Water-Steam Cycle Chemistry and

Corrosion
Paul McCann, Uniper
5th Energy from Waste and Biomass Workshop
Cycle Chemistry – Why is it important?

 “It is clear that the major Boiler/HRSG failure mechanisms are driven
by thermal and/or cycle chemistry influences” (EPRI, 2003)
 Effective cycle chemistry monitoring and control is required to:

 Operate plant safely.

 Protect plant integrity.

 Meet legal requirements, e.g. PSSR.

 Maintain reliability and availability.

 Reduce maintenance and loss of availability costs.

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Pressure Part Failures

Mechanism Chemistry Influence

Flow-Accelerated Corrosion Reducing conditions; low pH

Hydrogen Damage Waterside deposits; low pH

Acid Phosphate Corrosion Waterside deposits; Deficient phosphate control
Caustic Corrosion Waterside deposits; High pH
Waterside Deposits Cycle chemistry not optimised ; Condenser
leaks
Corrosion Fatigue Cycle Chemistry not optimised
Pitting Inadequate shutdown conditions
Overheating Internal waterside deposits
Stress Corrosion Cracking Carryover; Steam contamination

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Basic Reactions of Iron with Water

 Metals occur naturally as oxides and

sulphides.
 Metal ores are produced by reduction.
 In the presence of water and air, there is a
natural tendency to revert to the oxidised
state since this condition is more
thermodynamically stable.
 This is the process of corrosion.

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Corrosion Cell

From https://chem.libretexts.org/

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Formation of Protective Oxides

 In boilers with deaerated,

20 µm
mildly alkaline conditions, the
surfaces of clean mild steel
react with water to form
magnetite and/or haematite
 Magnetite, Fe3O4 (black,
stable in more reducing
conditions.
 Haematite, Fe2O3 (red/brown,
stable in more oxidising
conditions).
 At boiler operating, these
oxides are compact, non
porous and protective.

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Corrosion of Carbon Steel

 Boiler/evaporator
tubes are mainly
carbon steels.
 Corrosion rate
depends on pH and
oxygen content.
 High pH and low
oxygen results in
lowest corrosion
rate.
 Minimum corrosion
with a pH of 9 - 12
(at 25oC).

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Magnetite Solubility and pH

Aim for water phase pH of 9.4 or higher in all-ferrous systems

 pH 8.8
 pH 8.9
 pH 9.0
 pH 9.2
 pH 9.4
 pH 9.6

Sturla, P., (1973)

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Copper Materials

Resch, G. and
Zinke, K., (1980)

Minimal corrosion occurs in the pH range 8.8 - 9.2 under deaerated conditions.
Ammonia forms complexes with copper which destabilises the metal.

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Feedwater Treatment

There are three internationally recognised standard treatment regimes:

1. AVT(R) All-Volatile Treatment (Reducing Conditions)

Uses ammonia (pH control) and hydrazine (oxygen scavenger)
Should be used in systems containing copper materials

2. AVT(O) All-Volatile Treatment (Oxidising Conditions)

Uses ammonia only, no hydrazine
Recommended for all-ferrous (copper-free) systems

3. OT Oxygenated Treatment
Uses ammonia and oxygen injection
Tends to be used with once-through boilers with very high purity
feedwater.

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Boiler Water Treatment

Possible treatment regimes:

1. All-Volatile Treatment (AVT) – Ammonia/Hydrazine or Ammonia alone

2. Phosphate Treatment (PT) – Various regimes based on use of several
sodium phosphate salts; only the use of Tri-Sodium Phosphate is
recommended.
3. Caustic Treatment (CT) – Sodium Hydroxide

Where boiler pressure (and discharges to water) allow, the use of Tri-Sodium
Phosphate is preferred instead of Caustic as the corrosion risks are usually
lower (e.g. from mechanical drum carryover).

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Flow-Accelerated Corrosion (FAC)
 Flow-Accelerated Corrosion (FAC) can result in damage and failures of carbon
steel materials in boiler feedwater systems and evaporators.
 Process Safety: Serious failures of high energy pipework.
 Availability: Recognition of FAC at around 70% of fossil organisations.

Elbow

Valve

Mihama, Japan, (2004) Iatan, USA, (2007)

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Factors
Design, operational and chemical conditions in water circuits where the
protective oxide is removed from a metal surface quicker than it can reform.

Plant risk influenced by:

 Temperature – occurs up to 300oC with peak rate
at 150oC;
Design
 Flow regime – turbulent flow;
 Pipework geometry – sharp bends, bifurcations;
 Water chemistry – pH, oxygen;
 Material composition – carbon steel susceptible; Can be used in
low Cr alloys improve resistance – carbon steel mitigation
susceptible; low Cr alloys improve resistance.

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LP Evaporator FAC Failures

Two tube failures in one HRSG

Only 20,000 hours operation

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Steam Drums

No FAC present

Severe FAC damage resulting in loss of

oxide and metal - only bare metal
remaining
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Feedwater Pipework

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Effect of Material

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FAC in Air Cooled Condensers

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FAC in Air Cooled Condensers

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Under-Deposit Corrosion

Deposition on the internal

surfaces of boiler tubes can result
in exposure to high heat fluxes
due to insufficient cooling from
steam or water flows.
 Steam is generated within the
deposit and flows outwards.
 It is replaced with boiler water
carrying non-volatile
contaminants.
 A highly concentrated liquid
phase can accumulate within
the deposit.
 Can lead to concentration of
aggressive species.

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On-Load Internal Corrosion – HP Evaporator
Failure

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Window Failure Due to Hydrogen Damage

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Steam Contamination – Stress Corrosion
Cracking
 Stress corrosion cracking (SCC)
requires three factors:
 mechanical stress
 poor water chemistry
 susceptible material

 Tube failures in superheaters.

 Serious SCC in steam turbine

(LP rotor disc and blading).

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Steam Turbine Corrosion

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Stress Corrosion Cracking – Steam Turbine

Crack close to rotor Crack at mid depth

surface position on rotor
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Steam Turbine Deposition and Loss of
Efficiency, e.g. silica

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What is required for cycle chemistry to be
effective

Plant Design
Enables the optimum cycle
chemistry to be applied

Site Competency Chemistry Regime

Operators, managers and & Targets
chemists adequately trained Correct selection

Monitoring and
Operational Control Local Operating
Instructions
Operating within approved targets.
Adequate sampling, monitoring and Including corrective actions
dosing equipment

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Conclusions

 Effective management of cycle chemistry is important.

 Chemistry interacts with plant design and materials throughout the water-
steam cycle.
 What happens in one plant area will affect components downstream.

 Chemistry control is key to:

Safe plant operation.
Protecting plant integrity.
Maintaining unit reliability and availability.
Reducing maintenance costs.

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Thank you!

For further information, please contact:

Uniper
Technology Centre
Ratcliffe-on-Soar
Nottingham, NG11 0EE

www.uniper.energy

paul.mccann@uniper.energy
+44 7525 241358

Uniper disclaimer:
This presentation may contain forward-looking statements based on current assumptions and forecasts made by Uniper
SE management and other information currently available to Uniper. Various known and unknown risks, uncertainties
and other factors could lead to material differences between the actual future results, financial situation, development or
performance of the company and the estimates given here. Uniper SE does not intend, and does not assume any liability
whatsoever, to update these forward-looking statements or to conform them to future events or developments.

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