used in once through boilers, and in high
pressure super-critical boilers (pressure >230 bar at steam temperatures
up to 650 °C, avoids all the caustic and phosphate related problems.
However reliable only with constant use of high quality demin water. Also
no protection against occasional contamination like seawater ingress.
There are three different kinds of AVT methods, briefly described below.
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3.0 HRSG CHEMICAL CONDITIONING
3.3 Boiler water Treatment

Types of Chemical Treatment Regimes cont’d

• All volatile treatment (Reducing) – AVT(R):This treatment involves the

addition of ammonia (or an amine or blend of amines of lower volatility
than ammonia) and a reducing agent (usually hydrazine or one of the
acceptable substitutes) to the condensate or feedwater of the plant. In
combination with a relatively low oxygen level (from air in-leakage) of ~10
μg/kg or less in the condensate the resulting feedwater will have a
reducing redox condition (usually measured as Oxidation-Reduction
Potential, ORP)
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3.0 HRSG CHEMICAL CONDITIONING
3.3 Boiler water Treatment

Types of Chemical Treatment Regimes cont’d

• All volatile treatment (Oxidizing) – AVT(O): This all-volatile treatment In

this case, a reducing agent is not used during any operating or shutdown
period. Ammonia (or an amine or blend of amines of lower volatility than
ammonia) is added at the Condensate Pump Discharge or polisher outlet
(if a polisher is included within the cycle). In combined cycle/HRSG plants
with relatively good control of air in-leakage (oxygen levels in the range
10–20 μg/kg), the resulting feedwater will yield a mildly oxidizing
electrochemical potential (ORP).
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3.0 HRSG CHEMICAL CONDITIONING
3.3 Boiler water Treatment

Types of Chemical Treatment Regimes cont’d

• Oxygenated treatment – OT: This treatment method involves oxygen

injection at the condensate polisher outlet (CPO), operating with the vents
on the feedwater heaters and deaerator closed. Ammonia is added at the
condensate polisher outlet. There is often a minimum level of 9ppb
oxygen which is required to provide full passivation of the single-phase
flow locations in the main feedwater line and the drain lines, and to
maintain this protection. For drum units this is usually between 30 and 50
ppb at the economizer inlet, and for once-through/supercritical units this
is usually 30–150 ppb at the economizer inlet.
4.0 HRSG Condition Monitoring
Feedwater Quality

Source: CMI Manual – HRSG Water Survey 63

4.0 HRSG Condition Monitoring
Boiler water quality

Source: CMI Manual – HRSG Water Survey 64

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4.0 HRSG Condition Monitoring
STEAM PURITY LEVELS FOR NORMAL, UPSET, EMERGENCY AND
SHUTDOWN CONDITIONS.
Operating ppb* Cation
Conditions Sodium Conductivity** Comments
(max.) (max)
Desirable 10 0.1 Desirable for continuous operation

Allowed 20 0.2 Acceptable for continuous operation

Upset 100 0.4 Allowed for up to 72 hours of operation

Emergency 500 2.0 Allowed for 24 hours of operation

Shutdown Over 500 Over 2.0 Shutdown Turbine

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5.0 HRSG preservation when shut down

When the boiler is to be shut down for more than one week, the
boiler should be put under preservation. This means the drum
and tubes of the boiler must be maintained under conditions
that will prevent corrosion, scale and deposit formation. It must
be said however that, during shutdown, the greatest risk to the
boiler is corrosion.
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5.0 HRSG preservation when shut down
5.1 Kinds of Boiler Preservation
• There are two main kinds of boiler preservation.
– Wet preservation and
– Dry preservation.

• When the boiler is shut down from between one week to one
month, and it is desired to bring it into service quickly, wet
preservation is the preferred option. If the boiler is not
required back into service quickly, the dry preservation is a
suitable option.
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5.0 HRSG preservation when shut down
5.1 Kinds of Boiler Preservation
Wet Preservation
• To preserve the boiler under wet preservation, the boiler drums and
tubes should be drained to get rid of any dissolved salts and filled
with fresh demineralized water.
• The drums should then be dosed with ammonia or amine (any
suitable volatile alkalizing agent). The drums contents are then re-
circulated through the tubes for mixing and to ensure that the
preservation solution in the drums and tubes is homogenous.
• The target pH of the preservation solution after mixing should be
higher than 10.5. Dosing and mixing should continue if this target pH
is not achieved.
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5.0 HRSG preservation when shut down
5.1 Kinds of Boiler Preservation
Wet Preservation cont’d
• The boiler is then capped with nitrogen (i.e. nitrogen under pressure
is introduced into the drums to displace air in any available spaces).
• The vents on the boiler are then closed and the nitrogen supply lines
maintained under pressure to prevent air ingress into the boiler in
the event of leaks. Air ingress will introduce oxygen and carbon
dioxide, which will encourage corrosion.
• The preservation solution should be checked weekly to ensure that
the pH is suitable. If the pH drops below 10.5, dosing and mixing
should be carried out to attain a pH greater than 10.5
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5.0 HRSG preservation when shut down
5.1 Kinds of Boiler Preservation

Dry Preservation
• There are two methods employed in maintaining dry
preservation on the HRSG. These are:
a. Dry nitrogen preservation method
b. Dry air preservation method
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5.0 HRSG preservation when shut down
5.1 Kinds of Boiler Preservation
a. Dry nitrogen preservation
• To carry out dry nitrogen preservation, the HRSG drums and tubes
should first be drained completely and refilled with fresh
demineralized water, dosed with ammonia or amines to a pH above
10.5.
• The HRSG vents should be overflowing to ensure complete filling,
then the vents valves shut and the pressurized nitrogen injection
lines opened to introduce nitrogen into the HRSG.
• The HRSG is then drained slowly by opening the drains. This will
ensure that water leaving the HRSG is replace with nitrogen and will
also prevent any air ingress into the HRSG.
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5.0 HRSG preservation when shut down
5.1 Kinds of Boiler Preservation

a. Dry nitrogen preservation cont’d

• Since the water in the HRSG prior to draining is well
conditioned for preservation, any water retained in the HRSG
in the inert nitrogen environment will not support corrosion.
Therefore complete dry out is not necessary in this method.
• The nitrogen supply lines should remain opened and
pressurized to prevent any air ingress in the event of leaks. Air
ingress will introduce oxygen and carbon dioxide which will
facilitate corrosion.
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5.0 HRSG preservation when shut down
5.1 Kinds of Boiler Preservation
b. Dry air preservation
• In this method, the HRSG is blown dry under pressure with all
drains and vents open when shutdown. The residual heat in the
HRSG will continue the dry-out, but not completely.
• Condensation will also occur when the HRSG becomes cold, causing
pockets of water to be trapped in the HRSG, which could support
corrosion.
• It is therefore mandatory to remove all pockets of water for
successful dry air preservation. The relative humidity of air in the
HRSG must be kept below 30% at which the corrosion rate is nil.
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5.0 HRSG preservation when shut down
5.1 Kinds of Boiler Preservation
b. Dry air preservation
• The humidity target must be strictly maintained throughout
the preservation period.
• Although this method is efficient when the low humidity
levels are maintained, complete drying is difficult to achieve.
Hence this method is difficult to put into practice, especially in
high humidity climates like ours. It is more practically applied
in low humidity areas or areas with sub-zero temperatures.
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End of Presentation

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