Managing Chemistry to Mitigate Flow Accelerated Corrosion

Presented at the 2013 Fossil FAC International Conference

Washington, DC

March 26 – 29, 2013

Randy Turner

Technical Director

Swan Analytical Instruments

Introduction

FAC is a corrosion mechanism that increases operating and maintenance costs, impacts unit reliability,
and most importantly can be a safety concern. Cycle chemistry must be customized for each unit to
address its unique design and operating issues. This requires representative sampling, accurate and
reliable continuous monitoring, and meticulous control of the chemistry to minimize and hopefully
mitigate FAC. Many factors in today’s environment impact unit operations and chemistry control:

 Requirements for increased operational flexibility call for sampling systems that can cope with
start‐stop or load following operation with minimal operator intervention.
 Shortage of qualified chemical staff: with drastically reduced staffing levels in power plants,
many sites, especially smaller units, cannot afford a chemist on all shifts. As a result, reliable
online measurements and diagnostics systems become more important.
 Thermal power plants using renewable fuels are on the rise. They tend to be smaller
decentralized stations (e.g. biomass, waste to energy, thermo‐solar units with typical capacities
<100MW).

Many plants struggle with the implications on the water chemistry management. As a result, water
chemistry operations are neglected and continuous monitoring is no longer assured. In the long term,
accumulated damage to the equipment and loss of generation capacity will occur.

The key topics addressed in this paper are:

 The role of water steam chemistry monitoring in the context of Power Plant Life Cycle
Management
 Framework for the water chemistry monitoring and diagnostics in modern power plants:
o Sampling system design / automation level
o Monitoring / Recording of water‐steam chemistry data
o Operator awareness / trainings
o Maintenance and service of sampling systems
 State‐of‐the art online water chemistry monitoring:
o Making the most out of flexible plant operation
o The hidden potential of remote monitoring systems

Practical examples from different power plants show good practice and typical pitfalls. References are
made to the recommendations in the new VGB guidelines (VGB R450L / VGB‐S‐010‐2011, VGB‐S‐006‐
2012‐DE), EPRI Cycle Chemistry Guidelines, and IAPWS Chemistry Guidelines for water chemistry and for
online sampling and analysis in the water steam cycle.

This paper illustrates the value of proper sampling, monitoring, and data validation to identify chemistry
issues to optimize chemistry issues allowing the chemist to optimize the chemistry and chemistry
control.
FAC Overview

Flow‐accelerated Corrosion (FAC) involves magnetite dissolution, mass transport, and wall
thinning with local conditions becoming increasingly reducing. It is a continual process whereby
the root cause must to be addressed with a comprehensive corporate/plant program. The
nature and behavior of the oxide on the metal surface is a function of the chemistry of the fluid
contacting the surface. Knowledge of Fe3O4 and FeOOH solubility is fundamental to the
understanding and chemistry control of the FAC mechanism

Factors influencing FAC include:

• Water Chemistry

− Oxidizing/Reducing Potential, ORP (Oxygen + Reducing Agents)

− pH
− Temperature
• Hydrodynamics

− Flow
− Component Geometry & Upstream Influences
− Steam Quality
− Mass Transfer
• Pipe/Vessel Material Composition

− Chromium
− Copper
− Molybdenum

Figure 1 illustrates areas prone to experience single phase FAC in traditional fossil plants.
 1‐ Phase FAC Prone
Areas

Figure 1. Areas prone to experience single phase FAC in traditional fossil plants.

Figure 2 illustrates areas prone to experience two phase FAC in traditional fossil plants.
 Areas Prone to
2‐Phase FAC

Figure 2. Areas prone to experience two phase FAC in traditional fossil plants.

Typical locations for single and two phase FAC to occur are listed below:

• Feedwater heater drains & alternate/emergency drains (S,T)

• Piping around boiler feed pump (S)
− Includes de‐superheating supply piping
• Piping to economizer inlet headers (S)
− Especially associated/near valves & supply tees
• Economizer inlet header tubes (S)
• Most frequent are usually those nearest header supply
• High pressure (HP) feedwater heater tube sheets fabricated in carbon steel (S)
• Low pressure (LP) feedwater heater shells (T)
− Especially near cascading drain entries
(S = single phase T = two phase)
• Deaerator Shells (T) near to fluid entry (HP cascading drains) piping
• Reducers & expanders on either side of control valves (S,T)
• Locations near to thermo‐wells in piping
• Turbine exhaust diffuser (T)
• Air‐Cooled condenser (T)
(S = single phase T = two phase)
Typical Fossil Feedwater Chemistries

Two types of chemistries are employed; reducing and oxidizing. A reducing environment is
employed in systems that contain mixed metallurgy or copper containing alloys. A reducing
environment is required to minimize corrosion of the copper alloys. It typically employs
ammonia for pH control and a reducing agent which results with an oxidation reduction
potential (ORP) value of < 0 mV. An oxidizing environment is employed in all ferrous systems
which typically employs ammonia for pH control with no reducing agent and has an ORP value >
0 mV.

FAC is influenced by feedwater chemistry. The pH affects oxide film solubility of carbon steel. The
FAC rate increases at lower pH values. The pH depends on ammonia or amine concentration
and the pH decreases with increasing temperature. The typical pH range for mixed metallurgy
systems is 9.0 – 9.3. Since a reducing agent is employed the dissolved oxygen is kept low, ≤ 10
ppb in the condensate and ≤ 5 ppb at the economizer. The ORP is typically controlled in the
range of ‐150 ‐ ‐250 mV. The target value for iron corrosion product transport is 2‐ 5 ppb. The
typical pH range for all ferrous systems is 9.2 – 9.6. The dissolved oxygen is controlled at ≤ 20
ppb in the condensate and 5 – 10 ppb at the economizer. The ORP is maintained > 0 mV. Iron
corrosion product transport should be < 2 ppb.

It is critical to optimize feedwater chemistry to mitigate or at least minimize FAC. If operating

with AVT‐R you should optimize the pH to reduce FAC and optimize the reducing agent to
reduce FAC and copper corrosion. One should monitor corrosion product transport which
changing one parameter at a time to optimize chemistry. If operating with AVT‐O or OT it is
important to optimize pH to reduce FAC and to optimize dissolved oxygen to reduce FAC
Also, monitor corrosion product transport which changing one parameter at a time to optimize
chemistry.

Hydrogen Monitoring to Indicate Active Corrosion

Parameters such as pH, oxygen, iron, hydrogen etc. are directly related to corrosion control and
monitoring for corrosion. According to the Schikorr reaction (Eq. 1), hydrogen is released as a
by‐product during the formation of the magnetite and hematite layer in the power plant.

Hydrogen concentration can be measured in the steam or feedwater[4] to ensure that

corrosion rates are kept at an acceptable level. The hydrogen level is not well defined in most
of the guidelines and may vary from plant to plant. Available research indicates hydrogen levels
between a few ppb (part per billion) of dissolved hydrogen and several hundred ppb has been
recorded during normal operation and commissioning respectively.
Permanent damage to the boiler is possible if the measured hydrogen values are greater than
10 ppb‐50 ppb under normal operating condition. Figure 3 illustrates the Online Hydrogen
measurement in Superheated Steam for Once‐Through Boiler in 1100MW Lignite‐Fire Unit Power Plant.

Hydrogen Measurement in Once Through Boiler Superheated

Steam
[µg/kg] H2
3.50

3.00

2.50

2.00

1.50

1.00

0.50

0.00
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Time

Figure 3: Online Hydrogen measurement in Superheated Steam for Once‐Through Boiler in

1100MW Lignite‐Fire Unit Power Plant.

Figure 3 illustrates the online hydrogen measurement in feedwater (or Economizer inlet) in
660MW Coal‐Fired Unit Power Plant.
 Hydrogen Measurement in Feedwater
[ug/kg] H2
1.00
0.90
0.80
0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.00
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27/07/12 00:00:00
Time

Figure 4: Online Hydrogen measurement in Feedwater (or Economizer inlet) in 660MW Coal‐
Fired Unit Power Plant.

Chemistry Optimization

It is important to optimize feedwater chemistry to mitigate or minimize FAC. To effectively do

this proper online monitoring is essential. Proper online monitoring includes the following:

• Stronger focus on online monitoring (more than key parameters only).

• Sampling systems must cope with load changes without operator intervention.
• Reliable online measurements and self‐diagnostics systems are required.
• Need for remote water chemistry monitoring and diagnostics.
• Automatic control of chemistry parameters is critical.
• pH
• Reducing agent if employed
• Dissolved oxygen for AVT‐R, AVT‐O, and OT
• Use of systems such as PI allows the chemist to review trends, identify problems, and
optimize chemistry control.
• Application of expert systems aids the operator/chemist detect trends and identify
potential root causes of excursions, and poor control of chemistry.
• Analyzers that employ self‐diagnostics with analyzer status ensures data is accurate and
reliable.
 Figure 5 illustrates the declining spiral when proper monitoring is not available.

 Online analyser
do not perform

Failure,
unplanned  Monitoring by
periodic grab
sample only

 Damage
accumulation  Reduced
frequency,

 Undetected
upset conditions

Figure 5 Declining spiral due to improper online chemistry monitoring

Prerequisites for proper online monitoring are:

 WSC chemistry concept fitting plant type, operating regimes and staff
 Clearly defined key parameters and diagnostic parameters
 Reliable and representative sampling
− Sample location
− Sample transport
− Sample conditioning
 Self‐diagnostics capability of online analyzers
 − Sample flow ok?
− Reagents ok?
− Sample T ok?
− Sensor ok?

 Adequate communication to DCS /local chemistry flight‐deck indicating the following:

STATUS BAD  Measurement must not be used.

 Instrument in operation
with error message (e.g.
 Instrument requires immediate
maintenance
lack of reagents)
 Maintenance required.

STATUS UNCERTAIN  Measurement cannot be

 Some conditions (e.g. sample
flow) not in desired range or
unknown
 Measured values on hold due to
instrument maintenance
trusted. Risk of “false truths”
 Instrument will require
maintenance shortly

STATUS GOOD  Measurement can be trusted.

 measurement are fulfilled No risk of “false truths”
 all conditions required to  Any related process alarm is
ensure a valid measurement
are fulfilled really related to the process

Utilization of proper online monitoring and SCADA system allows the chemist to effectively monitor and
evaluate chemistry data to identify trends and problems and take corrective action. Figure 6 illustrates
poor control of phosphate chemistry resulting in a change of chemistry to AVT‐O resulting in improved
chemistry control as shown in Figure 7.
 Single pressure drum boiler • Erratic dosing of Na3PO4 in drum
AVT + Na PO in drum • Unclear if spikes are instrument
errors of process related
Feedwater SC
Drum water SC
Steam SC
Steam AC
Steam AC degassed Chemistry parameters out of
recommended normal bandwidths

Frequent blind spots

Figure 6 Illustrating poor phosphate residual control.

Single pressure drum boiler ‐ Conductivities in feedwater, drum water and steam after
improvement to monitoring and chemistry
• Change to AVT(O) regime
• Reduction of CO2 ingress
Feedwater SC • Monitoring of instrument status
Drum water SC
Steam SC
Steam AC
Steam AC degassed

Smooth sailing, stable normal conditions

Well monitored key parameters

Figure 7 Illustrates chemistry control after changing to AVT‐O.

Conclusion

In order to have an effective FAC mitigation plan it is important to implement the following:

• Implement a corporate/plant FAC monitoring and mitigation program.

• Select proper chemistry regimen to mitigate FAC
• Optimize chemistry to mitigate FAC
• Continuously monitor cycle chemistry
− Appropriate cycle monitoring concept
− Adequate sampling system design
− Self‐diagnostics at instrument level for measurement validation
− Availability of status information for validated process values (Digital bus communication)
• Automatically control chemical feed to mitigate FAC
• Consider application of new technologies such as hydrogen monitoring to monitor corrosion in
effort to mitigate corrosion.