Instruction

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Risto Sonninen 1.11.2006

PERTONAS PENAPISAN MELAKA SDN BHD COGENERATION PROJECT,

THE MAGNETITE LAYERING INSTRUCTION OF THE HEAT RECOVERY STEAM
GENERATORS

1 GENERAL
After the alkaline boil-out of the heat recovery steam generators (HRSGs) the inside
surfaces of the boiler tubes are very sensitive to corrosion. Because of this a protective
oxide layer shall be formed on the inside surfaces of the boiler tubes in each HRSG as
soon as possible after the alkaline boil-out. This oxide layer is called magnetite layer
and it gives the best known protection against corrosion to the cycle components
made of carbon steel during the later utility service of the HRSGs.
In order to get the best possible corrosion protection the magnetite layer shall be thin
and non-porous. This goal can be achieved only if the magnetite layering of the
HRSGs is made correctly and under the favourable chemical conditions.

2 THEORETICAL BASIS

2.1 Magnetite formation mechanism in water and steam

When oxygen free water is in contact with the inside surfaces of boiler tubes made of
carbon steel, water reacts with iron forming a magnetite layer (F3O4 layer) on the
metal surfaces according to the reaction equations 1 – 6.
In oxygen free water, when water temperature is < 100 oC, iron reacts with water
forming ferrous hydroxide and hydrogen ions as follows:
Fe Fe2+ + 2e- (1)
2 H2O 2H+ + 2OH- (2)
2 H+ + 2e- H2 (3)
______________________________

F e + 2H2O Fe(OH)2 + H2 (4)

When water temperature is about 100 oC and the oxygen content of water is <0.010
mg/kg, ferrous hydroxide starts to decompose to magnetite. Hydrogen and water are
produced as the other reaction products according to the reaction equation 5.
3Fe(OH)2 Fe3O4 + H2 + 2H2O (5)

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The decomposition rate of Fe(OH)2 to Fe3O4 depends on temperature as follows:

• When water temperature is about 100 oC magnetite formation takes place very
slowly.
• At elevated temperature magnetite formation speed up and at the temperature
range between 200 – 240 oC the formation rate of Fe3O4 is optimal.
• When water temperature is >250 oC magnetite formation takes place very fast.
• In steam phase, when the inside surface of boiler tube is in contact with steam,
magnetite formation takes place instantly in one reaction step according to the
reaction equations 6.
3Fe + 4H2O Fe3O4 + 4H2 (6)
If water contains free oxygen, Fe(OH)2 become oxidised immediately to FeOOH (so
called rust). At elevated temperatures, when water temperature is >200 oC, rust
decomposes thermally to hematite (Fe2O3), which does not give proper corrosion
protection to carbon steel.

2.2 Effects of pH and temperature on magnetite formation

The correct pH and temperature of boiler water during magnetite layering are of great
importance. In order to get a thin and non-porous magnetite layer on the water side
surfaces of boiler tubes special attention must be paid on these parameters during
magnetite layering.

2.2.1 Effects of boiler water pH

During magnetite layering water shall be as neutral as possible for the following
reasons:
• If pH of boiler water is has been too high during magnetite layering (the pH of
boiler water has been >9.5), the oxide layer formed under these chemical
conditions consists of big magnetite crystals. Because of this the magnetite
layer is very thick and porous. In this case during the later utility service of
the HRSGs water can diffuse through porous magnetite layer to hot metal
surface, where it reacts continuously with iron causing abnormal magnetite
growth and poor magnetite quality. Sooner or later this abnormal magnetite
growth will lead to the continuous iron problems (high iron content of boiler
water and steam) and to repeated acid cleanings of the HRSGs.
• If the pH of boiler water has been almost neutral (pH of boiler water has been
between 6 and 8), magnetite layer consists of very small magnetite crystals.
Because of this oxide layer is very thin and non-porous. In this case abnormal
magnetite growth, described above, is not possible and oxide layer gives very
good corrosion protection during the later utility service of the HRSGs.

ÅF-Enprima Oy
PL 61, Rajatorpantie 8, 01601 Vantaa
Puh. 040 348 5511. Fax (09) 3487 0810. www.afconsult.com
Y-tunnus 1800189-6. Kotipaikka Helsinki.
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• According to the well known rule of thumb “If the pH of boiler water drops
for some reason to the lower pH level maintained during the magnetite
layering of the boiler, the failure of magnetite layer occurs”. On the basis of
this rule the following conclusions can be made:
o If the pH of boiler water has been maintained between 9.5 and10
during magnetite layering, relatively small pH drop of boiler water
during the later utility service of the HRSGs can cause the failure of
magnetite layer. The pH of boiler water fluctuates usually between 9.0
– 9.5.
o If the pH of boiler water has been maintained at the pH level of 6 - 8
during the magnetite layering, the failure of magnetite layer can occur
only if the pH of boiler water drops suddenly to the pH level of <6.
This is possible only in the case of very serious water chemistry
problems.

2.2.2 Effects of water temperature

Magnetite formation rate depends on water temperature as follows:
• Best temperature for magnetite formation is about 240 - 250 oC (pressure in
the drum is about 35 - 40 bar). In this temperature magnetite formation takes
place so slowly that boiler water can be changed sufficiently during magnetite
layering. In this case the favourable chemical conditions of boiler water
(correct pH, low oxygen content and low iron content ) for magnetite
formation can be controlled and maintained properly.
• If boiler water temperature is 250 – 300 oC, magnetite formation takes place
so fast that boiler water cannot be changed enough during magnetite layering
and the chemical conditions during magnetite layering cannot be controlled
properly.

3 MAGNETITE LAYERING

3.1 Measures after the chemical cleaning of each HRSG

After the alkaline boil-out of the HRSGs the following measures shall be carried out:
• The drums of each HRSG are opened and the cleanness of metal surfaces is
inspected visually. Magnetite layering can be started not until all water side
iron surfaces of the HRSG are completely clean of grease.
• After the visual inspection of drums each HRSG is normalized so that the
water pressure test of each HRSG can be made. The water-pressure test of
each HRSG is made in order to inspect the tightness of the water and steam
cycle of the HRSGs.

ÅF-Enprima Oy
PL 61, Rajatorpantie 8, 01601 Vantaa
Puh. 040 348 5511. Fax (09) 3487 0810. www.afconsult.com
Y-tunnus 1800189-6. Kotipaikka Helsinki.
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Risto Sonninen 1.11.2006

• Before water pressure test each HRSG is filled completely with warm
demineralised make-up water. Normally the temperature of filling water in
water pressure tests is about 50 oC. At this temperature filling water contains
always some oxygen and due to this water must be overdosed with some
volatile oxygen scavenger so that the oxygen content of water is >0.010
mg/kg. Due to the chemical overdosing of the oxygen scavenger chemical the
pH of filling water is usually >10.
• If the pH of filling water during the water pressure test of the HRSGs has been
between 8.5 – 9,5, water shall be replaced with feed water of good quality (pH
= 8 – 8.5 and oxygen content is < 0.010 mg/kg) until the pH of boiler water is
about 8.0 – 8.5 if possible. If the pH of boiler water has been >9.5, the HRSG
shall be drained and refilled with feed water of good quality (pH = 8 – 8.5 and
oxygen content is < 0.010 mg/kg).

3.2 Measures before magnetite layering

The magnetite layering of the HRSGs is made separately. Before magnetite layering
of each HRSG the following measures shall be carried out:
• The pH of feed water is adjusted to 8 – 8.5. Usually low pressure steam, used
for deaeration of feed water, contains sufficient amount of volatile chemicals
to maintain the correct pH of feed water. If low pressure steam alone cannot
maintain the sufficient pH of boiler water, in this case some volatile alkalising
agents (ammonia or some equivalent neutralising amine) and some volatile
oxygen scavenger (hydrazine or equivalent volatile oxygen scavenger) are
dosed to feed water. Some commercial volatile chemical mixtures, which
contain both some volatile alkalising agent and some volatile oxygen
scavenger can be used for this purpose, too.
• In each HRSG boiler water is replaced with feed water of good quality
specified above until the pH of boiler water is about 8.5 if possible. After that
each HRSG is filled to normal water level in the drum with deaerated feed
water
• After filling boiler water is analysed (oxygen content, pH, specific
conductivity, cation conductivity and total iron content). If the iron content of
boiler water is very high (water is dark or grey), water shall be replaced with
feed water of good quality. In this case water is drained from the bottom
blowdowns to the blowdown tank and at the same time pure feed water is fed
to the HRSG until boiler water drained from the HRSG is almost colourless. If
boiler water is completely black or the pH of boiler water is <6 or > 9.5 the
HRSG shall be drained and refilled with feed water of good quality.

3.3 Measures during the magnetite layering

During magnetite layering the following measures shall be carried out:

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PL 61, Rajatorpantie 8, 01601 Vantaa
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• The pH of feed water shall be about 8 – 8.5.The same pH of feed water is

maintained all the time during magnetite layering.
• When boiler water quality is good enough (boiler water is almost colourless
and the pH of boiler water is about same as the pH of feed water), the gas
turbine (later called GT) is started-up.
• During magnetite layering boiler water is changed as much as possible using
continuous blowdowns and periodical bottom blowdowns in order to change
water in the HRSG. The bottom blowdowns are made from each bottom
header two times an hour. The duration of each blowdown is about 1 – 2
minutes depending of boiler water quality. Bottom blowdown are stated
immediately after the start-up of the gas turbine (GT).
• After the start-up the GT the pressure in the drum is increased about to 35 – 40
bar (water temperature is about 240 – 250 oC) slowly during few hours if
possible. The duration of this time period depends on boiler water quality (pH
and iron content). If boiler water quality is good, pressure in the drum can be
increased in 1 - 2 hours, in certain cases even faster. During this time period
boiler water is often more or less black and pH can be 6 – 7 or even lower. In
this case the pressure in the drum must be increased slowly enough, so that
boiler water can be changed sufficiently.
• When pressure has increased to 35 – 40 bar, same pressure in the drum is
maintained throughout the magnetite layering.
• During magnetite formation the quality of feed water, boiler water and steam
is analysed, see the water chemistry monitoring instruction shown in the
section 3.4.
In the beginning of magnetite layering the pH of boiler water is about same as the pH
of feed water (pH is 8 – 8.5). After the star-up of each GT the pressure in the drum
increases and the actual magnetite formation starts. Because of hydrogen formation
during magnetite layering (see equations 4 – 6 shown above) the pH of boiler water
drops normally to the pH level of 6.5 – 7 or even to lower pH level depending on the
formation rate of magnetite and boiler water quality. This pH drop indicates that real
magnetite layering has started. At this time boiler water is usually more or less black.
During this time it is necessary to monitor the pH of boiler water for the following
reasons:
• If the pH of boiler water decreases to the pH level of <5, magnetite layering
must be stopped and the boiler must be drained and refilled with feed water of
good quality. Such a low pH of boiler water indicates that there are too much
acidic compounds, probably organic acids formed as the thermal
decomposition products of organic matter in boiler water. Under these
chemical conditions magnetite formation is not possible.
• If the pH of boiler water decreases to the pH level of 5 - 5.5, some solid
alkalising chemical (trisodium phosphate or sodium hydroxide) must be dosed
ÅF-Enprima Oy
PL 61, Rajatorpantie 8, 01601 Vantaa
Puh. 040 348 5511. Fax (09) 3487 0810. www.afconsult.com
Y-tunnus 1800189-6. Kotipaikka Helsinki.
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Risto Sonninen 1.11.2006

to boiler water so that the pH of boiler water increases to the pH level of 6 –

8.
• If the pH of boiler water degreases to the pH level of 5.5 - 6, the dosing of
volatile alkalising chemical (ammonia or equivalent neutralising amine) to
feed water is increased so that the pH of boiler water increases to the pH level
of 6 – 8.
• If the pH of boiler water is 6 – 8, the chemical conditions of the HRSGs are
ideal for magnetite layering. In this case magnetite layering is continued
without additional chemical dosing.
• If the pH of boiler water increases to the pH level of >9.5, it indicates that the
dosing rate of neutralising amine has been too high. In this case boiler water
must be replaced with feed water of good quality so that the ph of boiler water
drops to the pH value of <9. In the worst case boiler water must be drained
and refilled with feed water of good quality.
Magnetite layering is continued and boiler water is changed using bottom blowdowns
as described above. After several hours the pH of boiler water starts to increase to the
to the pH level of feed water (pH 8 – 8.5) without additional chemical dosing to feed
water. This indicates that there is a thin magnetite layer everywhere on the water side
surfaces of the boiler tubes so that water cannot be in contact with pure iron surface
anymore. It means that iron cannot react with water and due to this hydrogen
formation degreases and finally stops. At the same time the pH of boiler water start to
increase to the pH level of feed water and total iron content of boiler water decreases.
After the pH recovery of boiler water the magnetite layering is continued for few
hours under the same operating conditions depending of the boiler water quality. Few
hours later, if the boiler water is more or less colourless, the pH of boiler water can be
increased to the normal level (pH of boiler water is 9.0 – 9.5) with some volatile
alkalising chemical.
Magnetite layering is continued until the normal iron content of boiler water is
reached (iron content of boiler water is < 0.100 mg/l). When the acceptable iron
content of boiler water has been reached the magnetite layering can be stopped.

3.4 Monitoring of magnetite layering

During the magnetite layering of the HRSGs water and steam samples are analysed as
shown in the table 1.
During the magnetite layering feed water quality can be monitored with on-line
analysers (pH, specific conductivity and cation conductivity). The other water and
steam samples are analysed in the laboratory because the total iron content of boiler
water, saturated steam and superheated steam is so high, that dissolved and solid iron
can foul the detectors of the on-line analysers.

ÅF-Enprima Oy
PL 61, Rajatorpantie 8, 01601 Vantaa
Puh. 040 348 5511. Fax (09) 3487 0810. www.afconsult.com
Y-tunnus 1800189-6. Kotipaikka Helsinki.
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Risto Sonninen 2.8.2006

Table 1. Water and steam analyses and measurements during the magnetite layering
Parameters Feed water Boiler water Saturated steam Superheated steam
pH On-line measurement, Laboratory analysis Laboratory analysis Laboratory analysis
readings are written once an hour once an hour once an hour
down once an hour
Cation conductivity On-line measurement, - - -
readings are written
down once an hour
Specific conductivity On-line measurement, Laboratory analysis Laboratory analysis Laboratory analysis
readings are written once an hour once an hour once an hour
down once an hour
Total iron / laboratory Laboratory analysis Laboratory analysis Laboratory analysis Laboratory analysis
analysis every third hour every third hour every third hour every third hour
2.) 2.) 2.) 2.)
Total iron / Millipore Once an hour Laboratory analysis Laboratory analysis Laboratory analysis
filtration (<0.45μ filter) once an hour once an hour once an hour
Silica as SiO2 On-line measurement, Laboratory analysis Laboratory analysis Laboratory analysis
readings are written once an hour once an hour once an hour
down once an hour
1. Total iron content = the content of dissolved and solid corrosion products in water and steam samples.
2.) Millipore filtrations are made only when the water and steam samples are colourless or almost colourless.

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PL 61, Rajatorpantie 8, 01601 Vantaa
Puh. 040 348 5511. Fax (09) 3487 0810. www.afconsult.com
Y-tunnus 1800189-6. Kotipaikka Helsinki.
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In Millipore filtration water and steam samples (feed water samples, boiler water
samples, saturated steam samples and superheated steam samples, volume of each
sample is 1 litre) are filtrated using a vacuum suction bottle through a filter membrane
(<0.45 μ filter membrane). After filtration the colour of each filter membrane, caused
by solid corrosion products of iron in water and steam samples, is compared visually
to the standard colour chart published by Millipore Ltd.
The conclusions concerning the progress of magnetite layering are made of the basis
of the analytical data collected during the magnetite layering of each HRSG as
described above. When the magnetite layer of HRSGs is ready, after that each HRSC
is ready for steam blowings (steam blow-outs).
If steam blowings cannot be carried out immediately after the magnetite layering the
HRSGs must be conserved as follows:
• The normal water level of boiler water is maintained.
• The normal pH of water is maintained.
• The HRSGs are kept under pressure using either steam blanketing or nitrogen
blanketing in order to prevent the ingress of oxygen to the water and steam
cycle.
• If the HRSGs cannot be maintained under pressure the HRSGs must be
conserved using so called wet preservation. In this case each HRSG must be
filled completely with deaerated feed water overdosed with some volatile
alkalising agent (ammonia or equivalent neutralising amine) and volatile
oxygen scavenger (hydrazine or equivalent volatile oxygen scavenger).

ÅF-Enprima Oy
PL 61, Rajatorpantie 8, 01601 Vantaa
Puh. 040 348 5511. Fax (09) 3487 0810. www.afconsult.com
Y-tunnus 1800189-6. Kotipaikka Helsinki.
137058906.doc