PPChem

Boiler Feedwater Oxygenated Treatment in Power Plants in China

Boiler Feedwater Oxygenated Treatment in Power Plants

in China
Zhigang Li, Wanqi Huang, Songyan Cao, and Hongbo Zhang

ABSTRACT
This paper presents the development of the oxygenated treatment (OT) technique application in power plants in China.
The oxide morphologies of boiler tubes (economizer and water wall) under three different feedwater treatment
techniques all-volatile treatment under reducing conditions (AVT(R)), all-volatile treatment under oxidizing conditions
(AVT(O)) and oxygenated treatment (OT) were analyzed, and it was found that the reddish brown Fe2O3 coating layer
formed by oxygen in feedwater only extended as far as the economizer inlet section. This paper also has a detailed
discussion about the CrO42 release phenomenon and demonstrates that the CrO42 detected in the steam cycle
comes from sampling tubing and apparently does not originate from the boiler tube material.

INTRODUCTION
The Status Quo of Oxygenated Treatment in China
In the 1980s, the Thermal Power Research Institute (TPRI)
realized the value of the oxygenated treatment (OT) technique, which was first proposed and implemented in
Germany, and researched the technology both in the
laboratory and by field testing. In 1988, TPRI successfully
conducted OT field tests for the first time in the Wang Ting
power plant subcritical boiler and achieved satisfactory
results. Subsequently, the application of OT has become
an effective solution to the problem of iron oxide deposition on economizer inlet orifices of 300 MW subcritical
units made in China. In the 1990s, as China imported
many 300 to 600 MW supercritical units and put them into
operation one after another, OT was applied successfully
to solve the frequent problems of high boiler heating
surface corrosion rates and rapid increases in the boiler
pressure differential. In 1995, TPRI first applied the OT
technique to the Shanghai Shidongkou Power Plant 2 x
600 MW supercritical boilers, and achieved the desired
results [1]. The units have also become the longest OToperating supercritical units in China at present. In 2002,
TPRI formulated a "Once-through Boiler Feedwater
Oxygenated Treatment Guideline" to regulate the feedwater oxygenated treatment mode of boilers in domestic
power plants [2]. In the 21st century, with a large number
of domestic 600 MW supercritical units and 1 000 MW
ultra-supercritical units having been put into operation in
China, high corrosion rates of boiler heating surfaces,
deposits on water wall tube orifices and deposits plugging
high-pressure (HP) heater drain control valves have
become more prominent (Figures 1 to 4). Corrosion and

deposition of downstream equipment caused by flowaccelerated corrosion (FAC) is particularly prominent.

These units originally applied the all-volatile treatment
under oxidizing conditions (AVT(O)), but to solve the
abovementioned problems, OT has been more actively
utilized in these supercritical units [3]. At the same time,
when the feedwater is in the AVT condition, mixed bed
condensate polishing has a heavy operational burden, and
many units are forced to operate in ammonium form,
which causes severe leakage of chlorine and sodium into
the mixed bed effluent. The deposition and corrosion of

Figure 1:
Example of an economizer tube with a scaling rate of
260 g m2 per year.

2014 by Waesseri GmbH. All rights reserved.

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Boiler Feedwater Oxygenated Treatment in Power Plants in China

Figure 2:

Figure 3:

Oxide deposition in the last stage of HP heater tube inlets.

Water wall tube orifice deposits.

Figure 5:
Deposits on the blade of a HP rotor.

Figure 4:
Deposits on a drain control valve.

steam turbine blades is also very common (Figures 5

and 6). The advantages and effects of the OT technique
for solving these problems are obvious, and therefore
have become the driving force for the development of the
technology.
As of the end of 2011, there are more than 100 units with
OT in China, of which more than 80 % are ultra-supercritical or supercritical units. All the 1 000 MW ultra-supercritical units in operation are using OT for feedwater treatment. Statistics of the units with OT and unit capacity are
shown in Figure 7.

PowerPlant Chemistry 2014, 16(5)

According to the "Once-through Boiler Feedwater

Oxygenated Treatment Guideline," which was mainly
prepared by TPRI , the dissolved oxygen in feedwater is
limited within the range of 30 to 150 g L1 for units on
OT. In practice, the oxygen content in the feedwater of
operating units with OT is in the range of 30 to 80 g L1.
The merit of OT is fully reflected in these units, as demonstrated by data showing that the iron content in the economizer inlet and HP heater drain is less than 1.0 g L1
(Figure 8), and the average deposit rate in the tubing of the
economizer and water wall after running for six years in
this mode is less than 30 g cm2 per year. In addition, the

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Boiler Feedwater Oxygenated Treatment in Power Plants in China

300 MW subcritical
once-through units
8%

300 MW600 MW
subcritical drum units
10 %

1 000 MW ultrasubcritical units

24 %
600 MW subcritical units
58 %

Figure 6:

Figure 7:

Corrosion on the blades of a low-pressure rotor.

Statistics on unit capacity of thermal power plants using OT in

China.

Iron Concentration [g kg 1]

10.0

8.0

AVT(O)
pH: 9.2~9.6

CPD
MS
DI
EI
HPD

OT
pH: 8.8~9.0

Condensate pump discharge

Main steam
Deaerator inlet
Economizer inlet
High-pressure heater drains

6.0

4.0

2.0

0
CPD

MS

DI

EI

HPD

Figure 8:
Iron concentration of AVT(O) vs. OT in a 1 000 MW unit.
CPD
MS
DI
EI
HPD

condensate pump discharge

main steam
deaerator inlet
economizer inlet
high-pressure heater drains

regeneration cycle for the condensate polishing system

has been extended 4 to 5 times compared with AVT operation, and the rate of boiler differential pressure increase is
significantly reduced (Figure 9). At the same time, the
deposits on the water wall orifice and oxide blockage in
the HP heater drain regulating valve have been significantly mitigated.
However, the use of OT is still limited in many generating
units in China due to the concern about high-temperature
steam oxidation. To reduce the possible risk of introducing
increased oxygen concentration into the steam system,
hypoxia (low-oxygen) treatment in feedwater, also called
weak oxygenated treatment (WOT), has been adopted in

296

some units, and the dissolved oxygen content in the economizer inlet is generally controlled at 5 to 20 g L1. It is
evident that hypoxia treatment cannot protect the HP
heater drain system. High iron content in the drains
caused by two-phase flow-accelerated corrosion (FAC)
and drain valve blockage still cannot be avoided with lowoxygen treatment. In addition, the frequent regeneration of
the condensate polishing mixed beds is a difficult problem
for power plant chemistry workers.
Oxygen injection to feedwater systems often uses the
auto-adjustment mode. An automatic oxygen feed device
developed by TPRI for units with OT is popular in China.
Normally, the dissolved oxygen content in the feedwater

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Boiler Feedwater Oxygenated Treatment in Power Plants in China

3.5
O2 + NH3 conditioning

Pressure drop of Unit No. 1

Pressure Drop [MPa]

3.2

Pressure drop of Unit No. 2

2.9

2.6

2.3
O2 + NH3 conditioning
2.0
3

10

15

18

20

23

27

27

28

29

29

30

30

Month

Figure 9:
Pressure drop from the feed pump to the steam-water separator section in a 1 000 MW unit.

2 000

400

Oxygen flow

Feedwater Flow [t h1]

300
1 200
200
800

100
400

Dissolved Oxygen Content [g L1]

Feedwater flow
1 600

DO in feedwater
Set value

0
0

12

15

18

21

24

27

30

Time [h]

Figure 10:
The control effect of the automatic oxygen feed device in running a unit on OT.
DO

dissolved oxygen

can be controlled within the setting range 20 g L1

even in the case of unit load fluctuations, because this
unique oxygen feed device is equipped with a trace gas
regulatory agent and a differential pressure stabilization
adjusting device, as shown in Figure 10.

THE INVESTIGATIONS
Change in the Metal Oxide Film in the Low-Temperature Zone of the Boiler Heating Surface
At the water temperature of the condensate low-pressure
heaters and the first high-pressure heater, the magnetite

PowerPlant Chemistry 2014, 16(5)

film has higher solubility and it is in an active state.

Magnetite solubility reaches the highest point at about
150 C. When the local flow conditions deteriorate, dissolution of the oxide film can cause FAC at local metal
surfaces in the feedwater system under reducing conditions, and that is why the iron content is higher (average 8
to 10 g L1) in the feedwater systems of boilers treated
with AVT(R) (all-volatile treatment, reducing conditions).
When the feedwater treatment was changed from AVT(R)
to AVT(O) (all-volatile treatment, oxidizing conditions), the
FAC was only partly mitigated, and the iron content of the
feedwater was only lowered to an average of 4 to 6 g L1
due to less dissolved oxygen in the feedwater. The corrosion products deposit at various locations in the system,

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as previously mentioned, and this deposition is a widespread problem in supercritical boilers in China.
Metal Oxide Film Forming Mechanism
According to the oxide film formation mechanism, the
metal oxide film in pure water without oxygen below
300 C consists of a compact Fe3O4 topotactic layer and a
porous Fe3O4 epitactic layer due to the insufficient oxidizing effect of water. Oxide film forming reactions can be
divided into the following steps [4]: carbon steel is dissolved to form ferrous hydroxide and the magnetite and
hydrogen is released. The third step is the slowest.
Fe + 2H2O = Fe2+ + 2OH + H2

(1)

Fe2+ + 2OH = Fe(OH)2

(2)

3Fe(OH)2 = Fe3O4 + 2H2O + H2

(3)

As the water temperature increases above 200 C, the

third step of the Fe3O4 oxide film formation mechanism is
accelerated, but the presence of ferrous hydroxide is still
an intermediate link in the corrosion cell reaction. As
Fe(OH)2 has high solubility, suppression of Fe2+ will occur
if the pH of the water is elevated.
When oxygen is added to the water, the oxygen molecules
accept electrons to form OH in the corrosion cell cathode. While water as an oxidizer has insufficient oxidizing
strength to transform Fe2+ to Fe3+, oxygen molecules support the reduction reaction at the cathode and provide the
required energy for Fe2+ to convert to Fe3+. This increases
the phase interface reaction speed, and eventually accelerates the conversion of ferrous hydroxide to ferric oxide.
2Fe(OH)2 + O2 = Fe2O3 + 2 H2O

(4)

Because oxygen is continuously added to the feedwater,

the Fe2+ diffused through the Fe3O4 topotactic layer is
oxidized to form FeOOH or Fe2O3, as shown in Eq. (4),
which then is deposited in holes and surface pores in the
Fe3O4 epitactic layer. The Fe2O3 seals the porous Fe3O4
film, resulting in a dense and stable "double layer protective film" formed on the steel surface [5], as shown in
Figure 11a. The iron content in the feedwater is then
decreased to less than 1 g L1.
The Surface Difference on the Inlet Tube and Outlet
Tube of the Economizer
The status of the metal oxide films on the surfaces of the
feedwater system cannot be directly analyzed and compared. This is because the sampling is difficult, and it can
only be judged by means of the analysis of economizer
tubes. Before 2008 in China, all feedwater oxygenated
treatment was directly converted from AVT(O) while operating the boilers without first carrying out chemical cleaning. After the boiler treatment had been converted to OT
(the oxygen concentration in the feedwater was about 50
to 70 g L1) for a period of time, tubes were sampled and
metal surfaces were observed. It was found that the
surface color of all tubes from the economizer to the water
wall appeared brown-red due to heavy powdery iron
oxides, which resulted from performing the conversion
to OT without a prior chemical clean. This observed
phenomenon led to some confusion regarding the theoretical effective oxygen range for OT.
After 2008, power plants in China began to focus more on
saving energy and reducing the cost of running the unit. In
order to completely clear out the iron oxide deposits in the
feedwater system and boiler, chemical cleaning was
carried out prior to OT conversions. Some tubes from

Figure 11:
Surface appearance of boiler economizer tubes.
a) Brown-red color on economizer inlet zone tube surface of a 600 MW boiler operating under OT
b) Economizer outlet zone tube surface without brown-red color of a 600 MW boiler operating under OT
c) Economizer inlet zone tube surface of a 660 MW boiler operating under AVT(O)

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economizers of 600 MW supercritical boilers which were

treated with the abovementioned method were analyzed
and studied. It was discovered that with this approach,
when economizer and water wall tubes were sampled
from 600 MW boilers which were treated with OT, their
oxide film color and appearance characteristics were
obviously different the inner surface of the economizer
inlet section tube sample had a reddish brown layer, and
that of the economizer outlet section tube had a steel-grey
colored layer with very weak brown, as shown in
Figure 11b. The water wall tube also had a light steel-grey
colored layer on the surface. The color of the economizer
inlet zone tube surface in a boiler operating under AVT(O)
is dark steel-grey (Figure 11c).
The product on the metal surface has been analyzed by
X-ray diffraction (XRD), showing that the oxidation film
formed in hot water with O2 is different from that formed in
hot air. The product on the economizer inlet and outlet
zone tube surfaces in a boiler operating under AVT(O) is a
pure Fe3O4. The product on the economizer inlet zone
tube surface in a boiler operating under OT is -Fe2O3 and
some Fe2O3 with cubic crystals as well as a small amount
of Fe3O4. The product on the tube surface of the economizer outlet zone in a boiler operating under OT is Fe3O4
and a small amount of -Fe2O3.
These tube sample surface appearances were magnified
500 times by scanning electron microscopy (SEM) and the
images are shown in Figure 12. The reddish brown layer
on the surface of the inlet section tube is a dense covering
layer. This may suggest that a certain amount of ferrous
hydroxide still exists in the film, which is the driving force
for the oxygen reduction at the cathode. Due to the
increased oxygen concentration in the water, Fe2+ from the
metal matrix was oxidized to Fe3+ by oxygen and sub-

sequently a Fe2O3 oxide coating in the oxide layer was

formed under the conditions of the water temperature at
the inlet section of the economizer, which is very important
for inhibiting FAC at the economizer tube entrance.
This kind of Fe2O3 film is different from the -Fe2O3 formed
at high temperatures and is unstable at the temperature of
feedwater [6] and the high flow rate of feedwater; it
requires continuous oxygen feed (above 30 g L1) to
maintain its stability.
The oxide film color and appearance characteristics of the
economizer outlet tube samples are close to those of
water wall tube samples, showing a "clean" surface compared with that of the inlet section tube although there is a
very weak brown color on the tube surface. This phenomenon may also suggest that the effect of oxygen promoting the formation of a double protective layer on the metal
surface by means of cathodic reduction in a corrosion cell
has visibly begun to weaken. Thus, the Fe2O3 oxide coating layer formed by oxygen feed only extends as far as the
economizer inlet section where the water temperature is
still about 300 C (water temperatures of the economizer
inlet and outlet are 290 C and 320 C, respectively).
However, the oxidation-reduction potential (ORP) of the
water here has been kept at a positive value in the boiler
water solution due to oxygen feeding, until oxygen in the
water enters into the steam in the water wall evaporating
section of the boiler.
When the water temperature of the economizer outlet
exceeds 300 C, redox reactions occurring on the metal
surface may directly oxidize ferrous ions to ferric ions
instantly, as illustrated in the chemical reaction Eq. (5),
which also suggests that bivalent iron ion migrating outward from the metal matrix may be converted to ferric ions

Figure 12:
SEM surface appearance (magnified 500 times) of 600 MW unit boiler tubes under OT.
a) Economizer inlet tube surface with a dense covering layer
b) Economizer outlet tube surface
c) Water wall tube surface

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Boiler Feedwater Oxygenated Treatment in Power Plants in China

in an instant. The formation of dense magnetite oxide films

has no ferrous hydroxide as a transitional product here
(Eq. (5)):
3Fe + 4H2O = Fe3O4 + 4H2

face can be spontaneously oxidized to form a fine and

dense film by water and steam with sufficient oxidizing
strength. However, there are different surface appearances due to iron corrosion products depositing on tube
surfaces when boiler feedwater treatments are different;
Figure 13 illustrates boiler water wall tube surfaces with
feedwater treatments of AVT(R), AVT(O) and OT, respectively. The outside layer of the oxide film on a water wall
tube treated with AVT(R) (Figure 13a) has an oxide that has
a coarse granular particle size, since the iron oxide particle
comes from the upstream thermal system by corrosion
product transport. The outside layer of the oxide film on a
water wall tube treated with OT (Figure 13c) has a fine
granular particle size since the oxide film was formed in
situ and few iron oxide particles originate from the
upstream thermal system water. The outer layer of the
oxide film on the water wall tube treated with AVT(O)
(Figure 13b) has iron oxide particles of a size between the
above two scenarios; nevertheless, the oxide layer still has
obvious rippled characteristics.

(5)

As long as the ferric iron concentration is above a very low

threshold, it precipitates and becomes a stable solid
phase, because the solubility of magnetite is much lower
than that of ferrous hydroxide.
In this process, Eq. (5) is in balance with no excess bivalent ferrous ions or electrons, so the oxygen molecule here
has no way to participate in the formation process of the
oxide film reaction.
In other words, the metal oxide film is in a passive state
due to the temperature (above 300 C) and ORP (above
100 mV of the water, and an excess of oxygen in the water
and elevation of water pH are not important in this pure
water system. The scaling rate on the tube surface here
also indicates that the oxidation film is very thin in the
economizer outlet in Table 1. Among 4 boilers, the scaling
rate of the economizer of the boiler operating under OT is
the lowest.

The products on the metal surfaces have been tested by

XRD. The product on the water wall tube surface in a
boiler with AVT(O) is a Fe3O4. The product on the water
wall tube surface, including the economizer outlet section,
in a boiler with OT is Fe3O4 and a small amount of
-Fe2O3, because hot water is strongly oxidizing under
conditions of higher temperature and positive ORP; corrosive product migration and deposition can also impact the
products on the water wall tube surfaces.

This phenomenon indicates that in metal oxidation there is

a competitive relationship between hot water and a small
amount of oxygen at the temperatures in the thermal system. In the lower temperature zone, oxygen in the water
can promote the formation of a double protective coating
layer on the metal surface. In the middle temperature
zone, the oxidizing strength of the water is enhanced due
to higher temperature and positive ORP of the water;
water and oxygen may contribute jointly to metal oxidation. In the steam zone, the contribution of water steam
and oxygen to metal high-temperature oxidation mainly
depends on the gas partial pressure.

Change in the Metal Oxide Film in the High-Temperature Zone of the Boiler Heating Surface
It has been a concern to chemistry personnel whether
feedwater oxygenated treatment (OT) affects the oxidation
behavior of the internal surfaces of superheater and
reheater tubes. All collected data from field samples show
that OT did not increase the oxide growth rate of superheater and reheater tube interiors. There is almost no controversy regarding this result. With regard to the oxide layer
peeling off, it has been confirmed that oxide layer exfoliation of low-chromium alloy steel (T23), martensitic steel

Deposition on the Water Wall Tube Surface

The temperature of water or steam in supercritical boiler
water wall tubes is high (above 350 C), so the metal sur-

Unit
Treatment

#1

#2

#3

#4

AVT(O) 1 year
WOT 0.4 years

AVT(O)
0.83 years

AVT(O)
1 year

OT
1.17 years

Measuring point

EIS

EOS

EIS

EOS

EIS

EOS

EIS

EOS

Scaling rate (g m2 per year)

60.6

46.9

42.9

33.5

79.5

51.3

35.3

29.2

Table 1:
Scaling rate (g m2 per year) at the tube surface of the economizers in one power plant.
WOT
EIS
EOS

300

weak OT
economizer inlet section
economizer outlet section

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Boiler Feedwater Oxygenated Treatment in Power Plants in China

Figure 13:
Surface appearance (magnified 2 000 times) of 600 MW boiler tubes with different feedwater treatments.
a) AVT(R), operation for 4.5 years
b) AVT(O), operation for 1 year
c) OT, operation for 1 year

(T91) and high-chromium alloy steel (HR3C) has not been

affected by oxygen concentrations in steam. The focus of
the argument is whether oxygen in the steam promotes the
spallation of the metal oxide layer of 18 Cr series austenitic
stainless steel in high-temperature zones [7,8].
It was found from the investigations and surveys in China
that the issue of oxide removal from 18 Cr series austenitic
stainless steel is more prominent in boilers treated with
OT. The extent of serious oxide layer exfoliation is quite
different when the design of the unit includes the same
pipe material in boilers with or without OT. In some units,
exfoliation took place in the superheater, while in other
units exfoliation took place in the reheater, and in some
units, the exfoliation occurred in both the superheater and
the reheater, or in neither. After careful research and comparison, it was shown that temperature is the key factor in
addition to the specific metal alloy. The influential factors
for boiler tube temperature are the boiler model, type of
coal, combustion mode, heating surface design, arrangement of superheater and reheater, etc.
Chromium Acid Ion (CrO42) Release during OT
Conversion
An increase in cation conductivity in water and steam is a
common phenomenon during OT conversion. This is
because some anionic impurities are released from the
oxide film as phase transition occurs. These anionic impurities commonly include Cl, F, SO42, formic acid and
acetate ions as well as carbonate ions. As the concentration is low and release time is short, they do not jeopardize
the water and steam quality. TPRI has found another
anionic impurity, the chromium acid ion (CrO42) [9]
released in later phases of OT conversion, as shown in

PowerPlant Chemistry 2014, 16(5)

Table 2, which has a higher concentration than common

anionic impurities, and also contributes to the cation conductivity increase.
The source of chromium acid ion is a special concern
because boiler section materials contain the element Cr.
According to the data compiled after converting to OT in
dozens of units, TPRI has developed a summary of the
characteristic release of chromium acid ion as follows:
1. Chromium acid ion mainly appears in economizer inlet
and superheated steam samples (see Table 3 below). It
is usually accompanied by an oxygen content increase
in the feedwater and superheated steam samples after
oxygen is added to the feedwater, and the CrO42 content peaks in a short time. The higher the dissolved
oxygen (DO) content, the larger the peak value is. This
level gradually decreases, but this rate of decrease is
not related to DO. In fact, CrO42 release does not
appear in all units during the OT conversion process,
which may be associated with the sample tubing material.
2. There is no evidence of chromate ions in the water/
steam cycle. CrO42 is never detected in the condensate, low-pressure feedwater, boiler water, and highpressure drains, or reheat steam in either the OT
conversion process or under normal operating conditions of a unit. Chromium content is also not detected
in deposits in steam systems and turbines. When
running on normal OT, DO is 30 to 80 g L1, and
CrO42 is not detected in any sampling points of the
water/steam cycle. If the DO concentration is increased
intentionally for testing, CrO42 will clearly increase in
the economizer inlet sample. This reveals that the DO
concentration plays an important role in CrO42 release.

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3. In superheated steam sample tubing, CrO42 release is

only found when dry steam in the end part of the pipe
segment is gradually converted to wet steam or even
water. There is only a trace of CrO42 in superheated
steam sampling of some supercritical units. For one
unit, it has been confirmed that the sample tubing insu-

Unit

lation is good [10]. However, CrO42 has not been found

in low-pressure and low-temperature feedwater samples, even though the low-pressure heater tubing is
made of stainless steel. This also confirms that temperature plays an important role in CrO42 release.

Economizer Inlet
(g L1)

Unit Capacity

Steam
(g L1)

DO

CrO42

DO

CrO42

600 MW
supercritical once-through boiler

150200

< 0.3

< 10

< 0.3

500 MW
subcritical once-through boiler

200300

< 0.3

50100

5.1

300 MW
subcritical drum boiler

300350

4.6

150250

0.5

600 MW
supercritical once-through boiler

150200

18.4

7060

< 0.3

600 MW
supercritical once-through boiler

150200

211

~ 100

1.4

300 MW
subcritical once-through boiler

200300

17

50100

26

600 MW
supercritical once-through boiler

100200

50150

< 0.3

1 000 MW
ultra-supercritical once-through boiler

100150

23

3040

1.2

Table 2:
Dissolved oxygen (DO) and chromium acid ion content at some sample points during OT conversion.

Data

Deaerator Inlet
(g L1)

Economizer Inlet
(g L1)

Steam
(g kg1)

HP Heater
(g L1)

Reheater
(g kg1)

Condensate
(g kg1)

6-27

< 0.3

< 0.2

< 0.3

< 0.3

< 0.3

< 0.3

6-28

< 0.3

< 0.2

< 0.3

< 0.3

< 0.3

< 0.3

6-30

< 0.3

< 0.2

< 0.3

< 0.3

< 0.3

< 0.3

7-1

< 0.3

< 0.2

< 0.3

< 0.3

< 0.3

< 0.3

7-3

< 0.3

< 0.2

< 0.3

< 0.3

< 0.3

< 0.3

7-5

< 0.3

2.82

< 0.3

< 0.3

< 0.3

< 0.3

7-8

< 0.3

90.8

< 0.3

< 0.3

< 0.3

< 0.3

7-17

< 0.3

148.5

1.4

< 0.3

< 0.3

< 0.3

7-18

< 0.3

211.0

< 0.3

< 0.3

< 0.3

< 0.3

7-20

< 0.3

171.1

< 0.3

< 0.3

< 0.3

< 0.3

7-23

< 0.3

54.5

< 0.3

< 0.3

< 0.3

< 0.3

Mode

AVT(O)

OT
convertion

Table 3:
CrO42 content at cycle sampling point in Unit E during OT conversion.
Note: < 0.3 indicates that the CrO42 content is less than the detection limit (0.3 g L1) for the chromatograph.

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Boiler Feedwater Oxygenated Treatment in Power Plants in China

The analysis above reveals that CrO42 only comes from

the sample tubing surface film. One possible mechanism
is as follows:

REFERENCES
[1]

Li, Z., Shen, B., Thermal Power Generation 1998,

27(6), 42 [in Chinese].

In the stainless steel sample tubing of the economizer

inlet, the water temperature is at 270 C to 290 C; there
are Cr2O3, Crx FeyO3, Cr(OH)2 and Cr(OH)3 present, from
the inside to outside of the metal oxide film under AVT
conditions. The higher the temperature, the higher the
ratio of chromium oxide in the oxide film, due to the accelerating diffusion of chromium ions in the material. During
the unit conversion to OT, as oxygen passes through the
sampling tubes, the redox potential rises, and the water
changes to a more oxidizing state. The metal oxide film on
the surface of the sampling tube changes accordingly.
Low-valence oxides in the oxide film are oxidized to highvalence oxides, such as Fe2+, Cr2+ and Cr3+ being converted to Fe3+ and Cr6+. Part of the high-valence chromium
compounds dissolve and combine with water to form
CrO42. Under a certain water temperature and fluid flow
velocity, if the oxygen concentration is beyond a certain
range, the higher the oxygen concentration, the faster the
chromium ion release from the metal [11]. Therefore, for
feedwater sample tubing made of stainless steel material,
specific high temperatures, water flow rate and DO concentration prove to be three key conditions for chromium
acid ion release; without any of these three conditions,
chromium acid ion release will not happen.

[2]

Guideline for Cycle Chemistry in Fossil Power Plant:

Part One, Oxygenated Treatment of Once-Through
Boiler, 2002. Thermal Power Research Institute,
Xi'an, P. R. China, DL-T 850.1 [in Chinese].

[3]

Li, Z., Chen, R., China Electric Power 2004, 37(11),

47 [in Chinese].

[4]

VGB Guidelines for Boiler Feed Water, Boiler Water,

and Steam of Steam Generators with a Permissible
Operating Pressure >68 bar, 1988. VGB Kraftwerkstechnik GmbH, Essen, Germany, VGB-R 450 Le.

[5]

Li, Z., Thermal Power Generation 2002, 31(6), 26 [in

Chinese].

[6]

Evans, U. R., Corrosion and Oxidation on Metal,

1976. China Mechanical Industry Press [in Chinese].

[7]

Jia, J., Li, Z., China Electric Power 2008, 41(5), 37 [in
Chinese].

[8]

Dooley, R. B., Bursik, A., PowerPlant Chemistry

2011, 13(4), 236.

[9]

Li, Z., Shen, B., Huang, W., Thermal Power

Generation 2012, 41(2), 47 [in Chinese].

[10] Shanghai Shidongkou Power Plant Report, 2004.

Thermal Power Research Institute, Xi'an, P. R. China
[in Chinese].

CONCLUSION
The application of feedwater oxygenated treatment technology in China is successful and has achieved technical
and economic benefits. Feedwater oxygenated treatment
for the pre-boiler system can significantly reduce the iron
content in the feedwater system and then reduce the
boiler differential pressure drop and deposit rate on boiler
tubing, which eventually results in the improvement of
boiler efficiency and energy savings.
Feeding oxygen to the water makes the metal surface
form a reddish brown Fe2O3 coating layer. This layer
requires continuous oxygen feed to maintain its stability.
Research has confirmed that oxygen promotes the formation of a double protective film on the metal surface
through the cathodic reduction effect in the corrosion cell.
This mechanism is closely related to water temperature,
and its effective temperature range is from room temperature to about 300 C.
The CrO42 detected at some water sampling points during OT conversion and/or normal operation with OT does
not come from the thermal equipment material but most
likely is released from stainless steel sample line tubing.

PowerPlant Chemistry 2014, 16(5)

[11] Effertz, P.-H., Die kombinierte Ammoniak-, Sauerstoffkonditionierung von Wasser-, Dampfkreislufen
in Kraftwerken: Tagungsbericht d. Allianz-Workshops
im Allianz-Zentrum fr Technik Ismaning bei
Mnchen, 8./9. November 1982 (Editor P.-H. Effertz).
Allianz-Berichte fur Betriebstechnik und Schadenverhtung, 1985, 23. Allianz-Versicherungs-AG,
Mnchen, Germany.

ACKNOWLEDGMENTS
We acknowledge Mr. Andrew Howell from Xcel Energy and
Mr. Peigang Cao from Ontario Power Generation for
reviewing and revising this paper.

THE AUTHORS
Zhigang Li (B.S., Metal Corrosion Protection, Dalian
University, China) is a senior committee member of the
Chinese Society of Electrical Engineering and has been
responsible for research and development of power plant

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Boiler Feedwater Oxygenated Treatment in Power Plants in China

chemistry for fossil plants in China since 1980 as a engineer of the Thermal Power Research Institute, China. He
has been a director engineer of the Chemical Engineering
Research Department of Xi'an Thermal Power Research
Institute since 2011. He was a researcher and deputy
director of the Chemical Engineering Research Department of Xi'an Thermal Power Research Institute, P. R.
China, from 1999 to 2010.
Wanqi Huang (B.S., Power Plant Chemistry, Wuhan
University of Hydraulic and Electrical Engineering, China)
is a senior engineer and has been working at the Thermal
Power Research Institute (TPRI) Co. LTD. since 1999. He
is a director of a department of TPRI which is responsible
for the technology of metal corrosion and protection of
thermal equipment and water treatment for power plants.
Songyan Cao (M.S., Applied Chemistry, University of
Northeast China Institute of Electric Power, M.E., Thermal
Power Engineering, Xi'an Thermal Power Research
Institute) started her career in 2004 in a power plant in
Jiangsu province in China. Since 2006, she has been

working at TPRI Co., LTD. with emphases on water chemistry treatment, corrosion and protection of thermal equipment. In 2011 she obtained a Master's degree from TPRI.
Hongbo Zhang (M.S., Environmental Engineering, M.E.,
Chemical Engineering, University of Northeast China
Institute of Electric Power) has been working at TPRI Co.,
LTD. in China with emphases on water chemistry treatment, corrosion and protection of thermal equipment
since 2011.

CONTACT
Zhigang Li
Thermal Power Research Institute
32, Xiying Road
Xi'an, Shaanxi Province
P. R. China, 710043
E-mail: lizhigang@tpri.com.cn

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