Evaluation of the Steam-Water Cycle Condition for Sustainable Water Chemistry Operation

Evaluation of the Steam-Water Cycle Condition for Sustainable Water

Chemistry Operation
A. Drexlera, F. Roumiguierea, U. Rammingera, J. Fandricha
a
AREVA NP GmbH,
IBOC-G,
Paul-Gossen-Str. 100
91052 Erlangen, Germany

Abstract. Water and steam serve in the water-steam cycle as the energy transport and work media. These fluids
should have no influence, through corrosion processes on the construction materials and their consequences, on
the normal service of the plant. All these objectives are especially valid for the steam generators (SG). The SGs,
act as a barrier between the radioactive primary side and the non-radioactive secondary side of pressurized water
reactors. Their condition is therefore a key factor for plant performance, high plant availability, plant safety, and
regarding life time extension.

1. Introduction

Water and steam serve in the water-steam cycle as the energy transport and work media. These fluids
should have no influence, through corrosion processes on the construction materials and their conse-
quences, on the normal service of the plant. In a more detailed form, the main objectives of the steam
water cycle chemistry can be stated as follows:

— The metal release rates of the structural materials shall be minimal

— The probability of selective / localized forms of corrosion shall be minimal.
— The deposition of corrosion products on heat transfer surfaces shall be minimized.
— The formation of aggressive media, particularly local aggressive environments under deposits,
shall be avoided.

All these objectives are especially valid for the steam generators, which have to be considered as the
key component of the secondary side from the viewpoint of chemistry. The above mentioned
objectives require the fulfillment of one main goal: keeping the corrosion product inventory of steam
generator as low as possible. This goal can be achieved by

(a) preventive measures: cycle chemistry focusing with due priority on reduction of corrosion
product generation of and their deposition inside steam generators,
(b) control measures: Set-up and performing regularly a steam generator condition assessment with
the focus on cleanliness, to enable a condition-related SG maintenance and
(c) corrective measures, i.e. removal of deposits from steam generator by mechanical and/or
chemical cleaning measures.

AREVA has developed a systematic approach of evaluation of SG cleanliness condition for step (b) of
the above mentioned sequence following the scheme of, based on a consequent analysis of:

Plant operating data

— Chemistry parameters (normal operation, start-up, out of spec events),

— Hide-out measurements whenever possible
— Hide-out return chemistry, and
— Thermal performance data. Fouling measurements

Outage activity results

— Visual inspections
— Analysis of tube sheet lancing results

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Evaluation of the Steam-Water Cycle Condition for Sustainable Water Chemistry Operation (cont.)

— Oxide thickness measurements/ evaluation

These data are used for an expert assessment of the SG status applying AREVA’s Fouling Index Tool
Box [1] [2].

Water Chemistry Data Inspection Results Thermal Performance

(e.g. iron ingress, hide-out) (e.g. visual, sludge mapping) (e.g. heat transfer)

Steam Generator Assessment

No measures required Measures required

Steam Generator Cleaning

Preventive Chemical Cleaning Curative Chemical Cleaning

Mechanical Cleaning
(e.g. Tube sheet and/or inner bundle lancing, upper bundle flushing)

Improvement of Water Chemistry

Continuous Steam Generator Surveillance

FIG. 1 Steam generator cleanliness management

A cleanliness management program is in principle a closed cycle process that first assesses the current
SG situation and the long term trend. In the subsequent steps appropriate measures which improve the
current status or counteract on identified relevant issues are identified, defined and applied. These
measures cover a wide range of counteractions, starting by preventive water chemistry improvements
(a) or corrective measures as SG mechanical and/or chemical cleanings (c)

This paper describes the AREVA approach on improvement of water chemistry treatment. The correc-
tive measures, mainly SG chemical cleaning are treated in a separate work [3].

2. Water Chemistry Basics

The corrosion product ingress into the steam generator depends on the corrosion rate along all the
water-steam cycle and during all plant operation conditions, i.e.

— power operation,
— shut-down condition (especially outages) and
— start-up transients.

2.1 Corrosion product control during power operation

The pH(25°C) in feedwater has been traditionally used as reference to assess the degree of alkalinity in
the secondary cycle. As known, the pH which really accounts is the pH at the real temperature at each
location of the cycle. The different alkalizing agents will have a different pH variation with tempera-
ture and they will distribute along the cycle according to their different volatilities. The pH at
temperature at each system in the secondary side of a PWR will be then a function of two parameters:

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 Evaluation of the Steam-Water Cycle Condition for Sustainable Water Chemistry Operation

— dissociation constants Kb of used amine (basicity)

— distribution coefficients Kd of used amine (volality)

2.1.1 Reduction of the corrosion product generation and transport

The alkaline conditioning pursues two main targets concerning corrosion product control.

(a) Minimization of the general (C-Steel) corrosion along all the secondary cycle and
(b) Minimization of flow-accelerated corrosion in wet steam areas

To achieve the first target i.e. minimization of the overall general corrosion and transport of the corro-
sion products into the steam generators, a high overall pH value is required. The optimum pH(25°C) is
higher than 10 (see FIG. 2), and a lower pH is associated with a significant increase of the metal
release, especially at lower temperatures (FIG. 3).

A pH(25°C) > 10.0 cannot be practically achieved with weakly basic amines at reasonable concentra-
tions. From this point of view, the amines having a relative high basicity, i.e. a high Kb at the tempera-
ture of interest, are in principle the best choice. Also a high volatility is required to ensure a good
distribution also in the steam systems and main condenser.

4
Metal release rate [mg dm-2 month-1]

Test Conditions
Temperature: 232°C
Flow velocity: ~ 0.3 m/min
3 Oxygen (O2): < 0.1 ppm

0
7,5 8,0 8,5 9,0 9,5 10,0

pH(25°C)

FIG. 2. Measured metal release rate of carbon steels as a function of pH(25°C), redrawn from[4]

100
Fe ion concentration [mg kg-1]

T = 200°C
T = 250°C
80
T = 270°C
T = 300°C
60

40

20

0
7,0 7,5 8,0 8,5 9,0 9,5 10,0 10,5

pH(25°C)

FIG. 3. Soluble iron concentration of a carbon steel / water system as a function of pH(25°C)

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Evaluation of the Steam-Water Cycle Condition for Sustainable Water Chemistry Operation (cont.)

To achieve the second target, i.e. minimization of flow-assisted corrosion (FAC) on wet steam
surfaces, the pH (T) of the liquid film in contact with the carbon-steel (C-steel) surfaces must be kept
high. As steam expands at the high-pressure (HP) turbine, a two-phase system is formed (wet steam),
affecting mainly the HP turbine outlet, cross-under line, steam extraction lines and moisture-separator
(MSR) region. There, a water film is formed on C-steel surfaces. Amines may be stripped out from the
water phase in contact with the metal depending on their volatility, resulting in a local pH(T) decrease.
This phenomenon, associated with a low oxygen concentration may cause flow accelerated corrosion
(FAC) [5] - [10] on unalloyed carbon steel materials.

If ammonia is used as alkalizing agent, the relationship between FAC rate and pH(25°C) on the water
film is shown in FIG. 4, showing the dependence of FAC rate with the pH value in the water film in
contact with the metal, and the existence of a rather sharp pH threshold value of pH(25°C) ≈ 9.4 – 9.6
above which FAC becomes effectively suppressed. This corresponds with a pH(T) ≈ 6,5 – 6.6 at the
typical cross-under temperatures.

101
material loss [mm/a]

100

10-1
A pH shift from 9.4 to 9.6
reduces material loss rate
by factor of 10.

10-2 Material: C-Steel (0.3% Mo)

Temperatur: 180°C
V(Steam): 39 m/s
alkalizing agent NH3

10-3
6 7 8 9 10 11

pH(25°C) in water film in contact with the metal

FIG. 4. Dependence of flow accelerated corrosion and pH(25°C) in water film

when NH3 is used as alkalizing agent (redrawn from [9])

Therefore, for FAC suppression, contrarily to the first target a low volatility amine is required to avoid
amine stripping from the water film on the carbon steel surfaces at the wet steam areas.

The selection of the alkalizing agent must be made under consideration of this opposed requisites.

2.1.2 Measures and strategies

Beside the above mentioned targets regarding pH values another requirement for steam generator
safety has to be considered. The steam generator shall be operated under reducing conditions. To
ensure this prerequisite Hydrazine (N2H4) is added in secondary side. A combination of this prerequi-
site using hydrazine with necessity of dosing an amine to achieve a high pH value is realized by using
the High-AVT chemistry treatment.

Hydrazine is dosed into the main condensate for which reacts with oxygen to nitrogen and water (1).
For that a hydrazine concentration in the range of 50 – 100 µg/kg is necessary. But N2H4 decomposes
also thermally into ammonia (2). Depending on plant conditions, the NH3 concentration in feedwater
can achieve values of 5 - 10 mg/kg. This corresponds to pH(25°C) = 9.80 – 9.95 in feedwater. These
ammonia amounts in feedwater will result on about 6 times lower concentrations in wet-steam water
film of 0.85 mg/kg to 1.65 mg/kg resulting in a pH(190°) = 6.4 – 6.6. That means the hydrazine
requirements satisfy simultaneously the need of high pH for general corrosion control and FAC.

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 Evaluation of the Steam-Water Cycle Condition for Sustainable Water Chemistry Operation

N2H4 + O2 → N2 + 2 H2O (1)

N2H4 → x N2 + y H2 + z NH3 (2)

A prerequisite for ammonia-only high-AVT chemistry treatment is the absence of copper materials in
the secondary side. This may be a handicap for existing plants from the economical point of view,
because replacement of copper materials from their secondary side may become expensive, depending
on the amount of components having copper bearing materials which need to be replaced. In that case
the use of a second, less volatile, amine complementary to ammonia like Morpholine or Ethanolamine
(ETA) needs to be applied. These organic amines have a better distribution coefficient Kd between the
water and steam phase. Consequently the target of a pH(190°C) in the water film of two phase flow
system can be better achieved. However, these amines cannot replace ammonia since

— ammonia will be anyway present at considerable amount from the hydrazine decomposition (2),
which cannot be reduced below the amounts required to ensure reducing conditions, and
— ammonia is required to improve the overall pH in the circuit including steam systems and main
condenser.

In any case the final ammonia equilibrium concentrations along the systems will depend on the two
factors, i.e.

— production rate from hydrazine decomposition and

— ammonia elimination by condenser exhaust (jet) pumps and SG blowdown.

Plants having blowdown enthalpy recovery (blowdown flash tank) will recover about 75% of the
ammonia present in blowdown having correspondingly lower NH3 losses. On the other hand, plants
having a high condenser exhaust flow rate (normally due to increased air in-leak in the sub-pressure
areas) may cause big ammonia losses resulting in a too low NH3 equilibrium concentration in the
system.

Complementarily to an adequate pH strategy, an effective corresponding improvement can be intro-

duced consisting on the application of film-forming amines in the secondary side as a very effective
measure to counteract corrosion. The use of film-forming amines (FFA) has become very popular in
the fossil power plant sector, showing a decrease of corrosion product generation by improving the
surface conditions.

An adherent hydrophobic, temperature-resistant film is built acting as a shield that limits the access of
water and hydrated species to the metal or metal oxide surface. This barrier lowers the corrosion rate
by inhibiting the mass transfer between surface and solution. The hydrocarbon chain imparts a hydro-
phobic character while the amine group bounds to the metal (FIG. 5).

Water

Protective Film of Amine

Base Material

FIG. 5. Principle of film-forming amines

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Evaluation of the Steam-Water Cycle Condition for Sustainable Water Chemistry Operation (cont.)

Besides, by formation of the film other substances adsorbed / adhered on the surfaces like colloidal
iron-oxide deposits and ionic impurities can be released at variable extent (cleaning effect). This effect
has been clearly observed in field applications.

Water Water

Base Material Base Material

FIG. 6. Principle of mobilization of adsorbed / adherent

colloidal deposits (e.g. iron-oxides) and ionic impurities (e.g. chloride)

2.2 Corrosion product control during Shut-Down Period

During plant shut-down condition (outages) the systems and components are flooded with air as they
are opened to atmosphere. Combined with incomplete draining this yields to wet surfaces, moisture
condensation, etc. which will result in general corrosion of the carbon steels surfaces. Additional
localized corrosion might also occur in case of formation of anodic sites (preferentially in presence of
impurities), like for instance at the intersection between the metal, air and liquid in water puddles.
Water and air are the pre-requisite.

To avoid this normally lay-up measure are performed which could be distinguished in

— Dry lay-up (applied to empty systems) bringing their inner environment to a dew point of
< 10°C or < 50% relative humidity (RH). Water is excluded, thus making the corrosion process
not possible.
— Wet lay-up (applied to filled systems) with conditioning agents excluding oxygen thus impeding
the corrosion process.

Beside this well known lay-up strategies AREVA developed a lay-up concept using film-forming
amines. The advantages of the film-forming amine application for lay-up are:

— Significant reduction of lay-up efforts

— Effective inner surface protection during outage works
— No or minimum contact between liquid water and C-steel surfaces
— Long-term stability of the protective film even in aggressive environmental conditions
— No influence on existing oxide layers
— No negative influence on plant operation and performance
— No environmental hazards of the waste water after system lay-up
— The protective effect continues after restarting the unit.

AREVA performed successful the non-continuous FFA dosing in the whole secondary side of two
PWRs during power operation with significant reduction of corrosion product generation and transport
into the steam generator. Results are shown in FIG. 7

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 Evaluation of the Steam-Water Cycle Condition for Sustainable Water Chemistry Operation

FIG. 7. Surface of secondary side systems of a PWR after application of FFA

(left side: condenser, right side: feedwater pumps steam turbine)

2.3 Corrosion product control during Start-up Transients

Corrosion products generated during outage periods may be transported inside the SGs during start-up
of the plant especially if no or insufficient layup is practiced, and the condensate-feedwater train is not
properly flushed before switching the feedwater line to feed the SGs. The impact of the start-up tran-
sient can reach unacceptable levels, requiring the implementation of a careful shutdown and start-up
chemistry concept. FIG. 8 shows the integrated magnetite ingress amount along a cycle with two
outages, where the outage input is a relevant fraction of the total ingress.

FIG. 8. Ingress of corrosion products during plant start-up [11]

3. Summary

This paper describes the AREVA approach on improvement of the secondary side water chemistry
treatment with the target to reduce the corrosion product ingress into the SG, identified as one of the
main concerns regarding SG integrity. The alkaline treatment is performed in order to minimize the
general (C-Steel) corrosion along all the secondary cycle and to minimize the flow-accelerated corro-
sion in wet steam areas. The first target requires an amine having a relative high basicity (i.e. a high Kb
at the temperature of interest) and having high volatility to ensure a good distribution also in the steam
systems and main condenser. Contrarily, for FAC suppression, a low volatility amine would be suit-

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Evaluation of the Steam-Water Cycle Condition for Sustainable Water Chemistry Operation (cont.)

able to avoid amine stripping from the water film on the carbon steel surfaces at the wet steam areas.
The selection of the alkalizing agent must be made under consideration of this opposed requisites. The
ammonia-only high-AVT water chemistry treatment using 50 – 100 µg/kg hydrazine as the only
conditioning agent combines the prerequisite of ensuring reducing conditions at the SGs and genera-
tion of sufficient amount of ammonia to achieve the necessary high pH value required to minimize the
overall general corrosion as well as effective protection against FAC. A prerequisite for its application
is the absence of copper materials in the secondary side. Plants having copper bearing materials in the
circuit are restricted in the use of hydrazine to keep low the ammonia concentration, jeopardizing the
establishment of sufficiently reducing conditions and impeding the establishment of a high pH,
making necessary the use of a less volatile complementary amine to avoid FAC.

AREVA involved in an ongoing improvement process, has developed additional techniques for the
maintenance and supervision of the SG condition. A very effective complementary measure has been
introduced, consisting on the non-continuous dosing of film-forming amines in the secondary side.
AREVA performed recently such non-continuous dosing of a specific film-forming amine in the in the
whole secondary side of two PWRs during power operation with success, resulting in a significant
further reduction of corrosion product generation and transport into the steam generators. Additionally
AREVA developed a lay-up concept using film-forming amines with considerable advantages,
reducing the iron ingress during start-up significantly.

The plant specific pH strategy in combination with the application of film-forming amines developed
and performed by AREVA was proven to reduce significantly the iron ingress into the steam genera-
tors. Concerning supervision of the SG condition, AREVA has developed a systematic approach of
evaluation of SG cleanliness condition following a systematic and consequent analysis of plant
operating data and outage activity results, to obtain an expert assessment of the SG status applying
AREVA’s Fouling Index Tool Box [1] [2].

REFERENCES

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Chemistry Conference 2010, Quebec, Canada (2010)
[2] ODAR, S. SCHNEIDER, V., SCHWARZ, T., BOUECKE, R., Cleanliness Criteria to Improve
Steam Generator Performance, International conference on water chemistry of nuclear reactor
systems, Jeju Island, Korea (2006)
[3] WEISS, S. DREXLER, A. FANDRICH, J., Steam Generator Maintenance Measures as Part of
an Integrated Management in PWRs, 3rd International Conference on Nuclear Power Plant Life
Management (PLiM), Salt Lake City, USA (2012)
[4] HEITMANN, H.G., Praxis der Kraftwerk-Chemie, Vulkan Verlag, Essen (1986)
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Erosionskorrosion, VGB Kraftwerkstechnik 64 No. 5, p. 452–465, (1984).
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Decisionmaking tools for counteracting material degradation, VGB Kraftwerkstechnik 70 No.
11, p. 939–948, (1990).
[9] KASTNER, W., HOFFMANN, P., NOPPER, H., Erosionskorrosion in Kraftwerksanlagen -
Entscheidungshilfe für Maßnahmen zur Schadensvermeidung, VGB, Essen (1990).
[10] HEITMANN, H.G., KASTNER, W., Erosionskorrosion in Wasser-Dampfkreisläufen: Ursachen
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[11] IAEA-TECDOC-1668, International Atomic Energy Agency, Vienna (2011)