’

S
Corrosion
and
Chemistry
Guidebook
Table of Contents
Load Cycling and Boiler Metals: How to Save Your Power Plant........................................ 4
As many coal-fired power plants designed for baseload service are asked to cycle, unforeseen
stresses have been introduced to boiler pressure parts. Understanding the effects and implement-
ing mitigation strategies could prevent premature component failure and keep facilities operating
reliably.

The Role of Fireside Corrosion on Boiler Tube Failures, Part I........................................... 5

The Role of Fireside Corrosion on Boiler Tube Failures, Part 2........................................ 24

Corrosion Protection for FGD Vessels................................................................................. 36

Defeating Concrete Reinforcing Steel Corrosion............................................................... 37

Four concrete cooling towers at a coal-fired electrical generation plant exhibited reinforcing steel
corrosion that was causing concrete deterioration. This case study follows the repairs to those tow-
ers—how the corrosion control solution was selected, how repairs were made, and how follow-up
tests found the repairs to be effective three years later.

Winning the Cooling Tower Trifecta: Controlling Corrosion, Scale, and Microbiological
Fouling.................................................................................................................................... 41
In cooling water chemistry for power plants, it is not enough to control one or two of the major
chemistry issues. Successful treatment requires simultaneous control of corrosion, scale, and mi-
crobiological fouling. These three are so strongly tied to each other that if one is allowed to go out
of control, the other two soon will be.

Protect Your Stack Linings from Corrosion......................................................................... 45

Prevent Contamination and Corrosion in Demineralized Water Storage Tanks Using

Nitrogen Sparging and Blanketing....................................................................................... 48

A Primer on Gas Turbine Failure Modes.............................................................................. 50

When a gas turbine goes down, recovery can be an expensive, time-consuming process. Knowing
what can go wrong and how to anticipate turbine failures can help you avoid a difficult unplanned
outage.

Covered Piping Systems O&M Programs for CCGT Plants............................................... 53

Cation conductivity monitoring: A reality check................................................................ 59

Preventing Dust Accumulation on Beams........................................................................... 65

Robotic Underwater Debris Remover.................................................................................. 65

Nut, Bolt, and Flange Face Corrosion Protection............................................................... 65

How to Measure Corrosion Processes Faster and More Accurately................................. 66
Maintaining reliable and efficient plant operations requires good control of corrosion and corro-
sion product transport in power plant water systems. The Electric Power Research Institute rec-
ommends oxidation-reduction potential for passivator control in feedwater systems, as do many
industry experts. Here’s how to turn that recommendation into a robust feedwater monitoring
program.

More Strategies for Inspecting HRSGs in Two- Shift and Low-Load Service................... 79

Microbial Control in Cooling Water Improves Plant Performance..................................... 88

Microbial inhibition, as part of a robust cooling water treatment program, presents a special chal-
lenge because of the variability in makeup water sources, plant processes, and discharge permits.
Failure to maintain a proper microbial inhibition program will affect your bottom line as a result of
heat rate degradation.

Selecting a Combined Cycle Water Chemistry Program.................................................... 93

The lifeblood of the combined cycle plant is its water chemistry program. This is particularly true
for plants designed for high pressures and temperatures as well as fast starts and cycling. Even
though such plants are increasingly common, no universal chemistry program can be used for all
of them.

Battling White Rust.............................................................................................................. 103

Cycle Chemistry Commissioning Deserves Its Own Strategy........................................ 107

ORP as a Predictor of WFGD Chemistry and Wastewater Treatment.............................. 114

Recent studies have shown that system oxidation-reduction potential (ORP) is not only an impor-
tant factor for predicting wet flue gas desulfurization (WFGD) absorber chemistry but also may be
a predictor of process equipment corrosion and wastewater treatment requirements.
 OPERATIONS & MAINTENANCE
Load Cycling and Boiler Metals:
How to Save Your Power Plant
As many coal-fired power plants designed for baseload service are asked to cycle,
unforeseen stresses have been introduced to boiler pressure parts. Under-
standing the effects and implementing mitigation strategies could prevent
premature component failure and keep facilities operating reliably.
Rama S. Koripelli, PhD
O
n August 3, 2015, the U.S. Environ-
mental Protection Agency finalized the
Clean Power Plan, which calls for cuts
in carbon pollution from existing power plants.
This rule, coupled with low natural gas prices,
could result in natural gas–fired facilities be-
ing used more frequently for baseload power
and coal-fired plants being cycled, more than
ever before, to meet grid requirements.
The majority of coal-fired units were de-
signed and constructed as baseload units, with-
out any anticipation of significant load changes.
But combustion turbines and heat recovery
steam generators offer higher thermal efficien-
cies (about 60%) than coal-fired boilers (the
best steam plants may operate at a maximum
efficiency of about 40%), which is also contrib-
uting to a change in dispatch tendencies.
Although coal-fired power plants are still
in high demand, alternative sources are very
attractive from an environmental point of
view. Increasing variable renewable energy
resources, such as solar and wind power,
are placing additional pressure on coal-fired
plants to load follow. However, load cycling
in coal-fired plants causes negative long-term
and short-term effects on equipment reliabil-
ity and availability.
Load Cycling and Its Effects
Load cycling may include low-load condi-
tions, hot startup, warm startup, and/or cold
startup. Just as the term suggests, a low-load
condition occurs when output is reduced and
the unit is operated at a minimum load with-
out being shut down. When a unit is cycled
on and off daily, it usually undergoes a hot
startup. Warm startups generally occur in
units that operate for four to five days contin-
uously and then shut down during weekends,
while a cold startup follows an extended
maintenance shutdown (usually the plant
will have implemented a layup procedure for
these lengthy upkeep periods).
Following are the most common undesirable
effects of these sorts of cycling operations.
Creep Fatigue. Utility boilers are con-
structed using different materials and thick-
38
nesses. These materials expand and contract
at different rates. In addition to creep dam-
age, high-temperature components, such as
superheaters and reheaters, experience ther-
mal and mechanical fatigue. The cumulative
effect is known as creep fatigue.
The resulting damage is much more se-
vere than standalone creep or fatigue dam-
age. Under cyclic loading, tube-to-header
welds develop cracking due to a combination
of fatigue stresses and hoop stresses. Fatigue
stresses can result from relative movement
between the components, specifically dur-
ing warm-up or cool-down, or when load
changes occur due to transient stresses. Fa-
tigue stresses can also be present as a result
of inadequate tube leg flexibility, defective
supports/attachments, or rigid attachments
on the pressure parts.
Ligament Cracking. Individual high-tem-
perature superheat (SH) and reheat (RH) tubes
may operate at different temperatures because
of variations in heat distribution, slagging, foul-
ing, and misalignment. Therefore, steam enters
into the header at different temperatures.
Load cycling exacerbates the temperature
difference between the individual tubes, be-
cause the firing rate is adjusted during load
changes to maintain pressure and temperature.
During load increase, the boiler is temporarily
overfired, and the condition reverses when load
is reduced. This causes transient thermal shocks
to the header, resulting in ligament cracking.
High-Temperature Circuit Thermal Fa-
tigue. In addition to these thermal stresses,
the external stresses associated with header
expansion and contraction can cause damage
to cycling units, resulting in fatigue cracks at
the attachments. An additional fatigue com-
ponent can exist wherever components are
joined via welding, because different parts
expand and contract at different rates. Al-
though the fatigue component is within the
endurance limit, it will affect the creep prop-
erties of the components.
Over-Tempering. Creep-strength-enhanced
ferritic steels (CSEFs), like T91 and T23, are
very popular in modern power plants because
www.powermag.com
they offer higher allowable stresses and supe-
rior creep properties than their ancestor grade
steels, such as T22 and T11. However, there
are some inherent long-term maintenance is-
sues with the CSEF steels. The use of CSEFs
in heavy-cycling units, specifically in reheat
circuits, significantly affects the superior prop-
erties obtained through precise heat treatment,
resulting in premature failures.
Dissimilar-Metal Welds. Dissimilar-
metal welds (DMWs) are very frequently
used in high-temperature circuits to facilitate
material transitions. Load swings produce
significant transient thermal and differential
stresses on the DMWs. These welds are not
only subjected to creep but also are suscepti-
ble to creep fatigue failure. Load cycling sig-
nificantly reduces the useful life of a DMW.
Condensate in Low Points. Conden-
sate usually collects in the remote sections
of SH and RH circuits, resulting in two ma-
jor issues: thermal fatigue and short-term
overheating. The temperature difference that
exists between the headers and steam can
produce thermal fatigue cracking and liga-
ment cracking. Warm startups produce sig-
nificant thermal fatigue damage because the
1. Condensate in loops. This image
shows several secondary superheater tubes
that failed due to short-term overheating after
only eight months of service. Courtesy: David
N. French Metallurgists
|
POWER November 2015

2. Corrosion fatigue. This cutaway
view shows a tube that experienced corrosion
fatigue in the transition bend near the lower
slope of a plant that cycled daily. Courtesy:
David N. French Metallurgists
temperature difference is usually higher.
Rapid startup conditions may lead to short-
term overheating failures, because conden-
sate in system low points can cause increased
metal temperatures downstream (Figure 1).
The tensile strength of the steel decreases
significantly once it is beyond design temper-
atures. Also, rapid startups and shutdowns, as
well as load changes, can cause exfoliation of
the inner diameter oxide scale. If the exfolia-
tion is excessive, it may lead to pluggage of
bends or erosion damage in the turbine.
Low-Temperature Circuit Thermal Fa-
tigue. In low-temperature regions of the boiler,
load cycling also causes thermal fatigue crack-
ing in economizer inlet headers or tubes, lower
furnace wall tubes or headers, and steam drum
internals. This fatigue cracking primarily oc-
curs from the ingress of relatively colder water
into hot boiler components or vice versa.
Corrosion Fatigue. Load cycling exacer-
bates corrosion fatigue on waterwall tubes be-
cause the differential stresses on waterwall tubes
are higher during startups and load swings.
Corrosion fatigue is not only a reliability issue,
but it also is a safety concern because failures
usually occur on the cold side of the boiler.
Conditions necessary for corrosion fatigue
to occur include either having the boiler wa-
ter oxygen concentration too high or the pH
outside of the control range at the same time
that stresses are high enough to break the
magnetite layer (Figure 2). Corrosion fatigue
occurs when operating or residual stresses
break the protective magnetite (Fe3O4) layer,
exposing the bare steel to the corrosive envi-
ronment (Figure 3). These stresses are high-
est during transient periods.
Caustic Gouging. Caustic gouging is a
well-known issue in natural circulation units,
specifically during low-load conditions. In
natural circulation units, the coolant flow is
biased to certain tubes because it operates on
the density difference between the hot and
cold fluids. Low-load conditions and load
|
November 2015 POWER
OPERATIONS & MAINTENANCE
3. Taking a closer look. This micro- 4. Caustic gouging. This cutaway view
scopic view shows a tube surface that has shows a tube that experienced caustic attack in
begun to crack as a result of corrosion fatigue. a cyclone inlet roof tube. The plant commenced
Courtesy: David N. French Metallurgists load cycling about one year prior to this failure.
Courtesy: David N. French Metallurgists
swings play a major role in caustic gouging
because constantly changing conditions re-
sult in repetitive upsets to coolant flow. The
flow upsets cause caustic to concentrate at
the edges of steam bubbles. Caustic concen-
trations remove the protective layer of iron
oxide, resulting in tube wastage (Figure 4). Hideout becomes evident during load swings
Phosphate Hideout. Phosphate hideout, or startups while changing heat input. Dirty
one of several forms of underdeposit corro- boilers are susceptible to phosphate hideout
sion, usually occurs when units are operating and acid phosphate corrosion.
with phosphate-based treatment. Phosphate
hideout causes ionic phosphate to disappear Mitigation Strategies
or absorb during high-heat-input conditions, There will always be some adverse effects
but it returns or dissolves into boiler water on equipment reliability due to a low-load
when the heat input is reduced. Phosphate condition, hot startup, warm startup, or cold
hideout promotes acid phosphate corrosion. startup. Each of these conditions will affect
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CIRCLE 17 ON READER SERVICE CARD
www.powermag.com 39
 OPERATIONS & MAINTENANCE
the integrity of pressure parts one way or an-
other. It has been observed across the board
that warm startups cause the most damage
to equipment, because the temperature dif-
ference is higher and there is greater suscep-
tibility to air in-leakage than what is found
during other cycling conditions.
Following are some useful strategies for
mitigating equipment damage.
Add More Tube Flexibility. Fatigue
stresses often occur as a result of inadequate
tube leg flexibility between tube penetrations
and the header, and also from rigid attach-
5. Bigger is better. Larger ligaments
ments on the tube. More flexibility and bet-
are less susceptible to creep fatigue damage.
ter attachment design will reduce the fatigue Source: David N. French Metallurgists
stresses. Sometimes header relocation may
be required to provide more flexibility.
Use Slip-Type Attachments. Many
older units were designed with rigid attach- Small Large
ments. Slip-type attachments should be used ligament ligament
in place of rigid attachments to accommodate
differential thermal expansion.
Redesign for Symmetrical and Widely
Spaced Tube Penetrations. Several older Upgrade lower
Present
ligament stress

6. Design changes. Elimination of the

I am
lack-of-fusion notch at the end of tube pen-
etrations and including a smooth chamfer at
the inner diameter of the header bore hole
can improve creep fatigue resistance. Source:

IN CONTROL David N. French Metallurgists

Large lack of
fusion notch
Chamfer Smaller lack of
fusion notch

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and reduce long term maintenance costs. symmetrical tube penetrations, which are sus-
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Reliable, durable and engineered for performance, when it that evenly spaced, larger ligaments are less
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Contact us today and we’ll show you how you can be in total control. Redesign of tube-hole penetrations and
tube-to-header weld configuration, especially
eliminating the lack-of-fusion notch at the end
of the tube penetration, can also increase creep
fatigue resistance. The inclusion of a smooth
chamfer at the inner diameter of the header
bore hole reduces stress concentration (Figure
6), improving creep fatigue resistance.
Make Periodic Inspections. The majority
of piping-related problems are associated with
hangers and support systems. Good attachment
design is vital to minimizing creep fatigue. Peri-
odically inspecting attachments and correcting
deficiencies will reduce fatigue-related issues.
Terminations of attachments should taper to the
surface to reduce localized stress concentra-
tions. Lack of penetration in attachment welds
can result in hot spots where heat is unable to
effectively dissipate or can increase stress con-
centrations. Good weld design and adherence
Continuously Improving to welding procedures is essential.
Lower Ramp Rates. Transient stresses
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due to load cycling affect the useful life of
a DMW. Transient stresses can be reduced
with slower startups.
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metal, which will have a finite life. DMWs
made with EPRI P87 or Inconel filler metal
are expected to have a longer life than those
CIRCLE 18 ON READER SERVICE CARD

40 www.powermag.com |
POWER November 2015
 OPERATIONS & MAINTENANCE
without filler metals. A DMW made using
nickel-based filler metal lessens the effects

gotmussels?
of the thermal expansion differences between
stainless steel and ferritic steel.
Relocate DMWs. Stresses and temperatures
are the critical factors in the lifespan of a DMW;
performance can be improved by controlling
these factors. The weld joint can be relocated to
a position where it is exposed to lower tempera-
tures. Frequent inspection and maintenance of
tube hangers, supports, and spacers can be per-
formed to reduce secondary loads.
Bake Tubes. Condensate in high-temper-
ature circuits creates major problems during
startup periods. The tubes should be baked
for long enough to evaporate the condensate
before increasing the heat input. Reduce the
thermal gradient between the fluid and metal
during startup periods. Although load cycling
plays a major role in thermal fatigue, once
the component reaches equilibrium, thermal
fatigue will not be a significant factor.
Use Rifled Tubing. The use of rifled tub-
ing in areas susceptible to underdeposit corro-
sion can provide better flow mixing to avoid
potential corrosion issues. Load cycling sig-
nificantly increases the susceptibility of water-
wall tubes to corrosion fatigue. Fast startups
increase transient stresses because different
parts expand and contract at different rates,
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Marrone Bio Innovations, Inc. U.S. Patent No. 6,194,194; Canada Patent No. 2,225,436.
for David N. French Metallurgists
CIRCLE 19 ON READER SERVICE CARD

|
November 2015 POWER www.powermag.com 41
The Role of Fireside Corrosion on Boiler Tube
Failures, Part I
04/01/2010 | By Dr. Rama S. Koripelli, Dr. David C. Crowe, Dr. David N. French, and Jonathan
Brand

One of the primary challenges of reliably burning coal is managing the corrosion experienced by the
furnace heat transfer surfaces. Fireside corrosion remains a leading cause of failure in superheater
and reheater tubes. Also, tubes affected by the fireside corrosion mechanism may lose 15 mils per
year (mpy) and more in extreme cases. Five case studies (three presented here in Part 1) examine
the different failure modes experienced by tubes located throughout the furnace.

Furnace Corrosion Fundamentals

Fireside corrosion in the superheaters and reheaters of coal-fired units is known as coal ash
corrosion, in oil-fired units as oil ash corrosion, and in refuse-fired boilers as ash corrosion.
Sometimes, fireside corrosion is also referred to as hot corrosion. The mechanism in each case is
similar, but the low-melting species in each is different. In coal ash corrosion, the low-melting
species would be sodium or potassium iron trisulphates (Na3Fe(SO4)3 or K3Fe(SO4)3); in oil ash
corrosion they would be V2O5-Na2O or V2O5-Na2SO4; and in refuse-fired boilers they would be
chlorides of iron and zinc along with other possibilities [see references 1 and 2 in the sidebar]. High
temperatures (above 1,000F) of the superheater/reheater favor the formation of these low-melting
compounds.

The corrosion rate in coal ash corrosion, between 1,100F and 1,250F, is very high. In this
temperature range, Na2SO4/K2SO4 reacts with surface oxides in the presence of SO3 to form complex
liquid sulfates (Na3Fe(SO4)3 or K3Fe(SO4)3) that result in rapid corrosion [3, 4]. Above 1,250F the
corrosion rate is decreased significantly due to decomposition of these complex liquid trisulfates.
Once the liquid phase has been removed, the corrosion is due to oxidation in contact with flue gas.

The corrosion constituents in oil ash corrosion are vanadium, sodium, potassium, and sulfur. The
combustion of fuel oil may produce low-melting species V2O5-Na2O, V2O5-K2O, V2O5-Na2SO4, and
V2O5-K2SO4. The melting points of these compounds range between 1,000F and 1,550F, depending
on composition [4, 5, 6]. The oil ash corrosion mechanism is similar to coal ash corrosion: a low-
melting-point liquid forms and it dissolves the protective iron oxides.

In refuse-fired boilers, chloride and sulfate species lead to the formation of low-melting- point liquids
on the tube surface that may contain iron, zinc, lead, and sodium. These species dissolve the
protective iron oxide and expose the bare steel to the corrosive environment, resulting in significant
wall loss [7]. Reducing conditions inside the furnace may lead to the formation of iron sulfide instead
of iron oxide. The presence of carbon and iron sulfide within the ash deposits indicates the presence
of reducing conditions. Hydrogen chloride can more easily attack iron sulfides, rather than oxides, to
form iron chloride as a corrosion product. This iron chloride has a relatively low boiling point, and
therefore iron chloride vapors form in the superheater/reheater temperature range, and the corrosion
mechanism is by loss of iron as a vapor. The porous sulfide formed in reducing conditions allows
easier formation and removal of iron chloride vapor.
Furnace wall tubes are also subject to fireside corrosion, but the low-melting species differ from
superheater/reheaters. Sodium and potassium pyrosulfate (Na2S2O7 or K2S2O7) have been
responsible for furnace wall corrosion [1]. Both of these species melt below 800F, where the furnace
wall tubes operate. The melting points of Na2S2O7 and K2S2O7 are 750F and 570F, respectively [4, 8,
9]. Mixtures of these two compounds could melt at even lower temperature. Melting points as low as
635F to 770F have been measured.

Case Study 1: Coal Ash Corrosion of a Superheater

One finishing superheater tube sample, from a coal-fired unit, was received for metallurgical
analysis. The tube was specified as 1.875-inch outer diameter (OD) x 0.330-inch medium wall tubing
(MWT), SA-213 T22 Cr-Mo steel. It had been in service for 23 years. Figure 1 illustrates the as-
received tube sample and the inner diameter (ID) view. Significant wall thinning was observed on the
flanks of the tube, characteristic of coal ash corrosion. Very hard scale was observed on the tube
OD. On the steam side, there was a thick oxide.

1. As-received tube and view of ID. Courtesy: David N. French Metallurgists

The tube sample was cross-sectioned, mounted, polished, and etched for metallographic
examination. A 3% nital etchant (100 ml ethanol and 3 ml HNO3) was used to reveal the existing
microstructure. Metallographic examinations were conducted via optical microscopy. Figure 2 shows
thick scales at the tube OD and ID. A thick ID scale can raise the tube wall operating temperature
significantly. Figure 3 is a view of coal ash corrosion that had occurred on the OD.

2. Cross-section of the tube wall facing the gas flow at 4.5x magnification. (Note that numbers on the
images do not necessarily correspond to the numbering in this article.) Courtesy: David N. French
Metallurgists

3. View of coal ash corrosion at 100x magnification. Courtesy: David N. French Metallurgists
As shown in Figure 4, the microstructure of the T22 tube had transformed to ferrite with spheroidized
carbides. Metallographic examination was also performed at the 8:00 orientation of the tube to look
for creep damage, if any. The microstructure was the same, irrespective of the specimen location,
and there was no evidence of creep.

4. Ferrite with spheroidized carbides, mid-wall at 400x magnification. Courtesy: David N. French
Metallurgists

Tube wastage will often be evident and manifested as flat spots on either sides of the upstream of
flue gas flow, as can be seen in Figure 5a. A ring sample, Figure 5b, was sectioned from the tube for
dimensional and hardness measurements (Table 1). The tube had thinned significantly at the 4:00
and 8:00 positions due to coal ash corrosion. The thinnest section of the ring (0.291 inch at the 8:00
position) was at 88% of MWT. The hardness, averaging 73 Rockwell B (RB), showed that the tube
had softened after 23 years of service.
5a.
5b.

5. (a) Schematic representation of fireside corrosion. (b) Sectioned ring from the tube with corroded
areas noted. The dark spots are the locations of hardness measurements. Courtesy: David N.
French Metallurgists

Table 1. Case 1 dimensional and hardness measurements. Source: David N. French

Metallurgists
Alkali oxides react with SO3 in the furnace atmosphere to form alkali sulfates (K2SO4 or Na2SO4) on
the oxide scale. Some of the SO3 diffuses through the alkali sulfates, and reaction occurs at the
oxide-sulfate interface to form alkali-iron-trisulfates (K3Fe(SO4)3 or Na3Fe(SO4)3) according to the
following two chemical reactions:

In this process, the thickness of the oxide scale decreases and the metal oxidizes further to renew
the oxide layer. The tube metal temperature decreases as slag thickens. At room temperature, low-
melting compounds sinter the ash particles to form a tightly bound inner layer. After the slag
thickness reaches equilibrium, deslagging increases because the liquid layer on the tube cannot
support a thick layer of ash. This deslagging increases the tube-metal temperature. This process
(slagging and deslagging) repeats in a cycle that leads to create the corrosion pattern known as
"elephant hiding" or "alligator hiding."

Coal ash corrosion of the tube analyzed in Case 1 resulted in significant wall loss. The temperature
range for formation of trisulfates is between 1,000F and 1,250F. The decomposition of trisulfates
occurs when the temperature exceeds 1,250F. Above this temperature, coal ash corrosion reduces
significantly. Numerous empirical equations have been proposed for estimating the tube operating
temperature based on the oxide scale thickness in superheaters and reheaters. Using one of these
equation with the measured ID scale thickness (25 mils) and hours of operation (171,300 hours)
results in an estimated tube temperature of 1,100F [11]. This estimated tube temperature was within
the susceptible temperature range for trisulfate formation and coal ash corrosion. The metallography
confirmed that the tube had operated in this temperature range. The tube microstructure had
transformed to ferrite with completely dispersed carbides, and the hardness had decreased.

Log X = 0.00022 (T+460) (20+Log(t)) -7.25

Where:

X = steam-side scale thickness in mils

T = absolute temperature (F+460), and

t = time in hours

Case 2: Oil Ash Corrosion of a Reheater Tube

A high-temperature vertical reheater tube was received for failure analysis. The tube was specified
as 2.25-inch OD x 0.180-inch MWT, SA-213 TP-304H stainless steel. It had been in service for 15
years. The fuel type was No. 6 Bunker C oil. Figure 6 is the as-received tube with specimen
locations illustrated, including a close-up view at the failure site and the ID view. Significant wall
thinning was observed at the failure.
6. As-received tube with specimen locations illustrated, close-up of failure, and the ID view.
Courtesy: David N. French Metallurgists

Figure 7 is a specimen at Location F1 with fracture face on the left. The tube is darker in the outer
one-third of its cross-section due to carburization. Intergranular corrosion (Figure 8) occurred along
the grain boundaries due to chromium depletion. The depletion of chromium content due to carbide
formation along the austenite grain boundaries and within the surface grains reduces the corrosion
resistance of stainless steel. Within and below the carburized layer, the intergranular cracking is
typical of creep. Higher stresses due to significant wall loss at the failure contributed to intergranular
creep cracks. The tube wall was thinned down to approximately 0.075 inch at the edge of the failure.
There was no evidence of plastic deformation at the fracture face, which is typical for creep failure.

7. Location F1, oxalic at 4.5x magnification. Courtesy: David N. French Metallurgists

8. Location F1, fracture face at 42x magnification. Courtesy: David N. French Metallurgists

Location F2 also had intergranular cracks with some of the grains missing at the tube OD due to
pull-out during polishing (Figure 9). In Figure 10, the microstructure shows sensitized austenitic
grains with large carbides along the grain boundaries. Sensitization occurs from 800F to 1,500F,
with the most rapid sensitization at 1,200F.

9. Location F2, intergranular cracks along the grain boundaries at the OD at 200x magnification.
Courtesy: David N. French Metallurgists
10. Location F2, sensitized grains, mid-wall at 400x magnification. Courtesy: David N. French
Metallurgists

Similar carbides were observed in the mid-wall away from the failure at Location B (Figure 11).
Although sensitization decreases the corrosion resistance, it does not affect the mechanical
properties significantly.

11. Location B, sensitized grains, mid-wall, 12:00 at 400x magnification. Courtesy: David N. French
Metallurgists

Ring samples (Figure 12) were sectioned from the tube for dimensional and hardness
measurements. The tube had thinned significantly: Ring A is 72% of MWT at the 2:00 position, and
Ring B is 48% of MWT at the 12:00 position. The hardness, averaging 83 Rockwell B (RB), is slightly
above the range for new SA-213 TP304H, 72-81 RB, as expected for material that has been
carburized.

12. Sectioned rings. Courtesy: David N. French Metallurgists

Elemental analysis was performed on white deposit that was scraped from the OD surface. Analysis
was via energy dispersive spectroscopy in the scanning electron microscope (see ASTM E1508-98)
[10]. The carbon and sulfur content was determined by combustion analysis (ASTM E1019-03) [11].
The results are summarized in Table 2. The deposit was primarily iron oxide. Chromium, nickel, and
manganese were likely from the steel. High amounts of carbon and sulfur indicate the possibility of
reducing conditions. Unburnt carbon due to reducing conditions resulted in carburization of stainless
steel tube. Potassium, sodium, and vanadium in the deposit point to the presence of low-melting
species (such as V2O5-Na2O, V2O5-K2O, V2O5-Na2SO4, and V2O5-K2SO4) which may have contributed
for significant wall loss. Calcium and phosphorus, from water or water treatment chemicals, were
formed after the tube failure. Minor amounts of arsenic, magnesium, titanium, and chlorine were also
detected. The white color may be associated with aluminum and silicon in the deposit.

Table 2. Constituents of the whitish reheater tube OD deposit. Source: David N. French
Metallurgists
The reheater tube failed due to oil ash corrosion, resulting in thinning and creep. Reducing
conditions caused carburization of stainless steel. The microstructure had transformed to carbides
along the austenitic grains. Carburization and sensitization contributed to a reduction in corrosion
resistance that resulted in significant wall loss. The OD deposits also point to the presence of low-
melting compounds that caused oil ash corrosion.

Case 3: Oil Ash Corrosion of a Superheater

A secondary superheater tube was received for metallurgical characterization. The tube was
specified as 2.125-inch OD x 0.420-inch MWT, SA-213 T22 Cr-Mo steel. It had been in service for
43 years. Figure 13 illustrates the as-received tube with specimen locations, and the tube ID view.
The oxide scale is seen at the ID. Some roughening and pitting corrosion were observed on the OD.

13. As-received tube with specimen locations illustrated and the ID view. Courtesy: David N. French
Metallurgists
Figure 14 is the close-up view of pitting corrosion that had occurred on the OD. A specimen was
circumferentially cross-sectioned to determine the depth of pits. Figure 15 is the close-up view of
alligator hiding due to oil ash corrosion. A longitudinally cross-sectioned specimen was examined to
determine the significance of oil ash corrosion at Location B.

14. Close-up view of pitting corrosion at Location A at 3:00. Courtesy: David N. French Metallurgists

The pits observed in Figure 14 were shallow, and there was some intergranular attack along the
grain boundaries, as shown in Figure 16. The alligator hiding (circumferential ridges) shown in
Figure 15 was measured, and the deepest oil ash corrosion was 15 mils from the OD (Figure 17).
The cycling of metal temperature causes ash layers to form and shed, leading to the alligator hiding.
These circumferential grooves from the tube OD are typical for fireside corrosion. No creep damage
was seen at the OD or at the tip of the groove. This area of the tube was exposed to the highest
temperature, making it more likely to have oil ash corrosion.
15. Close-up view of alligator hiding at Location B at 1:00. Courtesy: David N. French Metallurgists

16. Location A, 3:00, superficial pit, OD at 100x magnification. Courtesy: David N. French
Metallurgists

17. Location B, 1:00, 15 mils depth of ash corrosion, OD at 100x magnification. Courtesy: David N.
French Metallurgists

The microstructure had transformed to ferrite with spheroidized carbides due to years of service
(Figure 18). Similar microstructure was observed irrespective of the specimen location.
18. Ferrite with spheroidized carbides, Location B, 12:00, mid-wall at 400x magnification. Courtesy:
David N. French Metallurgists

The thickest scale was measured as 20 mils (Figure 19). Based on the oxide thickness and years of
service, the tube temperature was estimated as 1,064F. This temperature is below the
recommended maximum for T22 material, 1,075F, but 43 years ago the maximum temperature may
have been 1,125F. The operating temperature was within the susceptible temperature range for
formation of low-melting-point constituents in oil ash corrosion, 1,000F to 1,500F. The low-melting
compounds in oil ash corrosion are V2O5-Na2O, V2O5-K2O, V2O5-Na2SO4, and V2O5-K2SO4. Unlike coal
ash corrosion, these compounds do not thermally decompose at higher temperature.

19. Location B, 6:00, ID with 20 mils of scale at 100x magnification. Courtesy: David N. French
Metallurgists
Superficial pitting and some alligator hiding were observed on the OD of the superheater tube due to
oil ash corrosion. V2O5-Na2O, V2O5-K2O, V2O5-Na2SO4, V2O5-K2SO4, or reducing conditions inside the
furnace may have contributed to alligator hiding in this superheater tube. The tube microstructure
had transformed to ferrite with spheroidized carbides after 43 years of service.

More to Come

In Part II we’ll explore several more case studies, including ash corrosion of a superheater and
fireside corrosion of a water wall tube.

References

1. David N. French, Metallurgical Failures in Fossil Fired Boilers, 2nd ed., John Wiley & Sons Inc.

2. R.C. Corey, H.A. Grabowski, and B.J. Gross, "External Corrosion of Furnace-Wall Tubes
III," Transactions of the ASME, vol. 71 (November 1949), pp. 951-963.

3. R.B. Dooley and W.P. McNaughton, Boiler Tube Failures: Theory and Practice, EPRI, vol. 3, ch. 33,
"Steam Touched Tubes" (1996).

4. W.T. Reid, External Corrosion and Deposits: Boilers and Gas Turbines (New York: American Elsevier
Publishing Co., 1971).

5. J.O. Collins and W.A. Herbst, "How Ash of Residual Fuel Oil Affects High Temperature Boiler
Operation," POWER, vol. 98 (November 1954), pp. 100-101.

6. H.W. Nilson, A Review of Available Information on Corrosion and Deposits in Coal and Oil-Fired Boilers
and Gas Turbines, Battelle Memorial Institute, 1958.

7. A.J.B. Cutler, W.D. Halstead, J.W. Laxton, and C.G. Stevens, "The Role of Chloride in the Corrosion
Caused by Flue Gases and their Deposits," Transactions of the ASME (July 1971), pp. 307-312.

8. R.W. Bryers, "Prospects of Fireside Ash Deposition While Firing Coal/Oil Mixture," Joint Power
Generation Conference, St. Louis, Missouri (October 1981).

9. P.D. Miller, C.J. Slunder, H.H. Krause, and F.W. Fink, State-of-the-Art Report on Control of Corrosion
and Deposits in Stationary Boilers Burning Residual Fuel Oil, Battelle Memorial Institute for Bureau of
Yards and Docks, Navy Department (May 1963), Accession Number: AD0422073.

10. ASTM Standard E1508 – 98, "Standard Guide for Quantitative Analysis by Energy-Dispersive
Spectroscopy," ASTM.

11. ASTM Standard E1019 – 03, "Standard Test Methods for Determination of Carbon, Sulfur, Nitrogen,
and Oxygen in Steel and in Iron, Nickel, and Cobalt Alloys," ASTM.

-Dr. Rama S. Koripelli (rkoripelli@davidnfrench.com) is metallurgical engineer, Dr. David C. Crowe

(dcrowe@davidnfrench.com) is technical director, Dr. David N. French is founder, and Jonathan Brand
(jbrand@davidnfrench.com) is a senior metallurgical technician for David N. French Metallurgists.
The Role of Fireside Corrosion on Boiler Tube
Failures, Part 2
04/01/2010 | By Dr. Rama S. Koripelli, Dr. David C. Crowe, Dr. David N. French, and Jonathan
Brand

One of the primary challenges of reliably burning coal is managing the corrosion experienced by the
furnace heat transfer surfaces. Fireside corrosion remains a leading cause of failure in superheater
and reheater tubes. Tubes affected by fireside corrosion also may lose 15 mils per year (mpy), or
more in extreme cases. In Part I of this two-part report, three case studies examined the different
failure modes experienced by tubes located throughout the furnace. We conclude with two additional
case studies.

Case 4: Ash Corrosion of a Superheater

An intermediate superheater tube was received for failure analysis. The tube had been removed
from the outlet and below the middle sootblower. The tube was specified as 2.125-inch outside
diameter (OD) x 0.290 inch MWT SA-213 T11 Cr-Mo steel. It had been in service for one year.
Agricultural waste was burned.

Figure 1 shows the as-received tube with specimen locations illustrated, including a close-up of the
failure site and the tube inside diameter (ID) view. The failure was thick-edged and fish-mouthed,
characteristics of creep failure. A shield had been installed recently on the tube to protect it from
erosion/fireside corrosion. The failure had occurred slightly below the shield. Significant wall thinning
was observed on the side facing into the gas flow. The tube suffered from significant fireside
corrosion on the side where the failure had occurred.

1. As-received tube with specimen locations illustrated, including close-up of the failure site and the
inside diameter (ID) view. Courtesy: David N. French Metallurgists

Very thick scale was observed on the OD, as shown in Figure 2. The severity of the fireside
corrosion was revealed by the orange peel texture on the tube. A significant amount of chlorine was
detected in the OD deposit. The chloride anions may have been formed during cathodic reaction of
chlorine. The presence of chloride led to the formation of the low-melting species on the tube surface
that contained iron, aluminum, and sodium chlorides. These chloride species would be expected to
have a low melting point and would dissolve the protective iron oxide, leaving the bare steel to be
corroded by hydrogen chloride.

2. Tube outside diameter (OD) with thick scale. Courtesy: David N. French Metallurgists

Elemental analysis was performed on deposit scraped from the OD surface. Analysis was via energy
dispersive spectroscopy in the scanning electron microscope (ASTM E1508-98 [2003]). The carbon
and sulfur content was determined by combustion analysis (ASTM E1019-03). The results are
summarized in Table 1.

Table 1. Outside diameter deposit. Source: David N. French Metallurgists

The OD deposit was primarily iron oxide. A high percentage of chlorine indicates the formation of the
low-melting liquids that may have contained iron chlorides. The low-melting iron chloride would
dissolve the protective iron oxide and expose the bare steel to the corrosive environment.
Magnesium and aluminum were present from the ash deposits. Chromium was likely from the steel.
The presence of carbon within the ash deposits indicates that the reducing conditions were present
at least at the surface of the tube where corrosion occurred. With reducing conditions, iron-sulfide
scales form rather than iron oxide. These iron-sulfide scales are less corrosion-resistant than oxides.

Figure 3 illustrates the failure at location F2, with the arrow indicating the fracture face. The wall
thickness at the fracture lip was measured as 84 mils. This wall thinning rate was 206 mils per year.
There was no significant plastic deformation at the edge of the failure. The tube failed due to
significant wall thinning, resulting in creep. Creep cusps were found where the wall was thinnest.
Creep had occurred from the tube OD to ID. Creep cusps formed on the tube OD because of the
high-temperature exposure on the OD (Figure 4). Numerous creep voids were observed adjacent to
the creep cusp and along the fracture face.

3. Location F2, 84 mils thick at 7x magnification. Courtesy: David N. French Metallurgists

4. Location F2, creep voids, OD, 200x magnification. Courtesy: David N. French Metallurgists
The microstructure in Figure 5 was ferrite with slightly spheroidized carbides, as expected for T11.
Still, the original pearlite colonies were clearly defined. Thus, there was no evidence of localized
overheating at the failure site. Similar microstructure was observed irrespective of the specimen
location. Intergranular attack was observed on the OD due to the lack of protective oxide scale
resulting from the fireside corrosion, as shown in Figure 6.

5. Location B, mid-wall, 12:00, 400x magnification. Courtesy: David N. French Metallurgists

6. Location B, intergranular attack, OD, 12:00, 200x magnification. Courtesy: David N. French
Metallurgists

Ring samples (Figure 7) were sectioned from the tube for dimensional and hardness measurements
(Table 2). Circles on the rings indicate thin spots. Significant wall thinning was observed, caused by
fireside corrosion. The thinnest section of Ring A (0.120 inch at the 1:00 position) was at 41% of
minimum wall thickness (MWT), Ring B (0.179 inch at the 11:00 position) was at 62% of MWT, and
Ring C (0.145 inch at the 10:00 position) was at 50% of MWT. If the tube had thinned below 65% of
MWT, the first choice should be tube replacement. Careful inspection via ultrasonic thickness
measurement was recommended, with replacement of tubes less than 0.190-inch thickness. The
hardness, averaging 78 Rockwell B (RB) was within the range for new tubing specification SA-213
T11, 76 to 85 RB, indicating that no overheating or metallurgical transformation had occurred.

7. Sectioned rings. Courtesy: David N. French Metallurgists

Table 2. Case 4 dimensional and hardness measurements. Source: David N. French Metallurgists

The tube failed due to significant wall thinning caused by fireside corrosion, resulting in creep.
Reducing conditions led to the formation of porous iron sulfides rather than iron oxides. Hydrogen
chloride had easily attacked iron sulfides to form iron chloride as a corrosion product. These iron
chlorides had a relatively low boiling point, and therefore iron chloride vapors formed, and the
corrosion mechanism was by loss of iron as a vapor. The porous sulfides formed due to reducing
conditions allowed easier formation and removal of iron chloride vapor. Significant wall thinning was
observed. The microstructure was ferrite with slightly spheroidized carbides, as expected for T11.

Case 5: Fireside Corrosion of a Waterwall Tube

A rear wall tube was received for condition assessment. The tube was specified as 2.97-inch OD x
0.240-inch MWT, SA-210 A1 carbon steel. It had been in service for only nine months. Figure 8
illustrates the ID view, which shows a uniform oxide covering. The tube appears to be very clean
inside. Figure 9 shows the tiny pits observed on the fireside OD surface. The surface deposits had
been removed with diluted hydrochloric acid containing a corrosion inhibitor to reveal the underlying
steel. These pits were observed between the 12:00 and 2:00 orientations of the tube.

8. Tube ID view. Courtesy: David N. French Metallurgists

9. Pits on the fireside OD surface. The green line marked the crown of the hot side of the tube.
Magnification is 2.5x. Courtesy: David N. French Metallurgists

Some intergranular attack was seen at the OD (Figure 10). This attack was a cross-section of a
longitudinal line of attack on the surface of the tube. Another linear indication, at the 11:00
orientation, was cross-sectioned and found to be 4 mils deep. Typical microstructure was observed
with ferrite and pearlite in Figure 11, without any thermal degradation. Similar microstructure was
observed on the other side of the tube.
10. The fireside showed intergranular attack: OD, 200x magnification. Courtesy: David N. French
Metallurgists

11. Ferrite and pearlite microstructure, fireside, mid-wall, 400x magnification. Courtesy: David N.
French Metallurgists
A ring sample (Figure 12) was sectioned from the tube for dimensional and hardness measurements
(Table 3). The tube had not bulged. Taking the difference between the thickest and thinnest
sections, the wall thinning was measured as 11 mils. This wall thinning is significant for waterwall
tube about nine months old and is a wastage rate of about 15 mils/year. None of the measured wall
thickness values was below MWT of 0.240 inch. The wall thinning resulted from the fireside
corrosion on the OD. The hardness, averaging 73 RB is within the range for new SA-210 A1, 72 to
78 RB, indicating that no overheating or metallurgical transformation had occurred.

12. Sectioned ring. Courtesy: David N. French Metallurgists

Table 3. Case 5 dimensional and hardness measurements. Source: David N. French Metallurgists

Elemental analysis was performed on deposit scraped from the OD surface. Table 4 shows that the
deposit was primarily iron oxide. The presence of carbon within the ash deposits indicates that
reducing conditions were present. The lead content was very high, and its melting point is 620F. This
may be a significant factor in the tube wastage. The presence of chlorine content indicates the
formation of the low-melting liquids that contained lead, zinc, and iron chlorides. Elemental results
also suggest that K2S2O7 may have been involved in the fireside corrosion. K2S2O7 and Na2S2O7 are
the primary susceptible compounds for fireside corrosion on waterwall tubes. The melting points of
K2S2O7 and Na2S2O7 are 750F and 570F, respectively. Mixtures of these two compounds could melt
at even lower temperature.

Table 4. Case 5: OD deposit. Source: David N. French Metallurgists

Scanning electron microscope (SEM) images were taken at high magnification on the OD of the
cleaned tube sample. In Figures 13 and 13, SEM images revealed a linear indication on the cleaned
tube sample, indicating some fireside corrosion. Inhibited acid was used for cleaning. This is a view
from the surface of a longitudinal line of intergranular corrosion like that shown in cross-section in
Figure 10. The corrosion may have followed a line of nonmetallic inclusions in the steel or a die
mark.

13. Scanning electron microscope (SEM) image (30x magnification) of the tube OD. The linear
indication is shown by the arrow. Courtesy: David N. French Metallurgists
14. SEM image of the tube OD with a close-up of the linear indication at 645x
magnification. Courtesy: David N. French Metallurgists

Hemispherical-shaped surface pits were observed on the cleaned sample. At high magnification
(Figure 15), some intergranular attack could be seen inside these hemispherical pits. This attack at
the grain boundaries is due to lack of protective scale there. The scale was apparently removed in
service, perhaps by a molten or semi-molten phase.

15. SEM image of the tube OD with a close-up of the linear indication at 1,810x magnification.
Shown is intergranular attack inside a pit. Courtesy: David N. French Metallurgists

The tube suffered wall thinning resulting from fireside corrosion at a rate of 15 mils/year. This is a
high rate of corrosion, though none of the measured wall thickness values was below the MWT of
0.240 inch. Reducing conditions in the furnace may have contributed to the OD corrosion. The
formation of low-melting species on the tube OD may also have led to rapid corrosion. Chloride and
sulfide species had dissolved the protective iron oxide, exposing bare steel to the corrosive
environment, resulting in significant wall loss. Potassium pyrosulfate may have formed in the OD
deposit and contributed to wall loss. The presence of lead and zinc may have further reduced the
melting points of OD deposit. Typical carbon steel microstructure, with ferrite and pearlite, was
observed without any degradation.

Controlling Fireside Corrosion

Irrespective of the boiler type, fireside corrosion affected the superheater/reheater tubes, resulting in
significant wall loss. As demonstrated, waterwall tubes are also susceptible to fireside corrosion.
Different methods have been proposed for controlling fireside corrosion, including reducing sulfur
content, installing shields, adding additives, and applying corrosion-resistant weld
overlays. Following are a few observations about potential options for minimizing fireside corrosion:

 Coal ash corrosion rates drop drastically above 1,250F due to decomposition of complex alkali
trisulfates. Shields decrease heat transfer from the flue gas to the steam, resulting in increase
of the tube outside temperature above the range of stability of complex trisulfates. To cause oil
ash corrosion, impurities in the fuel oil (Na, V, and Pb) along with sulfur must be present. Oil
ash corrosion can be minimized by reducing impurities in the fuel and by desulfurization of fuel
oil. Unfortunately, desulfurization of fuel oil is not an economical solution. Shields are also an
ineffective method of controlling oil ash corrosion, because low-melting species do not
thermally decompose, unlike in coal ash corrosion.
 Additives, such as calcium and magnesium, may be helpful to increase the melting point of
compounds that are formed on the tubes. The increased melting temperature would be higher
than superheater/reheater operating temperatures.
 Maintaining oxidizing conditions inside the furnace potentially eliminates the formation of
porous iron sulfide scales instead of protective iron oxides.
 Inaccurate burner angles may result in localized reducing conditions. Therefore, burners
should be adjusted per design to have the correct stoichiometric mixture.
 Installation of low-NOx burners in coal-fired boilers has resulted in accelerated waterwall
wastage. These low-NOx burners are expected to produce more H2S, instead of SO2 or SO3, in
the combustion gas that promotes increase in the corrosion rates.
 Weld overlays of more corrosion-resistant alloys like Alloys 625 and 622 have been proven to
be a long-term solution for fireside corrosion. The superior corrosion resistance of these
superalloys in both oxidizing and reducing environments containing mixtures of acids has been
attributed to the formation of Cr-rich oxides (Cr2O3).

—Dr. Rama S. Koripelli is metallurgical engineer, Dr. David C. Crowe is technical director, Dr. David
N. French is founder, and Jonathan Brand is a senior metallurgical technician for David N. French
Metallurgists.
Corrosion Protection for FGD Vessels
Roughly five years ago, the power industry readily embraced the 7. Typical flue gas desulfurization vessel that will be
new Alloy 2205 metal as a more lightweight and cost-effective lined to protect the substrate. Courtesy: International Paint
substrate for the construction of flue gas desulfurization (FGD)
absorbers and vessels than traditional heavy-duty stainless steel
and carbon steel substrates, including the more common Alloys
304 and 316. Assuming that the surfaces of the Alloy 2205 FGD
absorbers and vessels were properly prepared and lined, early test
reports indicated that the substrate would hold up well, except
perhaps under conditions such as crevice corrosion or corrosion
under film buildup (Figure 7).

New Substrate Gives Way to Old Corrosion

Challenges
Prior to lining, Alloy 2205 requires a clean surface with a sharp
profile and blast profile (depth). For most high-build linings or
coatings, a 3-mil profile is needed. However, for most alloys, ad-
jacent unlined surfaces also need to be protected during abra-
sive blasting to ensure that the surfaces are not contaminated
by iron.
Because most slag abrasives contain iron, garnet or aluminum
oxide abrasives are preferred choices, provided that they are able
to produce the required sharp profile. As with carbon steel, the 8. An installer spraying Ceilcote lining onto tank
surface must be tested for salt contamination, and cleaned if walls. Courtesy: International Paint
necessary, to the lining manufacturer’s requirements. One differ-
ent feature with alloys is that the surface must be coated or
primed soon after blasting, unless dehumidification control holds
the relative humidity to less than 40%, as the surface will not
show the typical discoloration, as carbon steel does, due to sur-
face oxidation.
Despite acceptable surface preparation and application of lin-
ings, many Alloy 2205 vessels located at more than 40 power
plants across the U.S. are now showing evidence of severe pitting
and corrosion under scale buildup, including “worm holing,” after
just one year in service. Apparently, much of the pre-testing of
Alloy 2205 did not take into consideration the effects of a high
concentration of chlorides/fluorides under the scale buildup, or
that it creates the same corrosive effects of crevice corrosion.

Not All Solutions Are Created Equal

Increased demand for corrosion-related repairs to Alloy 2205 ves-
sels has given rise to some new corrosion solutions with varying
degrees of efficacy.
9. An installer rolling fiberglass reinforcement into
One repair alternative used by plant owners is to clad the in-
wet basecoat. Courtesy: International Paint
terior of the FGD vessel with an alloy metal that is known to
perform well in these service conditions and costs less than other
alloys, such as Alloy C276. Nevertheless, common drawbacks to
this option include material availability. Alloy metal can often be
in short supply, which forces owners to wait for extended periods
until the material becomes available.
The biggest drawback to this repair solution, however, is cost.
Between the high price of the material and the skilled welders
needed for installation, some estimates put the cost of cladding
up to $75 per square foot. Furthermore, localized leaks can still
seep under the cladding and attack the alloy underneath virtu-
ally unnoticed. Worse, this repair process is fairly time-intensive,
resulting in significant downtime, which some plants estimate at
up to $1 million per day in lost revenues.
Over the past 10 years, vinyl ester linings have been the most
common method of corrosion repair for both carbon steel vessels
and many types of alloys. These linings can be very effective
and are increasingly being utilized in Alloy 2205 corrosion re-

26 www.powermag.com |
POWER February 2014
 COOLING TOWERS
Defeating Concrete Reinforcing
Steel Corrosion
Four concrete cooling towers at a coal-fired electrical generation plant exhib-
ited reinforcing steel corrosion that was causing concrete deterioration.
This case study follows the repairs to those towers—how the corrosion
control solution was selected, how repairs were made, and how follow-up
tests found the repairs to be effective three years later.
By Bruce A. Collins, Restruction Corp.
A
s early as the 1960s, corrosion of re-
inforcing steel in structural concrete
was recognized as a threat to concrete
structure durability. Steel embedded in newly
cast concrete is protected by the high pH of
the concrete. However, the passive film on
the surface of the reinforcing steel is broken
down over time by the infiltration of ionic
materials, typically salts. Carbonation of the
concrete, caused by diffusion of atmospheric
carbon dioxide, can also break down the rein-
forcing steel passivation, allowing the initia-
tion of corrosion.
Many variables affect the time it takes for
corrosion to begin, including the concrete
cover depth, temperature, concrete moisture
content, pH level of the concrete, the pres-
ence of oxygen, and others. When corrosion
begins, one region of reinforcing will become
anodic and other regions will act as a cath-
ode. The ensuing chemical reactions cause
oxidation of the metal at the anode.
The oxidation product occupies a larger
volume than passivated steel. As the bar oxi-
dizes, an expansive tensile force is applied to
the cover concrete, creating cracks and ulti-
mately a concrete spall (flaking or crumbling).
At this point, typically, the facility’s owner be-
comes concerned about long-term durability,
and repair project planning is launched.
Repair Project Planning
During June 2000, the engineering team of a
1,660-MW coal-fired electrical generation sta-
tion located in the southwest U.S. began plan-
ning a concrete repair project. The team had
been observing concrete spalling and corro-
sion of reinforcing steel on specific reinforced
concrete assemblies integral to the plant’s four
concrete mechanical draft cooling towers. Two
towers served Unit 1 and two served Unit 2.
The cooling towers are constructed primar-
ily of precast concrete elements, with some
conventionally reinforced elements. In the
plan, the cooling tower is a 12-sided shape
with an approximate 212-foot diameter.
48
1. Four of a kind. The configuration of one of four cooling towers repaired as part of the
project. Courtesy: Restruction Corp.
Each tower has 12 motorized fans designed
to draft air from the lower level up through 2. Much spalling found. The upper
and lower fan stack assembly and the areas
the tower. The moving air is heat exchanged
requiring repair on one of the four towers is
with hot process water, ejecting steam out the shown. Courtesy: Restruction Corp.
top of concrete fan stack assemblies (Figure
1). The fan stack assemblies are constructed
of a lower conventionally reinforced concrete
ring measuring 41 feet 2 inches in diameter by
4 feet tall. The upper assembly is constructed
of precast concrete panels bolted to the lower
assembly. Corrosion of the reinforcing steel
in the lower assembly was causing concrete
spalling. The plant engineering team wanted
to understand the source of deterioration and
institute a repair plan for the problem.
Investigation Program and Results
Investigation of the corrosion source consist- Visual assessment of the lower assemblies
ed of the following tasks: determined several items of concern, includ-
ing the high-temperature environment, mini-
■ Visual assessment of all 48 lower fan stack mum concrete cover of ¾ inch, and water
assemblies and field measurement of con- seeping down the outer face of the assembly at
crete cover. the joint between the upper precast and lower
■ Review of original structural drawings and cast-in-place concrete. Constant contact with
details for the lower fan stack assembly. steam was causing elevated concrete tem-
■ Chloride content analysis at depths of 1, peratures and high moisture content. Each of
4, and 7 inches through the depth of the these variables was contributing to the rebar
lower assembly concrete at six separate corrosion (Figure 2).
locations. A total of 18 chloride samples Review of the original structural drawings
were tested. detailed the location, size, and placement of
■ Delamination mapping of the assemblies. cement grout in the joint between the upper
■ Petrographic analysis of two cores removed precast and lower cast-in-place concrete.
from different fan stack assemblies. Reinforcing details for the lower assemblies
www.powermag.com |
POWER July 2011

3. Coating tower interior. Coatings were applied in the lower assembly interior after
repairs were completed. Courtesy: Restruction Corp.
showed designed cover for reinforcing was 1
inch. Number 4 bars were spaced at 12 inch-
es as stirrups over #4 hoop bars around the
lower assembly circumference.
Chloride content samples were chosen to
determine levels of water-soluble chlorides at
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July 2011 POWER
the level of reinforcing and to determine if a
chloride gradient existed in the concrete. The
measurements were also used to determine if
chlorides were cast into the mix. Average chlo-
ride content at 1 inch was 0.0581% by weight.
Maximum chloride content in any sample was
www.powermag.com
COOLING TOWERS
0.144% by weight. ACI 318 (the American
Concrete Institute’s Building Code Require-
ments for Structural Concrete) allows for a
0.15% chloride content in reinforced concrete
exposed to chlorides in service for new con-
struction. Generally, in the U.S., 0.30% chlo-
ride content is considered the threshold limit
for initiation of corrosion. All chloride mea-
surements fell below this limit.
Delamination mapping of the lower as-
sembly concrete determined that, on average,
15% of the 600 square feet for each assembly
was delaminated.
Petrographic analysis of the cores revealed
poor air entrainment and locally abundant
micro-cracks throughout the core body. The
concrete was generally of good quality. Car-
bonation depth was measured at 0.13 inches.
Based on this information, conclusions
were drawn regarding the source of corro-
sion. The effect of high concrete tempera-
tures, high moisture content, and the wetting
and drying action at the outside face of the
assembly concrete were cause of the corro-
sion found on the cooling towers.
Repair Program
It became apparent that reducing the mois-
ture content level within the concrete was
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49
 COOLING TOWERS
the primary defense against future corrosion.
Cutting off the moisture ingress would in-
crease the concrete resistance, lowering the
reinforcing steel corrosion rate. Reducing
the concrete temperature was not a realistic
expectation.
A coating system designed to lower con-
crete permeability was selected. The coating
system selected started with a 100% solids
moisture-tolerant epoxy primer applied at the
rate of 100 square feet per gallon. The body
of the coating was a 100% solids polyamide
based, flake-filled epoxy (Figure 3).
Access, surface preparation using 20,000-
psi water lances, and coating installation
would be accomplished during a 30-day
plant shutdown.
Access was built using prefabricated
wood joist and planks bearing on steel angle
assemblies attached to existing structure.
Partial removal of the grout joint between the
upper and lower assembly to facilitate water-
proofing was also completed during the shut-
down and would minimize water penetrating
through the outer concrete face. The grout
was removed to a depth of approximately 2
inches. Open cell backer rod was saturated
with urethane multi-grout, activated, and in-
Corrosion rate (micrometers/yr)
normal rate. To counter this effect, the repair
program included installation of passive ca-
thodic anodes inside the concrete repair ar-
eas. The density of the reinforcing steel was
evaluated and anodes were specified for in-
stallation at approximately 4 feet on center at
the partial depth repair perimeters. Standard
concrete repairs, per ICRI Guideline 310.1-
2008, formerly No. 03730 (the International
Concrete Repair Institute’s Guide for Sur-
face Preparation for the Repair of Deterio-
rated Concrete Resulting from Reinforcing
Steel Corrosion), were completed. Dry mix
shotcrete was measured for resistivity com-
patibility with the anodes and utilized as the
repair material. Dry-mix shotcrete was cho-
sen for ease of application and low shrinkage
characteristics.
A larger than normal amount of shrinkage
cracking was anticipated, and occurred, due
to the difficult curing conditions and elevated
substrate temperature. A 40% solids silane
sealer was applied to the outside face of the
5. Pre- and post-repair data. Data labeled “2B” are pre-repair values. Data labeled “1A”
and “1B” are immediate post-repair values. No data signifies that readings weren’t taken at that
location. Source: Restruction Corp.
300
assembly upon curing to assist in maintain-
ing low concrete moisture content from the
high-humidity environment outside the as-
sembly. Spall repair totals were 5,900 square
feet, and those repairs were completed in two
phases (Figure 4).
Reducing the concrete moisture levels,
installing passive anodes, and completing
concrete repairs to the outside face of the as-
semblies provided a complete rebar repassi-
vation project.
Corrosion Measurements
As the first repair construction phase of the
project was nearing completion in 2005, the
plant engineering team raised the question of
how to measure the repair program’s success.
Quickly, a plan was implemented to measure
corrosion. Luckily, the second phase, Unit 2
project was still in the active corrosion mode.
Unit 1, consisting of 24 assemblies in the first
phase, was repaired and the reinforcing steel
repassivated.

stalled in the joint. A polysulfide caulking

was installed over the top to provide a fin- 250
ished appearance.
200
The coating system was installed in two
topcoats to minimize pin-holing. A moisture 150
vapor test was completed prior to installation 100
to minimize the chance of debonding. The
project was completed in two phases and en- 50
tailed applying 14,400 square feet of coating 0
inside 24 separate assemblies in each phase. 2B04 2B08 1A09 1A02 1A06 1A04 1A07 1B05 1B09
The repair program included other rebar Sample location
repassivation techniques that would be con-
structed during plant operation. With the 2B04 2B08 1A09 1A02 1A06 1A04 1A07 1B05 1B09
0
vapor drive cut off, we believed the concrete
Corrosion potential (mV)

would “dry out” rather quickly. Our attention –50

was now focused on the outside face of the –100
assemblies.
The high concrete temperature would –150
continue to drive corrosion at a faster than –200
–250
4. Repairs completed. The spall repairs
are completed at the base of the cooling tow- –300
er. Courtesy: Restruction Corp. Sample location

300
Concrete resistance (kOhms)

250
200

150

100
50

0
2B04 2B08 1A09 1A02 1A06 1A04 1A07 1B05 1B09
Sample location

50 www.powermag.com |
POWER July 2011
 COOLING TOWERS
indicate with 90% confidence that no corro-
6. Follow-up test data. Corrosion data collected three years after repairs were made on sion activity is present.
each set of cooling towers found that the corrosion rates were significantly reduced from the
as-found condition. Source: Restruction Corp.
Three Years Later
2005 2008 The plant engineering team budgeted additional
300 funds for repair of Unit 2 assemblies to be com-
Corrosion rate (micrometers/yr)

pleted in spring/summer 2008. Three years had

250
passed since completion of Unit 1 repairs. Again,
200 corrosion measurements were taken upon com-
150 pletion. The same two locations on Unit 2 were
measured, providing a direct comparison of
100 pre-repair (year 2005) and post-repair readings.
50 Five of the original seven assemblies at Unit 1
were remeasured. This provided a comparison
0 of immediate post-repair and repair-plus-three-
2B04 2B08 1A02 1A07 1A09 1B05 1B09 1A05 1A04 2A04 2A08
Sample location years’-time readings. Two new locations at both
Unit 1 and Unit 2 were also recorded. Results
2005 2008
still indicated that the reinforcing steel was pas-
2B04 2B08 1A02 1A07 1A09 1B05 1B09 1A05 1A04 2A04 2A08 sive, as shown in Figure 6.
0
Concrete resistance increased in both Unit
Corrosion potential (mV)

–50 2 post-repair measurements and Unit 1 mea-

–100 surements recorded in 2008 versus 2005. Av-
erage concrete resistance increased over the
–150
three-year operation period. Unit 1 resistance
–200 increased from 49 kilo-ohms immediate
post-repair to 115 kilo-ohms measured three
–250
years later.
–300 A U.S. standard has not been developed
Sample location for corrosion current. However, a proposed
2005 2008 Norwegian standard indicates values of
350 11.5 to 58.0 micro-meters per year would
Concrete resistance (kOhms)

300 be considered low corrosion. Less than 11.5

250
200
150
100
50
0
2B04
The corrosion measurement plan was to
measure corrosion current, corrosion poten-
tial, and concrete resistance at two fan stack
locations on Unit 2. These locations would be
considered pre-repair and serve as the base-
line. Corrosion rates and potentials were not
taken during the investigation phase. It was
apparent that corrosion was occurring and
the source of initiation was the high concrete
temperatures and moisture levels. Further-
more, no future monitoring of the corrosion
was planned during the investigation phase.
Measuring corrosion rate, potential, and
concrete resistance at seven locations on Unit
1 would serve as the immediate post-repair
condition and provide a comparison to pre-
repair condition measured at Unit 2.
A Galvapulse corrosion rate meter was
used to record approximately 12 readings
per assembly. The results are illustrated in
Figure 5. An immediate concrete resistance
2B08 1A02 1A07 1A09 1B05 1B09 1A05 1A04 2A04 2A08
Sample location
effect was measured. All seven Unit 1 as-
semblies measured post-repair had higher
concrete resistance than the two Unit 2 pre-
repair assemblies. On average, resistance
increased 135%.
Corrosion rate measured in micro-meters
per year also showed immediate improve-
ment. Six of seven post-repaired corrosion
rates were below both pre-repaired rates. On
average, corrosion rate was reduced 80%.
Corrosion potential showed immediate
improvement as well. Adjusted for the sil-
ver/silver chloride half-cell, copper sulfate
electrode readings in the pre-repair were
–315mV CSE and –360 mV CSE (CSE or a
copper sulfate electrode is used as the base-
line). The average post-repair potential was
measured at –270 mV CSE. ASTM Standard
indicates that for potentials between –200
mV and –350 mV CSE, corrosion is “uncer-
tain.” Readings more positive than –200 mV
micro-meters per year indicates negligible
corrosion. The Norwegian standard converts
corrosion rate units of micro-amps per centi-
meters squared to cross-section loss of rein-
forcing steel using Faraday’s Law.
A low corrosion rate (11.5 to 58.0 micro-
meters per year) was found in Unit 1 imme-
diate post-repair measurement in 2005, and
the 2008 measurement showed low to neg-
ligible corrosion activity. The rebar in Unit
1 remains passive due to the implemented
repair scheme. Unit 2 assemblies that were
measured prior to repair in 2005 and then
again post-repair in 2008 recorded improved
corrosion currents in the low to moderate
corrosion activity levels.
The corrosion current levels have dropped
significantly. Corrosion potentials are also
expected to continue improving as the rebar
becomes more passive. These results dem-
onstrate that the repairs started in 2000 and
completed in 2008 were successful and the
towers’ concrete will remain serviceable for
many years to come. ■
—Bruce A. Collins (bruce@restruction
.com) is vice president of Restruction
Corp. Portions of this article are repro-
duced with the permission of the Jour-
nal of Protective Coatings & Linings,
published by the Society for Protective
Coatings (www.sspc.org).

52 www.powermag.com |
POWER July 2011
 WATER TREATMENT
Winning the Cooling Tower
Trifecta: Controlling Corrosion,
Scale, and Microbiological Fouling
In cooling water chemistry for power plants, it is not enough to control one or
two of the major chemistry issues. Successful treatment requires simul-
taneous control of corrosion, scale, and microbiological fouling. These
three are so strongly tied to each other that if one is allowed to go out of
control, the other two soon will be.
David Daniels

T
here is a synergistic relationship among
the three major cooling water treatment
issues: corrosion, scale or deposit for-
mation, and microbiological fouling. In order
to control one, you need to control all three
(Figure 1). And, to make things harder, some-
times the treatment strategies used to fight
one side of this triangle can actually wind up
enhancing another side.
Take, for example, the common use of
bleach as an oxidizing biocide. At the proper
cooling water pH, bleach can be an excellent
biocide. Its cost and availability certainly
make it the most commonly used. However,
bleach is inherently corrosive. It is a nondis-
criminating oxidizer. It will oxidize carbon
steel as quickly as it will oxidize biofilms.
Then, the roughened up surfaces of the cor-
roded carbon steel have many more nooks
and crannies and crevices available for mi-
crobiological colonies to be established in
places where they can hide from the bleach.
Bleach may also oxidize treatment chemicals
used to minimize scaling or corrosion.
Then there’s the relationship between
scaling and biocide effectiveness. Scaling
deposits in condenser tubes and in the cool-
ing tower provide excellent surfaces for bio-
films to attach and microbiological colonies
to develop. The biofilms consist primarily of
exo-polysaccharides, which are “sticky” and
will collect deposits and debris to use as a
food source and to create a shelter to protect
themselves from the elements and, in particu-
lar, biocides such as bleach. Some research
has even shown that the biofilm structure it-
self creates surface conditions that promote
incipient crystal formation and accelerate
growth.
Of course, the fact that microbiological
species accelerate corrosion is well docu-
mented. It even has its own name— microbio-
logically influenced corrosion (MIC)—and it
is ubiquitous. Biofilms cause can cause gen-
eral oxygen pitting by establishing a concen-
tration gradient between the fully oxygenated
cooling water and low-oxygen or even fully
anaerobic conditions under the biofilm. The
anaerobic conditions found at the base of the
well-established biofilm promote the growth
of anaerobic bacteria such as sulfate reducing
bacteria. These bacteria convert sulfate in the
cooling water to sulfide and produce an acid-
ic hydrogen sulfide molecule that is very cor-
rosive to a variety of steel alloys, including
stainless steel and even copper alloys, which
are generally more immune to attack from
the aerobic bacteria. Other bacteria that grow
in biofilms metabolize metals directly for en-
ergy or use metallic corrosion products.
Now that we see how these three factors
work together to cause trouble in cooling
systems, let’s attack each individually and
review aspects of a good cooling water pro-
gram that achieves control of all three.
How to Control Biofilms in a
Cooling System
Besides the specter of MIC chewing on the
1. Scaling, biofouling, or corro-
sion? Answer: Yes. Courtesy: M&M Engi-
neering Associates Inc.
metallic parts of your cooling system (Fig-
ure 2), accumulations of biofilms also inhibit
heat transfer in the condenser tubes and can
accumulate on cooling tower fill to the point
where it can collapse the fill support and
cause significant damage to a cooling tower.
The key to maintaining control over micro-
biological populations in power plant cooling
water is to provide a consistent level of treat-
ment throughout the year (see sidebar). That
is, the treatment needs to be consistently ef-
fective. The actual concentrations of biocide
required to provide this level of treatment
may change significantly, depending on cool-
ing water conditions and the environment.
Some power plants find that they can shock
treat the cooling water system for an hour a
day during most of the year and cut back to
once or twice a week during the winter while
still properly controlling biofouling in their
system. Other power plants not only require
daily or even continuous feed of bleach but
also need to add additional nonoxidizing bio-
cides during the summer months.
The most common (though still imperfect)
method for determining that you are adding
sufficient oxidizing biocide to control micro-
2. When being green is bad. Control
of microbiological fouling is critical. Courtesy:
M&M Engineering Associates Inc.

42 www.powermag.com |
POWER September 2015

Cleaning or Maintaining?
I’m indebted to one expert in this field
for a statement I’ve used many times in
discussing cooling water treatment with
clients. George Licina of Structural Integ-
rity taught me: “It’s just like your mother
told you—it’s easier to keep your room
clean than to get your room clean.” The
same goes for your cooling water system:
Consistent application of the right amount
of biocide or biocides for the conditions in
your cooling water will keep your “room
clean” and help control scaling and corro-
sion (Figure 3).
biological fouling is still the free chlorine test
(DPD test). This is a minimum and should
be performed during each chlorination
cycle, or daily for those that continuously
chlorinate. As conditions change (seasons
and temperatures) the amount of bleach re-
quired to produce the desired free available
chlorine residual will change, and the plant
should respond by increasing or decreasing
the biocide feed rate accordingly. Note that
oxidation reduction potential (ORP) is not a
good indication of microbiological control in
cooling water. ORP is no substitute for test-
ing free available chlorine.
Getting the Full Benefit from Chlo-
rine. A full discussion of the various types
of biocides (both oxidizing and non-oxi-
dizing) and optimizing strategies for their
use is beyond the scope of this article. But
it would be good to say a few words about
the most common biocide used in power
plants: chlorine.
Previously, the most common source of
chlorine was chlorine gas shipped to power
plants as a condensed liquid in 1-ton cylin-
ders. It was evaporated and swept into the
cooling water lines as a gas. When chlorine
gas dissolved in water, it formed hydrochlo-
ric acid and hypochlorous acid. The hydro-
chloric acid lowered the cooling water pH
slightly, which enhanced the effect of hy-
pochlorous acid as a biocide. Obvious con-
cerns about safety were the primary reason
that power plants moved away from the use
of 1-ton chlorine cylinders to liquid (sodium
hypochlorite) commercial bleach delivery.
Commercial bleach is typically supplied at
12.5% or 10% chlorine. One pound of chlo-
rine gas makes 0.74 pounds of hypochlorous
acid, whereas 1 gallon of 12.5% bleach has
the potential to generate 0.875 pounds of hy-
pochlorous acid, if there is sufficient hydro-
gen ion (low enough pH) in the cooling water
to form the acid.
|
September 2015 POWER
3. Clean bill of health. A clean cool-
ing tower is a good sign that corrosion,
scale, and microbiological fouling are under
control. Courtesy: M&M Engineering Asso-
ciates Inc.
Commercial bleach is generated by bub-
bling chlorine gas into a caustic solution.
Some extra caustic purposefully remains in
the bleach to attempt to slow the decomposi-
tion of hypochlorite to chlorates. The typical
pH of commercial bleach is between 11.5
and 13.5. Bleach solutions that have a pH of
11 or less decompose very rapidly.
Therefore, in strong contrast to the use of
chlorine gas, the use of bleach has the poten-
tial to increase the pH of the cooling water.
It is been mentioned numerous times that
hypochlorous acid (HOCl) is much more ef-
fective as a biocide than the hypochlorite ion
(OCl-); therefore, bleach in particular loses
its activity as a biocide in high-pH cooling
waters.
Sodium hypochlorite solutions start de-
composing the minute they are manufactured.
They decompose primarily along two chemi-
cal pathways: by the formation of chlorate
(ClO3-) and by the release of oxygen (ClO-
4. Bleach degradation rate versus time. Source: Bernard Bubnis, “Understanding
Bleach Degradation,” NovaCem Laboratories Inc., Oxford, Ohio
■ 68F ■ 90F
14
13
12
11
10
Wt%NaOCI
9
8
7
6
5
4
www.powermag.com
WATER TREATMENT
to Cl- + O2). In a good quality hypochlorite
solution, the formation of chlorate is the pri-
mary decomposition pathway. A variety of
factors can accelerate the decomposition of
bleach. The most critical are time, tempera-
ture, exposure to ultraviolet (UV) radiation,
and concentration:
■ Time. All bleach decomposes over time
(Figure 4). One source calculated that at
a 90F storage temperature, a 10% bleach
solution loses half its effective hypochlo-
rite concentration in 95 days. Although
you may use up a tank of bleach in a few
weeks, you may want to ask your supplier
how long your bleach has been in storage
prior to its arrival at your facility.
■ Temperature. In 60 days at 68F storage
temperature, bleach will have lost about
17% of its hypochlorite, whereas at 90F
it will have lost about 55%. The ambient
temperature should be a consideration in
the placement of a hypochlorite storage
tank.
■ UV radiation. The UV rays in sunlight are
very effective at decomposing bleach so-
lutions. All bleach tanks should be made
of UV-impervious materials or coated in
such a way to exclude UV light. Better
yet, put them inside.
■ Concentration. The more concentrated the
bleach solution, the faster it decomposes.
If your site is not large user bleach, it may
be best to stick with the 10% bleach solu-
tion instead of the higher concentration.
Other factors that can have an effect on the
degradation rate include the concentration of
salts (chlorides) and transition metals (Ni,
Cu, Co) that may get into the bleach from the
caustic used in its manufacture or in tank and
43
 WATER TREATMENT
piping materials where the bleach is stored. The level of nickel in the vendors. This eliminates the need to properly mix the bleach and so-
bleach should be less than 0.1 mg/l and copper should be less than 1 dium bromide on site. However, it is more expensive to buy the stabi-
mg/l. lized hypobromous acid than to generate it.
Testing Bulk Chemicals Is Essential. It behooves the chemistry
personnel at the plant to check the concentration of hypochlorite in Scale Prevention for Power Plant Cooling Water
each shipment of bleach before it is offloaded into their tank. One By far the most common cooling water scale is calcium carbonate,
plant questioned why it was suddenly not achieving a free available though other scales can often be just as detrimental and far more dif-
chlorine residual in its cooling water, as it had in the past. A check of ficult to remove. These include calcium sulfate, calcium phosphate,
the bleach bulk tank found that the concentration in the tank was only and various forms of silica deposits.
2.5% bleach. Evidently, the previous bleach delivery was not the 10% The Calcium and Conductivity Connection. The inverse solu-
bleach the supplier claimed it was. Simple hypochlorite test kits are bility of calcium compounds such as these cause scaling in condenser
available for this purpose. tubes, which can severely affect heat transfer across the condenser,
Bromine Is Not a Biocide. Sometimes I hear people referring increase the unit back pressure, and restrict the unit’s generation. In
to their cooling water chemistry as “bromine” chemistry. Bro- recirculating systems (cooling towers) the cooling tower blowdown is
mine is a reddish-brown gas and highly toxic (like its neighbor often controlled by the conductivity of the cooling water. It is impor-
in the periodic table—chlorine gas). Is not something that should tant to remember that conductivity is only a proxy for the real con-
ever be generated at a power plant. The use of sodium bromide trol parameter–calcium. Conductivity can be easily and continuously
to enhance the biocidal properties of bleach at higher cooling monitored and therefore has a much better chance at controlling the
water pH values, however, is very common. We discussed the cooling water calcium than any other parameter.
proper application and blending of these two chemicals to pro- However, there are cases where this proxy breaks down. If your
duce the maximum amount of hypobromous acid in “Biofouling cooling tower makeup water comes from multiple sources, or if the
Control Options for Cooling Systems” in the September 2007 chemistry of these sources has changed over time, then the assump-
issue (available in the Water Treatment Guidebook, available in tions for the cooling water chemistry control parameters (including
the Store at powermag.com.) the conductivity control limits and chemical feed rates) will also have
Is important to remember, however, that sodium bromide is not a changed.
biocide; it is a simple salt, with no biocidal properties. It is only when Besides conductivity and pH, there should always be a specified
it is properly reacted with hypochlorous acid (not bleach—which is limit on total hardness and calcium hardness in your cooling water
predominantly hypochlorite ion) that it will form hypobromous acid, program. The lab should test the cooling water regularly for these

TCS-CPRIA
Stabilized hypobromousAd
which is the desired biocide.
acid isPOW
available a2015-3.375x4.75.qxp_1/4 Page (ZLD) 4/14/15
plant occasionally12:38
fed water PM
parameters, and these limits should always override the conductivity
number of chemical limit. One zero-liquid discharge
from the ZLD clarifier/softener effluent back to the cooling tower
when it could not be used in the downstream portion of the ZLD.
This water was high in conductivity but very low in calcium, which

Maximize
dramatically skewed the conductivity control of the cooling tower and
the amount of anti-scalant being added.

Condenser Eiciency!
Ensuring Consistent pH. The pH of cooling water is the other
critical factor for preventing scaling. If pH control with sulfuric acid
is part of your cooling water chemistry program, it should be under-
stood that it is a critical part.
A sulfuric acid pump malfunction or problem with the pH control-
ler for the pump can cause serious scaling or corrosion issues in the

Absolutely!
cooling tower. Both the acid pump systems and pH control elements
on the cooling water should be redundant. There should either be two
separate cooling water pH probes at different locations, or the pH of
Conco tube cleaning services boost the performance of condensers by the cooling water should be checked frequently by the lab or opera-
removing the most diicult deposits and obstructions in the briefest down- tions and compared to the pH of the online analyzer. Both the lab and
time possible. Conco services also provide power generation plants with:
�Non-Destructive Testing
operations should be aware of the potential damage that can be caused

�Tracer Gas Leak Detection

when they are not operating properly and know what actions to take
�High Conidence Tube Plugging
if problems arise.
Anti-Scalant Best Practices. Anti-scalant chemicals are a tre-
Conco crews are available 24/7/365 for mendous benefit to maintain and clean a condenser. It goes without
Absolutely the Best! services with response
time that is second to none. Put over 90 saying that these chemical pumps are also critical.
years of Conco experience to work for you. Anti-scalants can be grouped into two broad categories: phos-
Check out our videos at: phonates and polymers. There are polymers that have anti-scal-
www.concosystems.com/media/videos ing properties and other polymers that act as a general dispersant
to keep silt from depositing on the condenser tubes. Often, a
cooling water treatment will contain both an anti-scalant and a
polymeric dispersant.
Conco Services Corp. Is important to remember that the critical area for precipitation
1-800-345-3476 is in the condenser tubes (see sidebar, next page). This is where
elevated temperatures will cause the precipitation. In some cases,
www.conco.net
overtreatment of these chemicals is not only expensive but also
detrimental to other plant processes. In cooling lakes, precipitation
CIRCLE 20 ON READER SERVICE CARD

44 www.powermag.com |
POWER September 2015

Anti-Scalant: Not Too
Much; Not Too Little;
Just Right
There are a variety of scaling indices
(Ryzner, Langelier, and Practical Scale
Index) and an excellent software pack-
age (www.frenchcreeksoftware.com) that
can be used to predict the potential for
scaling to form in the condenser tubes.
These can help a plant to adjust the anti-
scalant chemical feed to its “just right”
level. Use of these indices requires ac-
curate and regular testing of a number of
parameters that your laboratory should
be doing already.
of calcium carbonate in the shallow areas
of the lake is something to be encouraged,
as it reduces the soluble calcium levels in
the water. Overtreatment has prevented this
“self-softening” mechanism, resulting in a
sudden massive scaling when the anti-scal-
ant could hold no more.
In ZLD plants where the cooling tower
blowdown water is treated and recycled, the
amount of anti-scalant used in the cooling
tower can have severe consequences in the
precipitation processes generally used as part
of the ZLD treatment. Therefore, the amount
of phosphonate or polymer treatment that is
fed to the cooling water also needs to be ad-
justed frequently, based on a variety of chem-
istry and physical factors. Those chemistry
factors include pH, total hardness, calcium,
total alkalinity, phosphate, phosphonate (in
cooling towers), and silica. Physical factors
include the temperature of at the condenser
outlet and the velocity of the water through
the tubes.
In some power plants, velocity of the cool-
ing water through the condenser tubes can be
changed by the number of circulating water
pumps in use. The use of one pump versus
two, or two pumps versus three, can make
a significant difference in the ability of the
anti-scalant to keep the tubes free of scale for
the few seconds that the water is in the hot
condenser tubes.
Biofilms create a natural resistance to flow
through the tube, thus slowing the velocity.
Debris can also plug or partially plug tubes,
reducing the velocity through the tube. Keep-
ing the tubes clear and water boxes clean
gives anti-scalants the best possible opportu-
nity to prevent scale accumulation.
The condition of the cooling water in-
take screens can have a significant effect on
scaling of the condenser tubes. Some cool-
ing water systems get additional help from
|
September 2015 POWER
side-stream filtration of the cooling water.
Removing particulate from the cooling water
enhances the effectiveness of the chemical
treatment.
Because the critical area for the anti-scal-
ant is the condenser tubes, is important that
the anti-scalant chemical is well mixed in the
cooling water flow just prior to the tubesheet.
Adding the chemical too close to the water
box may not provide sufficient mixing; add-
ing it far away from the water box can reduce
its effectiveness by having it consumed on
the walls of the cooling water pipe before it
reaches the condenser.
Approaches to Controlling
Corrosion
Gone are the days when we could prevent
corrosion in cooling water systems with an
active corrosion inhibitor (remember the
days of zinc chromate?) More recently, the
two primary chemical methods for control-
ling carbon steel corrosion in the cooling
system have been to raise the pH of the
cooling water close to 9.0 or to add or-
thophosphate to the cooling water treatment
to form an iron phosphate protective layer
on the carbon steel.
There are issues with both of these ap-
proaches. Raising the cooling water pH to
around 9.0 drastically reduces the ability
of conventional bleach to control microbio-
logical growth. Even hypobromous acid ef-
fectiveness drops off significantly at high
pHs. Therefore, microbiological control of
these systems can be a daunting task requir-
ing higher treatment levels or the addition of
nonoxidizing biocides. And biofilm growth
leads to corrosion.
When the pH is controlled with sulfuric
acid, the additional orthophosphate used in
the treatment can have unwanted side effects.
In cases where the calcium level in the tower
becomes excessive, calcium phosphate or cal-
cium sulfate can precipitate out on a variety
of surfaces. These deposits can be tenacious
and difficult to remove. In cases where or-
thophosphate is used as part of the treatment
program, it is very important to determine the
amount of orthophosphate and the amount of
calcium hardness in the cooling water on a
regular basis and calculate the potential for
calcium phosphate saturation.
In cases where cooling tower makeup is a
treated wastewater, the incoming water can
have varying levels of orthophosphate, mak-
ing control of the orthophosphate level in the
cooling water very difficult.
Orthophosphate also acts as a “fertilizer”
for a variety of microbiological species,
and this may affect the amount and types of
biocides used to maintain a relatively clean
condenser and cooling tower. Cooling water
www.powermag.com
WATER TREATMENT
POWER POINTS
Best Practices for Control
of All Water Treatment
Challenges
Ensure consistent control of
biofilms in the cooling system.
Don’t get it clean—keep it clean.
Make the best use of your
bleach: Get it fresh, keep it cool
and out of the sun, and test
every delivery.
Test your cooling water treatment
program assumptions regularly
(with lab testing) and adjust
accordingly. Add just what you
need.
Monitor, monitor, monitor—for
corrosion, scaling, and biological
growth.
systems operating at pH values just above 7
need to carefully monitor a variety of param-
eters to ensure that they are neither corrod-
ing, nor scaling, nor accumulating biofilms.
For those condensers that have copper al-
loy tubing, or where the cooling water also
comes in contact with copper alloy tubed
heat exchangers, copper corrosion is typi-
cally controlled with a type of azole. Toly-
triazole (TTA) is in common use, though it is
been shown to be very sensitive to bleach.
One manufacturer (Mexel USA) claims to
have developed a type of filming amine ca-
pable of laying down the protective chemical
layer on the surface of the circulating water
piping to prevent corrosion. The company
claims that this slick surface has other ben-
efits, such as minimizing the ability of bio-
films to stick to the surface. This would be a
very interesting development, if it proves to
be durable and cost-effective for large cool-
ing water systems.
At the very least, it is critical that corro-
sion rates in the cooling water are monitored
on a regular basis. Corrosion coupon racks
are a minimum. But they only tell you what
has happened generally over the past 30, 60,
or 90 days. To determine the instantaneous
corrosion rates on the circulating water sys-
tem linear polarization resistance probes (for
example CORRATER probes) have been
shown to provide reliable information on a
real-time basis. ■
—David Daniels (david_daniels@
mmengineering.com) is a frequent contribu-
tor to POWER and senior principal scientist
at M&M Engineering Associates Inc.
45
Protect Your Stack Linings from Corrosion
08/01/2010 | Gary Bases

Stacks at power generating stations are much more than tall towers used as a landmark for locating
power plants. They are a necessary and essential piece of equipment needed to add buoyancy to
the exhaust gases as they exit to the atmosphere. Their height and diameter are selected to match
the specific requirements of each plant, and they are usually a low-maintenance item.

Stacks may be low maintenance, but they are not no maintenance. The cost of preventing corrosion
may be as little as $10,000, but the cost of repair or replacement could be many times that or even
put your plant out of commission until the stack problem is corrected. It pays to invest in stack liner
protection (Figure 8).

8. An unprotected stack. The protective coating on the stack liner must be selected based on the actual flue

gas temperature entering the stack. A well-applied coating system can prevent catastrophic corrosion that is

expensive to repair and may require a long outage. Courtesy: Bril Inc.
At a typical 800-MW power plant, the exit gas temperature leaving the boiler is approximately 700F.
The flue gas then passes through the economizer and the selective catalytic reduction system to
remove the nitric oxides in the gas. The gas then passes through a heat exchanger or air preheater
that transfers the thermal energy from the exhaust gases to the incoming boiler combustion air to
improve the overall unit combustion efficiency. The flue gas temperature leaving the air preheater
will be reduced to around 350F before next passing through a series of air quality equipment steps
to remove SO2, particulates, and perhaps mercury until the gas reaches the induced draft fan on a
balanced draft unit. This fan pulls the flue gases from the boiler through this equipment and sends it
to the stack. On the upstream side of the boiler, a forced draft fan provides combustion air to the
boiler combustors, pulverizers, and other equipment.

A typical small industrial facility like a hospital or school has boilers that are much smaller (75 MW or
less capacity). Flue gas leaving these boilers is much lower in temperature (typically between 351F
and 500F), and the unit may not be outfitted with an air preheater. These small facilities may have a
heat exchanger such as an economizer but not an air heater. The economizer extracts heat from the
flue gas to heat the water needed in the boiler. The gas leaving the economizer is usually above
350F, but, as is often the case with the smaller boiler systems, the flue gas goes directly to the
stack.

Corrosion Protection for Stacks

The rules for determining the required level of stack protection against corrosion are based on the
temperature of the flue gas entering the stack at full load.

130F to 350F. At these low temperatures it is recommended that the stack interior be painted or
sprayed with a high-solid type nonasphaltic mastic type coating three-sixteenth to a quarter-inch wet
thickness. This type of coating will prolong the life of the stack interior from hot sulfuric, hydrochloric,
and hydrofluoric acid solutions as well as from vapors present in the flue gas. The application of this
mastic is usually made by painters, not by bricklayers. Proper surface preparation includes sand
blasting the entire interior stack surface to a near-white condition per code SSPC-SP-10 to ensure
that the mastic material will properly adhere.

351F to 400F. At these mid-range temperatures, the stack interior does not require an internal
coating of mastic protection, but it does require external insulation and lagging to prevent moisture
condensation on the outside stack surface.

401F to 850F. For gas temperatures in this range, no internal or external protection is required for
the prevention of corrosion.

851F and above. At these elevated temperatures, the internal lining of the stack must be protected
with refractory. The refractory material should match the chemistry of the acids within the flue gas.
The refractory recipe is usually three parts acid-resistant aggregate and one part lumnite cement.
The refractory is typically pneumatically or gun applied and is usually 2 inches thick over a
reinforcing material such as road-mesh or chicken-wire mesh. The reinforcing mesh is held to the
stack interior using stand-offs such as slab spacers, t-slot studs, or studs and nuts.
The Cost of Repairs Can Be Steep

Stacks rarely need repair and are low-maintenance items that only require attention if they have
corrosion issues. However, a small investment made early in their lives can save on expensive
repair costs in the future.

Here’s an example of the potential savings. Installing a mastic coating, as described above, on a 7-
foot-diameter, 96-foot-high stack operating at 300F will require scaffolding, sand blasting, priming,
and coating with the mastic and will take approximately six days to complete. Compare that
maintenance cost to the $250,000 required to replace the stack and the lost revenue during the 30
days the plant will be out of service for repairs.

Also, pay attention to your exit flue gas temperature, especially if you change the size of the
economizer or air preheater, because the exit gas temperatures may change. This temperature
change could affect the level of stack protection required to prevent corrosion.

—Contributed by Gary Bases, president of BRIL Inc., an independent consulting firm specializing in
brick, refractory, insulation, and lagging. Bases is also the author of The Bril Book(a guide to brick,
refractory, insulation, and lagging systems) and The Bril Book II (a technical manual with application
drawings for the power generating industry).

2. High temperatures can change
the microstructure. Chain graphitization
in carbon-molybdenum steel can reduce ma-
terial strength and result in brittle failure, as
seen in this reheater tube. Courtesy: David N.
French Metallurgists
coal fineness reduce carbon carryover,
which minimizes the secondary combus-
tion issues. According to the modern
standards in coal-fired units, the follow-
ing coal fineness is required: at least 75%
of weight should pass through Sieve #200
(0.0029-in. opening) and up to 0.2% of
weight may remain in Sieve #50 (0.0117
in.). Coarse coal tends to increase car-
bon carryover and loss on ignition (LOI).
Reducing the coal particle size increases
the surface area to mass ratio, effectively
making the coal more reactive. Conse-
quently, improved coal fineness will im-
prove a plant’s efficiency as well as reduce
emissions.
Another option is relocating the DMW
joints to a position where they are ex-
posed to lower temperatures. Also, the
use of DMWs made with nickel-based filler
metal (P87 or Inconel) is recommended,
specifically in CSEFs. Nickel-based filler
metal compromises the differences in
thermal expansion between stainless steel
and ferritic steel.
Sootblowers are often used heavily when
higher FEGT exists. Therefore, sootblower
retrofits and “intelligent” sootblowing
systems may be adopted to increase ef-
ficiency and reliability.
Along with this long list of operational
and maintenance strategies it may be nec-
essary to consider material upgrades to
mitigate long-term issues. ■
—Rama S. Koripelli, PhD (rkoripelli@
davidnfrench.com) is technical director for
David N. French Metallurgists.
|
July 2015 POWER
Prevent Contamination Dynamic Duo: Sparging and
and Corrosion in Blanketing
Demineralized Water To prevent corrosion in boiler feedwater
Storage Tanks Using
tanks, nitrogen sparging and blanketing
Nitrogen Sparging and practices should be considered. Sparging
Blanketing and blanketing practices, when combined,
The electric power generation industry introduce near-pure nitrogen into the wa-
relies heavily on demineralized and de- ter tanks and maintain a protective layer of
ionized water during process operations. nitrogen. In other words, nitrogen sparges
Managing the water supply is critical not the water to remove any dissolved oxygen
only under normal operating conditions, and CO2, and humid air in the headspace
but also during outages. of the tank—contaminated with oxygen
When scheduled or unscheduled outag- and CO2—is replaced by pure, inert nitro-
es occur, many boiler and pre-boiler sys- gen. This may be maintained by a precise
tems are drained. After the outage, they valve-control system that automatically
are refilled with water that has been held adjusts the nitrogen content to maintain
in large storage tanks and is therefore the protective blanket as the tank is filled
aerated, typically with high concentra- or emptied, or by simply having a continu-
tions of dissolved carbon dioxide, carbon- ous purge of low-pressure nitrogen.
ates, and oxygen. When aerated water is Typically, when a water tank is sparged,
introduced at startup, components can sintered stainless steel plates or rods,
get corroded, thereby harming the boiler called sparging elements, are used to
system. Many demineralized water stor- purge the water on a continuous basis.
age tanks are dosed with ammonia and Advantages of nitrogen sparging and
hydrazine to reduce the oxygen content. blanketing are many. First and foremost,
These mitigation practices, however, in- by filling the boiler and feedwater system
crease by about 10 times the concentra- with deaerated water with low concentra-
tion of carbonate due to the formation of tions of oxygen and carbon dioxide, corro-
ammonium carbonate. sion and iron and copper oxide scale are
CORMETECH
CLEANER AIR THROUGH INNOVATION
SCR Catalyst Management Services
Regularly scheduled
Catalyst Performance Evaluations
and
Monitoring of SCR System Operations
are key indicators to the overall health of the SCR.
Contact us to discuss Cormetech’s full range of
SCR catalyst management services and ensure
low ownership cost associated with the
SCR system.
Reliability. Delivered.
CORMETECH, Inc. 919-620-3000
5000 International Dr. www.cormetech.com
Durham, North Carolina 27712 USA sales@cormetech.com
CIRCLE 12 ON READER SERVICE CARD
www.powermag.com 21
minimized. Furthermore, faster startups
are possible because of less iron and cop-
per. These practices also reduce energy
costs because they eliminate auxiliary
steam for deaerators, and they eliminate
storage tank contamination.
Nitrogen: Delivered or Produced on
Demand?
There are four ways industrial plants may
obtain nitrogen. The nitrogen can be re-
ceived from a supplier as a gas in high-
pressure cylinders, received as a liquid
in microbulk tanks (dewars), received as
a liquid delivered to bulk liquid tanks, or
produced on demand at the facility.
High-pressure cylinders typically do not
contain enough nitrogen for sparging and
would need to be replaced often. Microb-
ulk tanks may contain enough nitrogen for
sparging, but they continuously evaporate
nitrogen and would need to be regularly
replaced. Bulk delivered nitrogen is trans-
ported by tanker truck and stored in a large
insulated vessel mounted to a poured con-
crete slab and protected by a fence. The
generating company would typically need
to pay for the slab and fence, but the gas
company usually owns the tank.
CMC
Solutions
Boilers
Would you like to turn off your CEMS?
CMC Solutions provides PEMS that meet
all U.S. regulations and we guarantee
the certification of our product.
22
Delivered nitrogen requires very little
maintenance and creates the perception
that there is an endless supply. Gas com-
panies offer five-year delivery contracts,
ensuring a steady source of nitrogen.
However, these contracts do not guarantee
price, and cancellations are often required
one year in advance.
Alternatively, nitrogen can be cre-
ated by pressure swing adsorption ni-
trogen generators for an electrical cost
of about $0.15/ccf (hundred cubic feet)
versus delivered nitrogen’s cost of at
least $0.70/ccf (prices vary depending
on service—cylinders or dewars—and
distance from supply). One thing to con-
sider in cold climates is that an on-site
nitrogen generator must usually be in-
stalled in a weather-protected area and
may take up indoor space, so site plan-
ning is a must.
Nitrogen generators are capable of
producing up to 99.999% pure com-
pressed nitrogen at dew points to –70F
from nearly any compressed air supply.
The generators are designed to continu-
ally transform standard compressed air
into nitrogen at safe, regulated pressures
without operator attention, thereby elim-
A Leading Provider of Advanced
Emission Monitoring Systems
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CIRCLE 13 ON READER SERVICE CARD
www.powermag.com
inating unexpected shutdowns due to
“bad” or empty cylinders. It should also
be noted that in order to comply with
the American Society of Mechanical Engi-
neers (ASME) corrosion prevention speci-
fication CRTD-66, systems must generate
nitrogen of at least 99.6% purity.
Ensure a Safe Environment
There are safety issues to keep in mind
wherever nitrogen is being used. Although
78% of the air we breathe is nitrogen gas,
it is only safe to breathe when mixed with
the appropriate amount of oxygen. The
two gases cannot be detected by smell, so
a nitrogen-enriched environment, which
depletes oxygen, must be detected with
special instruments. If the concentration
of nitrogen is too high (and oxygen too
low), the human body becomes oxygen de-
prived, resulting in asphyxiation.
Nitrogen generators, such as those from
Parker, feature a built-in oxygen analyzer
that measures the oxygen concentration of
the nitrogen stream. The system requires
a nominal feed pressure of 110 psig and
can operate at pressures up to 140 psig.
The resulting nitrogen has a dew point as
low as –58F.
Gas Turbines
|
POWER July 2015
 GAS-FIRED POWER
A Primer on Gas Turbine Failure
Modes
When a gas turbine goes down, recovery can be an expensive, time-consum-
ing process. Knowing what can go wrong and how to anticipate turbine
failures can help you avoid a difficult unplanned outage.
Thomas W. Overton, JD
G
as-fired power is hot and getting hot-
ter. The Energy Information Adminis-
tration estimates that 2016 will be the
first year ever that the U.S. generates more
electricity from gas than coal. New com-
bined cycle plants, many of them over 1,000
MW in capacity, are starting up almost every
month, and as coal plants continue to close
across the nation, many workers who spent
much of their careers in coal are moving or
being transitioned by their employers to gas-
fired plants (see “Balancing Risk, Reliability,
and Safety at Plants Slated for Retirement” in
the April 2015 issue).
In this environment, the number of power
sector workers new to gas turbines is grow-
ing, and a review of what can go wrong with
this equipment is useful. Though both steam
turbines and gas turbines are types of rotating
machinery, their failure modes of are not the
same (this might seem obvious, but it bears
repeating anyway). Even experienced work-
ers can benefit from a refresher. This article is
not intended as a comprehensive overview—
books have been written on the subject—but
as a starting point for further discussion and
study. Note that while aeroderivative and in-
dustrial combustion turbines each have unique
challenges keeping their gas path clean, all
combustion turbines have a common set of
operational challenges.
Recoverable Losses
Whatever contaminants exist in ambient air
will wind up inside the turbine unless they
are filtered out. These can include dust, sand,
moisture, oils, and anything else that can be
suspended, even temporarily, in air. This also
includes anything dissolved in water that en-
ters the turbine (such as via inlet fogging),
as the heat of compression will separate dis-
solved materials from the water.
Turbine compressors are very effective
filters, and foreign materials entering them
often build up on blades and other surfaces.
Salts will bind to metals and cause corro-
sion. Oils and waxes will themselves collect
other contaminants and bind them to com-
pressor surfaces. Collectively referred to as
48
fouling, these effects roughen blade surfaces
and change blade profiles and compressor
airflow, reducing power and efficiency, clog-
ging tight clearances, and increasing fuel
consumption (Figure 1).
The importance of proper air filtration has
been known for many years, but continual
improvements in filter media have shown
that the advantages of using high-efficiency
filters generally outweigh negative effects
from increased pressure drop. Even small
amounts of particles under 1 μm will result in
fouling over time (see “Options for Optimiz-
ing Combined Cycle Plants” in the Decem-
ber 2015 issue).
On- and offline washing are common
procedures used to reduce fouling on com-
pressor blade surfaces in order to recover
lost performance and efficiency. Another
approach is the use of an abrasive cleaner
such as rice or walnut shells injected into
the compressor at low speed. Used properly,
these materials will remove deposits without
damaging the blades.
Foreign materials that pass the compressor
and enter the turbine form hot deposits that can-
not be removed through washing. These require
an overhaul to recover lost performance.
Non-Recoverable Losses
Other types of lost performance cannot be re-
covered except through repair or replacement
of the affected components.
Erosion and Abrasion. Some materials
that enter the compressor, rather than binding
to surfaces, can erode them away. As these
are typically larger particles, standard filter
media are usually able to remove them from
inlet air, though even particles down to 10
μm can cause erosion. It needs to be remem-
bered, however, than anything injected into
the air stream, such as water used for inlet
NOx control, cooling, or washing, can cause
erosion. Erosion can occur on both leading
and trailing edges of the airfoil. Like fouling,
erosion causes changes in blade profiles, air-
flow, and clearances.
Abrasion is a similar process to erosion,
caused by moving surfaces rubbing against
www.powermag.com
stationary ones. A new, properly tuned turbine
should not suffer from abrasion; it usually oc-
curs as a result of other types of degradation.
As clearances change and alignments shift
over time, vibration can increase and changes
in orbital amplitude can bring rotating ele-
ments into contact with other surfaces.
The causes of abrasion are many. Improper
maintenance and tuning, fouling, excessive
wear in bearings and seals, thermal creep,
misalignment in components and couplings,
and many other problems can all cause rotat-
ing elements of the turbine to come into con-
tact with stationary surfaces. Further, these
problems will build on one another, as abra-
sion can throw the rotor out of alignment,
which increases vibration, which places great-
er stress on bearings and seals, causing greater
misalignment and more abrasion, and so on.
Foreign Object Damage. This is es-
sentially a more serious version of erosion.
Though far more common with turbines used
on aircraft (which have open inlets), industrial
combustion turbines can also sustain severe
damage from objects entering the compressor.
Unlike aircraft engines, this damage occurs
almost entirely as a result of tools and other
debris left inside the air inlet during mainte-
nance or components that break free from
their mountings. Malfunctions in auxiliary
systems such as the water wash can also result
in blade damage if they cause solid materials
to enter the compressor (Figure 2). One thing
1. Gradual deposits. Fouling and oth-
er deposits can occur on both compressor
blades and those in the turbine section. Cour-
tesy: Seoul National University
|
POWER October 2016

2. Ice attack. The blades in this turbine compressor were damaged when water from a
leaky wash system froze in cold weather and the ice broke free and entered the turbine. Source:
POWER
to keep in mind is that such debris need not be
especially large. Turbines have been gradually
destroyed by small pieces of components—
such as inlet screens—corroding and breaking
apart over time. Proper maintenance proce-
dures are usually sufficient to prevent this sort
of damage, but when it happens, the results
can be catastrophic.
Corrosion. Anything that enters a turbine,
including fuel and ambient air, has the po-
tential to react with metal components. Many
types of chemical reactions are possible, and
these can lead to many different types of cor-
rosion. The effects of corrosion can resemble
both fouling and erosion. Some types of cor-
rosion cause a buildup of corrosion products,
while others cause metal to be stripped away.
Oxidation is a chemical reaction between
oxygen and metal components. Oxidation rates
increase with temperature, which means it is of
primary concern in areas of high temperature,
such as the combustor or hot sections of blades.
Hot corrosion is a specific type of oxidation that
occurs at high temperatures (>550C) between
metal components and salts deposited on them
(Figure 3). It is of particular concern for gas
turbines because it causes cracking in areas un-
der extreme stress, such as the bases of turbine
blades. For this reason, maintaining purity of
both fuel and water used for injection is of criti-
cal importance. Contaminants such as sodium
and potassium chloride, sulfur, vanadium, and
lead (the latter two often used as additives in liq-
uid fuels), can all cause hot corrosion.
Pitting is another form of corrosion that re-
sults in localized formation of holes in metal
surfaces. Pitting occurs when conductive impu-
rities, such as water, come in contact with mi-
|
October 2016 POWER
croscopic cracks. Over time, the crack widens
into a pit, which can then lead to much larger
cracks. The same process can occur in crevices
between turbine components. Pitting is most
often a problem in the compressor, where the
blades come into contact with inlet air impuri-
ties. Frequent cycling is also a source of pitting,
as water can condense on compressor blades
after the turbine is shut down.
Fatigue. The extreme temperatures that
turbine blades are subjected to can eventu-
ally result in thermal fatigue. This can be
caused or aggravated by many factors: fre-
quent cycling; deposits and corrosion that
interfere with heat transfer; combustion and
airflow problems that cause temperature
differentials; excessive vibration; failure to
follow manufacturer recommendations for
controlling thermal stress during startup and
shutdown; as well as others. Fatigue results
in microscopic cracks that can serve as sites
for corrosion as well as growing into large
cracks that result in blade failure.
A more in-depth discussion of degradation
modes can be found in “Gas Turbine Degrada-
tion,” a presentation given at the 2014 Texas
A&M Turbomachinery and Pump Symposia,
from which some of the above is adapted.
Keeping It Clean
The impacts mentioned above can be limited
through the use of anti-corrosion and anti-foul-
ing coatings and first-stage blades designed for
enhanced durability, but scrupulously main-
taining unit cleanliness over the long haul is
the best approach to prevention. Though some
contaminants can be removed with water wash-
ing, many cannot, and the washing process it-
www.powermag.com
GAS-FIRED POWER
3. Hot take. Hot corrosion results from
contamination of the turbine blades with salts
and other substances while at high operating
temperatures. Courtesy: Sulzer
self can cause additional fouling, erosion, and
corrosion if not conducted properly. For these
and other reasons, the use of demineralized or
better quality water is recommended for any
water that enters the turbine. The use of city
water or surface water, even temporarily, will
eventually result in problems.
Much the same concerns apply to fuel sup-
ply. Liquid fuels, because of impurities and
additives, are typically a greater risk than
natural gas, but impurities in gas are also ca-
pable of causing significant erosion and cor-
rosion. Gary Stansbury, general manager of
gas turbine services for MD&A, told POWER
in an August interview that one of the biggest
sources of problems he sees is dirty gas. “If
dirt and contaminants can get past the strainers
and into the combustor, that will cause a big
issue with the combustion process in the unit.”
Such contaminants in the gas supply can
come from both the pipeline supplying the
plant and the plant fuel supply system, if the
latter was not properly blown out during con-
struction or at any time it was opened since
then (Figure 4). In addition to cleanliness is-
sues, dirty gas can change combustion dynam-
ics and cause increased stress on the turbine,
such as elevated exhaust temperatures. Stans-
bury told POWER about a client he worked
with that was experiencing repeated trips as
a result of turbine exhaust temperatures. The
problem was eventually traced to a petroleum-
based product in the gas that the filters were
not properly configured to remove.
Dual-fuel units, particularly those that
operate on fuel oil only as a backup, require
special considerations, Stansbury noted. Liq-
uid fuel supply systems that sit unused for
months can degrade to the point that they
may not be available on short notice, such
as if the plant has committed to run during
a period when gas is suddenly not available.
“These operators need to understand that
you should run your liquid fuel system peri-
odically just to make sure all of those compo-
nents are working properly,” he said.
For more on these issues, see “Best Prac-
tices for Natural Gas Line Cleaning” in the
49
 GAS-FIRED POWER
4. Clean blow. Gas supply lines are blown out before operation to remove rust, corrosion,
and other debris. Imagine if the contaminants in this debris cloud had instead found their way
into a turbine. Courtesy: Chemical Safety Board
September 2011 issue, “The End of the Line
for Pipe Cleaning with Natural Gas?” in the
February 2012 issue, and “Real-Time Moni-
toring of Natural Gas Fuel Cleanliness” in
the June 2010 issue.
Design and Manufacturing
Problems
The design and engineering of gas turbines,
like nearly all technologies, has continued to
evolve. While this means that current state-
of-the-art designs are engineered to limit
known failure modes to the greatest extent
possible, it also means that older turbines and
previous designs do not have the preventative
elements of modern ones. Upgrades exist for
many issues, but not all older turbines have
been upgraded, or upgraded properly, for a
variety of reasons.
Ian Summerside, global product line man-
ager for Ansaldo Energia subsidiary PSM—
one of many companies offering aftermarket
upgrades—told POWER in an August inter-
view that they continue to see the results of
design oversights in the field.
Summerside also noted that many turbines
are being used for different roles than they were
originally designed for or are being called upon
to run longer periods or cycle more often. Older
units are often upgraded to increase their out-
put, which places greater stress on components
designed for lower power.
“If you are taking an older turbine and you
are trying to get more power out of it or in-
crease your efficiency, you might be relying
on a component that is 15 years old, and that
may have had an inherent flaw in it that hasn’t
been a problem up to now, but that can be-
come an issue after these upgrades,” he said.
Manufacturing and quality control have
improved considerably in the past few de-
50
cades, which also means older units were not
manufactured to the same standards as newer
ones. Additionally, Summerfield noted, older
units may have been serviced and modified
by several different companies, not all of
which perform work to the highest standards.
Attempts to save money on upgrades in past
years can come back to haunt current staff.
One of the most common ways these prob-
lems can crop up, Summerfield said, is in
thermal creep of turbine blades, especially in
areas that operate at the greatest temperatures.
“Even with all the cooling air and protective
design elements, the first-stage blades in the
turbine section are operating at such high
temperatures that the metal can almost be like
rubber at the end of the blade. It is very soft
and has lost much of its structural rigidity.”
Over time, the blade can deform, stretch out,
and start to rub. Gas turbines are designed to
account for this problem, but when operating
profiles change, that can take the turbine out-
side of its design envelope and cause damage.
Another area where older turbines may
suffer is with design oversights that can in-
crease fouling. Many older designs, Summer-
field said, can experience foreign material
buildup in the blade cooling system. Because
turbine blades are designed to experience a
certain amount of movement in the attach-
ment to the rotor, any changes in expected
movement can change behavior of the blades
during operation, sometimes with catastroph-
ic consequences. Such buildup in the cooling
system, over time, can restrict movement of
the blades, ultimately locking the blade in
place if it gets severe enough. In some cases,
Summerfield said, this can change resonance
of the blades enough to cause them to liber-
ate, a failure that usually results in severe-to-
fatal damage to the rest of the engine. Proper
www.powermag.com
filtration of cooling air can reduce the prob-
lem. Modern designs include a dirt trap that
will prevent buildup in critical areas, but it
must be cleaned out periodically.
As turbine designs change to meet new
market demands, they can change mainte-
nance practices in ways older staff may not
fully understand. Stansbury noted that some
operators can be unclear on how to properly
calculate maintenance intervals according
to original equipment manufacturer (OEM)
recommendations, especially on units that
have changed their operational profiles or that
cycle frequently. “A lot of customers take it
for granted that it’s easy to understand how to
schedule a particular outage.” In fact, it can
be deceptively complicated, he said. “They
think it is either hours or starts, but they need
to understand the impact of different modes of
operation on those maintenance intervals. For
example, if they’ve got a peak firing mode, or
a fast-start capability, there are other factors
that go into OEM recommendations.” Not all
starts and operating hours are created equal.
Murphy’s Law
Finally, operators need to be mindful that not
all goes according to plan, and mistakes—
some glaring—get made, whether during de-
sign, manufacturing, construction, operation,
maintenance, or upgrades. Summerfield told
POWER the story of one particularly frustrat-
ing episode. A client plant with three identical
units began experiencing severe emissions
excursions with one turbine. While the oth-
ers worked fine, the third simply could not be
tuned to keep CO emissions within limits dur-
ing low load. The problem was severe enough
that the plant could not run that unit during
low-load operation. Repeated testing did not
reveal the problem, nor was PSM able to find
the issue, even though the three units were sup-
posedly identical. The problem persisted for
three years of operations until PSM was called
back to overhaul the combustion systems.
When the combustors were disassembled for
service, the problem was finally uncovered: On
one of the air manifolds supplying one of the
combustion cans, a flange on the pipe was cov-
ered with duct tape. The tape had been placed
there during a previous outage to prevent debris
from entering the manifold, but it was not re-
moved when the system was put back together.
Though somewhat degraded from years of op-
eration, the duct tape—the staple of so many
repairs by craftsman amateur and profession-
al—had survived to interfere with airflow in the
combustor until it was discovered.
The moral, Summerfield said, is that prop-
er maintenance checks and documentation
matter now as much as they ever did. ■
—Thomas W. Overton, JD is a POWER
associate editor.
|
POWER October 2016
Covered Piping Systems
O&M Programs for CCGT rosion (FAC). Property damage as well as ■ Cold reheat (CRH) steam, including HP
Plants personnel loss resulted. steam turbine nozzle to HRSG reheater
inlet manifold, intermediate pressure
A great level of risk is present when oper- O&M Scope and Requirements (IP) steam from HRSG IP superheater
ating pressurized systems. Over the years, The ASME covered piping systems (CPS) outlet to merge with CRH steam, the
industry safety concerns have increased O&M program places the responsibility for portion of the HP bypass to CRH that is
with the occurence of catastrophic events. safe operation and maintenance of power downstream of the desuperheater spray
To help prevent further loss and damages, piping on the operating company. Manage- valve, extractions to gland steam sys-
expanded requirements for operations and ment is charged with implementing a CPS tems, extractions for combustion tur-
maintenance (O&M) were added to the O&M program plan and conducting surveil- bine steam injection, and extractions
ASME Code for Pressure Piping, B31. lances, preventive maintenance, and in- for condenser sparging.
Power Piping—ASME B31.1—“Chapter spection activities that identify potential ■ Low-pressure (LP) steam, including
VII Operation and Maintenance” was cre- problems before degradation progresses to HRSG LP superheater steam outlet
ated in 2007 to prescribe guidelines that component failure or leakage. manifold to steam turbine admission,
promoted early failure detection and over- A typical scope of a CPS program in- LP steam bypass to condenser, and LP
all safety. This was a fundamental change cludes pipe systems that have a 4-inch sparging steam to condenser.
to the scope of B31.1, which up until then nominal pipe diameter or greater and ■ Feedwater, including suction from LP
was strictly a design code; going forward, additional systems the owners deem im- drum (or condensate pumps discharge)
it now serves a dual purpose. portant. The most common systems and to boiler feedwater pump nozzle, HP
Plant management teams have relied components are: discharge from feedwater pump nozzle
on these standards for designing, as well to HRSG HP economizer inlet, IP dis-
as updating, their maintenance programs. ■ High-pressure (HP) steam/main steam, charge from feedwater pump nozzle to
Industry experience shows that combined including heat recovery steam genera- HRSG IP economizer inlet, feedwater
cycle gas turbine (CCGT) plants owned by tor (HRSG) HP steam outlet manifold to supply to fuel gas heater (if installed),
investment groups, municipal power com- steam turbine admission and HP steam feedwater supply to HP steam bypass
panies, and others without large in-house bypass from HP steam piping to cold (to CRH) desuperheater sprays, feedwa-
engineering staffs find themselves need- reheat (modern combined cycle plant ter supply to CRH/seal steam desuper-
ing to take action. This is less of an issue configurations). heater sprays, and feedwater supply to
for regulated utilities that have estab- ■ Hot reheat (HRH) steam, including other auxiliary spraywater services.
lished high-energy piping programs, which HRSG reheat steam outlet manifold to
may address most of the requirements, al- steam turbine admission and HRH by- Chapter VII covers the basic elements
though some of the failures, including in- pass to condenser. that a program should include. From O&M
cidents at W.A. Parish and Iatan, occurred
at plants operated by regulated utilities. 1. Hanger support anomaly. In this image, the variable spring pipe support is topped
out and needs to be adjusted. Courtesy: Tetra Engineering Group
Incidents Lead to Changes
The latest version of the ASME Power Pip-
ing code, published in 2014, has built a
foundation from tragic industrial experi-
ence. It was the work of committees and
experts that drew conclusions from some
unfortunate events. Formal amendments
were enacted in previous editions of the
B31.1 as their work progressed. Two well-
known incidents served as catalysts for
change.
One of them took place at the W.A. Par-
ish Station in 2003. A cold reheat steam
pipe failed and caused a great amount of
property damage. Extensive analysis, us-
ing such tools as metallographic exami-
nations, computational fluid dynamics,
finite element analysis, and fracture me-
chanics, concluded that fatigue cracking
caused the pipeline to explode. In 2007,
the Iatan power plant desuperheater at-
temperator spray line suffered a failure
incident caused by flow-accelerated cor-

20 www.powermag.com |
POWER April 2016
procedures to condition assessment and
CPS records, the code highlights the most
important facets of the program. Gener-
ally, the O&M section focuses on operation
modes, documentation, and assessment
of degradation. Although each operat-
ing company can establish its own O&M
procedures, the following aspects shall be
covered:
■ Operation of piping systems within de-
sign limits.
■ Documentation of system operating
hours and modes of operation.
■ Documentation of actual operating
temperatures and pressures.
■ Documentation of significant system
transients or excursions, including
thermal hydraulic events (for example,
steam hammers or liquid slugging).
■ Documentation of modifications, re-
pairs, and replacements.
■ Documentation of maintenance of pipe
supports for piping operating within
the creep regime.
■ Documentation of maintenance of pip-
ing system elements, such as vents,
drains, relief valves, desuperheaters,
and instrumentation, necessary for safe
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April 2016 POWER
2. Recordkeeping. This computer screenshot shows one way to adequately document
inspection data. Courtesy: Tetra Engineering Group
operation. ation is given to design temperatures
■ Assessment of degradation mechanisms, and pressures, pipe material specifica-
including, but not limited to, creep, tion, pipe diameters, and the like. The
fatigue, graphitization, corrosion, ero- CPS records emphasize the importance
sion, and FAC. of easy access to this information. Docu-
■ Quality of flow medium (for example, ments that extend from the beginning of
dissolved oxygen and pH). operation and later modifications are to
■ Documentation of the condition assess- stay available.
ment.
Initiating a CPS Piping Program
The condition assessment details the Typically, a CPS program incorporates a
items to be recorded. Special consider- scope (technical and administrative), deg-
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www.powermag.com 21

3. Nondestructive testing. The inspectors shown in this photo are looking for trouble
on Grade 91 piping welds using linear phased array ultrasonic testing techniques. Courtesy:
Tetra Engineering Group
4. Thermal shock. The failure shown here was found on a plant’s desuperheater attem-
perator piping. Courtesy: Tetra Engineering Group
radation mechanisms that affect piping, and
overall framework for managing reliability.
The technical side covers hanger inspec-
tions, Grade 91 and creep evaluations, FAC
inspections, thermal shock/impingement as-
sessments, and water/steam hammer.
The administrative scope includes man-
agement responsibilities, program plan,
inspections, fitness for service (using API
22
579-1/ASME FFS-1-Fitness-for-Service),
corrective actions, and alterations. This
article focuses on the technical part of
the program.
Hanger inspections evaluate the over-
all state of piping hangers. From visual
inspection to recordkeeping, this plan
determines hanger condition during op-
eration (hot) and offline (cold). Action
www.powermag.com
steps are addressed in the event a field
anomaly is present (Figure 1). Repairs
and alterations to hangers are not re-
quired to be performed by an “R-stamp”
holder and often are performed by
knowledgeable plant maintenance per-
sonnel. Hanger adjustments are made in
the cold condition while the settings are
confirmed in the hot condition. A record
of activities is to be kept in field reports
and/or in computer software (Figure 2).
Field inspection intervals are to be per-
formed by a piping engineer every three
years in addition to annual walkdowns
by plant personnel.
Grade 91 and creep evaluations have
become an integral part of power piping
scope. A great deal of industry attention
has been placed on issues related to de-
graded and failed Grade 91 piping compo-
nents at combined cycle plants (Figure 3).
Special issues arise when Grade 91 steel
components are welded to dissimilar ma-
terials, such as in the case of P91 to P22
or P91 to stainless steel.
Problems also appear when the weld-
ing and heat treatment process is in-
adequate. In such cases, the desired
microstructure is not obtained and the
strength and creep-resistant properties
are usually characterized as being sig-
nificantly worse than P22. An efficient
inspection plan should detail the proce-
dure and specific instructions for hard-
ness testing equipment, technique, data
requirements, and reporting.
FAC inspection plans are designed to
target key locations commonly affected
by flow velocity, temperature, compo-
nent shape, water chemistry, fluid qual-
ity, and pipe material. An effective FAC
inspection plan integrates the initial
audit, an assessment of all high-risk
areas, a water chemistry review and
consultation for reducing risk, periodic
inspections for FAC-susceptible piping
and equipment, and repairs of defec-
tive/deteriorated components. The time
interval for these inspections is between
three and five years.
FAC is commonly known to erode carbon
steel components carrying single-phase
water or two-phase water and steam. Nor-
mally, it does not occur in single-phase
steam. The rate of wear is greatest at tem-
peratures close to 300F, with low pH and
oxygen concentrations. Geometry changes
and other flow perturbations also have a
significant effect.
Thermal shock (Figure 4) and impinge-
ment assessments include piping that
is at risk of dynamic loading, such as
quench cooling. In combined cycle power
|
POWER April 2016

5. Highly susceptible areas. It is very
important to conduct inspections to identify
attemperator cracking downstream of spray
injection, such as in this high-pressure steam
bypass to cold reheat piping. Courtesy: Tetra
Engineering Group
poration process should pay attention to
earlier records of failures and past recom-
mendations. Currently, there is no rigid
mold that a program has to emulate. A
level of flexibility remains available to
upgrade the programs as plant managers
see fit.
Existing programs are allowed to
combine an old set of procedures with
new ones. For example, an active FAC
program can work with a new CPS pip-
ing plan and risk assessment, Grade 91
inspection plan, and hanger inspection
plan. Similarly, an active CPS piping
plan and risk assessment and a ther-
mal shock/impingement assessment can
work with a new Grade 91 inspection
plan and hanger inspection plan. There
are no restrictions on how to implement
an O&M program. What matters is that
every aspect of Chapter VII is taken into
consideration.
The sole mission of the ASME B31.1
is to promote safety. The B31.1 Code

Drive Efficiency Into

plants, components at risk continue to
be piping immediately downstream of the
Your Power Plant
sprays, including the HP steam bypass to
the CRH (Figure 5) and the HRH bypass
to the condenser. Ultrasonic shear wave
is one of the preferred nondestructive
testing methods to detect early failures.
These inspections are to be conducted
every three years.
The B31.1 code also deals with wa-
ter and steam hammer. Although these
events are not frequent, they are equal-
ly important to monitor for. By defini-
tion, water hammer involves large loads
that act aggressively on pipes. Any sud-
den change in velocity in a liquid-filled
line can produce large pressure pulses,
which can damage the integrity of the
system. Rapid valve closing or open-
ing is a major factor. Steam hammer
occurs for similar reasons. Rapid clo-
Chesterton® value-driven solutions
sure of turbine stop valves can result combine our technologies, products,
in large loads. Accumulated condensate services and experience to provide
can be driven through steam and drain innovative solutions for the power
lines at high speed, producing high- industry which increase equipment
impact loads when it hits pipe bends reliability and reduce energy
and valves. “Chapter VII Operation and consumption.
Maintenance” procedures emphasize the
need for recordkeeping and detailed de- Chesterton is a world leader in
scriptions of such events. mechanical seals, pump and valve
packing, industrial coatings, and
Implementation at CCGT Plants lubricants for the power industry.
If a CPS program is absent, immediate ac-
tion is required. A program that monitors Proud member of the FSA.
corrosion, creep, fatigue, and inadequate
piping support systems is appropriate for
all power generating facilities.
If a maintenance program is already
present, only an update is needed. A com-
prehensive review will establish the por- chesterton.com/power
tions that agree with the latest guidelines
and the ones that lack conformance. In
24279 © 2016 A.W. Chesterton Company.
addition to code compliance, the incor-
CIRCLE 13 ON READER SERVICE CARD

|
April 2016 POWER www.powermag.com 23
expands on the necessary guidelines for
operations and maintenance. If an en- 6. Vulnerable at ground level. There are countless opportunities for damage when
ergy facility lacks a program, immediate wind turbine blades are being transported. Courtesy: Creative Commons/Alexi Kostibas
action is needed. If it has one, a verifi-
cation of congruence can determine the
corrective actions needed to fortify the
plan. Whether it is creating or reinvent-
ing an active program, code compliance
is always required.
—Robert Rosario, PE (robert.rosario@
tetra-eng.com) is a mechanical engineer II
and Peter S. Jackson, PE (peter.jackson@
tetra-eng.com) is director of field services
for Tetra Engineering Group.

New Quality Assurance

Program Launched for
Wind Turbine Blades
Blades are probably the most delicate part
of a wind turbine and the most suscep-
tible to accidental damage. Some esti-
mates suggest that greater than 90% of
wind turbine blades are damaged to some
degree while in transit from the manu-
facturer to the wind farm or while being
installed. The damage could be wide and Blades Deserve Proper Quality owner in delays and added costs. That is
varied, from picking up stone chips during Control why blades should receive a high degree of
delivery (Figure 6) to unintentional harm Damage to any element of a turbine when attention to ensure they reach the instal-
to the vortex. moving from factory to site affects the lation site in perfect condition.

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When you install Corzan® Industrial Systems,

you can be assured the advanced technology
materials will reliably handle aggressive chemicals,
seawater and demineralized water at high
temperatures typical in power generation plants.

Contact us for a free process suitability and technical consultation:

1.216.447.7397 or corzan@lubrizol.com www.corzan.com
CIRCLE 14 ON READER SERVICE CARD

24 www.powermag.com |
POWER April 2016

7. Standing tall. Daniel Rowcroft, pic-
tured here, is a GEV Wind Power technician
with vast experience inspecting wind turbine
blades. Courtesy: GEV Wind Power
that at every stage of the process from
blade manufacture to installation and
commissioning, rigorous quality checks
are undertaken and opportunities to rec-
tify damage are factored in,” Ross said.
“This new service also provides clients
with accurate and detailed information
should they need to seek recourse for
damage or repairs.”
The key to success is that GEV Wind
Power can be counted on as a trusted and
impartial partner, Ross said. He noted that
all of the company’s technicians working
in the QA program have extensive knowl-
edge and skill—many have first-hand ex-
perience working in blade factories—so
he said their qualifications are perfect for
their roles as inspectors (Figure 7). Addi-
tionally, when problems are identified on
the ground prior to installation, the re-
pairs are easier, safer, more cost-effective,
and less disruptive to the operation. ■
—Aaron Larson is a POWER associate
editor.

Supporting
GEV Wind Power—a European wind tur-
Power.
bine maintenance company—has devel-
oped an innovative factory-to-site quality
assurance (QA) program that could offer One Generation
clients peace of mind during the transit of
wind turbine blades and generators. The
new scheme assists in maintaining the
to the Next.
industry’s exacting installation schedules,
which are often hindered due to unexpect-
ed repairs being necessary.
“The process involves carrying out QA
inspections on newly fabricated blades, You know our name. You know our company. Our engineering services span
which once inspected and signed off, are
the power plant industry. With 29 strategically located offices and over 1750
transferred to site. On arrival, our techni-
cians will inspect for transportation dam- employees ready to work 24/7, we live our credo—Excellence – Every Project.
age, which if evident, can be repaired Every Day. Our focus has helped us become one of the largest and most
instantly onsite. The blades will then be respected engineering and environmental firms serving the power industry.
certified and given the quality assurance
all clear,” said Steve Ross, managing di- With long term contracts in place to support power plant operators, we have
rector of GEV Wind Power. become known as the “go to company” for resources and technical expertise.
Seismic and flooding analyses are just two of the many areas we know and are
Quality Assurance Doesn’t Stop recognized as industry experts. Recently acquired TALISMAN and MARACOR
Upon Delivery expand our capabilities in the regulatory, licensing and PRA areas.
After construction, all wind turbine gen-
erators are also inspected as part of the
Call. Find out why ENR consistently ranks us as a top design firm in
QA mapping process using the company’s
panoblade camera system (for more on the United States.
photo scanning, see “Innovative Wind
Turbine Blade Inspection and Maintenance
Tools” in the May 2015 issue of POWER).
This step catches any damage incurred
during the installation process because
the ultimate goal is for blades to be per-
fect when the turbine enters service.
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“Our QA program is a very exciting
innovation for the industry and ensures
CIRCLE 16 ON READER SERVICE CARD

|
April 2016 POWER www.powermag.com 27
Cation conductivity monitoring: A reality check
05/15/2008 | David G. Daniels

The operators of a new combined-cycle plant being run in two-shift mode (on 16 hours, off 8) had
become used to the cation conductivity sample of the condensate pump discharge being in alarm for
a while following each day’s start-up. Normally, after a few hours of operation, the reading dropped
to an acceptable limit. So, when cation conductivity didn’t drop as usual and the alarm never cleared,
a problem wasn’t caught in time. Scratching their heads over the high reading, the operators
guessed, ―Maybe the cation column needs to be replaced.‖

Weeks later, what had been a small condenser tube leak suddenly became big enough to
contaminate the plant’s heat-recovery steam generator (HRSG) and steam turbine. Although the
large leak was quickly detected and the plant shut down, it took nearly three months to clean up and
recondition the turbine. Despite the repairs, the long-term damage done to the expensive new
turbine is still really anybody’s guess. Had the operators not ignored the high cation conductivity
reading at the condensate pump discharge, they would have known they had a problem. Locating
and plugging the leaking condenser tube would have been easy and would have avoided the repair
costs and millions of dollars in lost generation revenues.

Unfortunately, this kind of story has become commonplace. A change in cation conductivity has
been the first indication of many problems, but it has been ignored until major contamination occurs.
Nevertheless, some operators have said that it is unnecessary (and, in some cases, impossible) to
strictly follow ASME, EPRI, or a turbine manufacturer’s guidelines for cation conductivity. Their
comments might suggest to some that the parameter is no longer important.

To be sure, some conventional fossil fuel–fired boilers and combined-cycle plants have operated for
many years with the cation conductivity of feedwater or steam at levels well above what is
considered normal. Indeed, one combined-cycle plant has been run for more than 15 years with
cation conductivity more than an order of magnitude higher than the recommended limit of 0.25
µS/cm (microSiemens per centimeter) without causing corrosion or cracks in its turbine. Here’s why
this plant has avoided problems. Because its water supply has significant concentrations of naturally
occurring organic compounds, it adds both organic amines and a carbon-containing oxygen
scavenger (a reducing agent) when preparing makeup.

Another case of unexpected immunity occurred at an older plant that recently purchased its first
cation conductivity analyzer. Following installation, the unit immediately indicated a high level in
feedwater, and the cation resin columns were exhausting in a few days. This plant’s condensers
have stainless steel tubing that has never leaked. I have regularly inspected the boilers, deaerators,
and other equipment at this plant for several years. The steam drum and tubing are in excellent
condition. Every time the turbine is inspected, there are no signs of cracking or pitting. As at the
other plant, the additions of amine and the CO2 picked up by the condensate drive feedwater and
steam cation conductivity high.

Useful or not?

Is cation conductivity so important that high values justify taking a unit off-line? Or should the
parameter be ignored in favor of other analytical chemistry tools?
Based on the experience of M&M Engineering Associates, measuring cation conductivity remains
one of the most sensitive, simple, and reliable tools for detecting small amounts of contamination in
feedwater and steam. Working in concert with sodium and other monitoring, cation conductivity
monitoring can confirm that your feedwater is clean enough to be turned into steam that won’t
damage your turbine. However, many operators find it difficult to interpret cation conductivity
readings, particularly at plants whose steam generators use water containing either naturally
occurring or purposefully added organic compounds.

To understand the difficulty, it’s important to know what cation conductivity is and is not.

Actually, ―cation conductivity‖ is a misnomer. A more precise name would be ―cation-exchanged

conductivity,‖ because it is a measure of the conductivity of a solution after it has been passed
through a strong acid cation exchange resin. This resin exchanges all the cations in the sample for
hydrogen ions. In high-purity samples (such as of condensate, feedwater, or steam), the cation
exchanged is primarily ammonium ions. What passes through the resin unscathed are all the anions
in the sample. These are primarily anions of dissolved carbon dioxide (bicarbonate), the anions of
any organic acids such as formate or acetate, and (it is hoped) traces of chloride and sulfate.

Because the ammonium ion is removed and exchanged for hydrogen, the pH of the water exiting the
column is more acidic than it was entering. This has led some to use the term ―acid conductivity‖ to
describe cation conductivity.

Chloride and sulfate are known to contribute to corrosion fatigue in turbine blades, particularly those
in the final rows of the low-pressure section. It is chloride and sulfate contamination that cation
conductivity is really intended to detect. Early detection of this contamination can allow a plant time
to correct contamination before it causes deposits and corrosion on the turbine (Figure 1).

1. Scaled up. Proper attention to cation conductivity monitoring might have prevented this damage
to turbine blades. Courtesy: M&M Engineering Associates
What cation conductivity is not is a reflection of a single parameter, as in the case of sodium or silica
analysis. Similar to specific conductivity, cation conductivity represents the sum of the conductivities
of all the anions that remain in the solution, with a small contribution from hydrogen ions. In fact, if
cation conductivity measurements of steam represented the level of a single parameter, such as
chloride, they would not be sufficiently sensitive to be of much value.

The theoretical cation conductivity of a 2-ppb chloride (hydrochloric acid) solution is 0.063 µS/cm,
barely above the theoretical minimum of 0.055 µS/cm. Most turbine manufacturers call for the
chloride level in the steam to be below 2 ppb under normal conditions. The steam’s chloride
concentration would have to rise to nearly 20 ppb before the resultant cation conductivity would
exceed the generally accepted normal cation conductivity limit of 0.2 µS/cm. Steam entering a
turbine with a 20-ppb chloride concentration would be considered grossly contaminated.

What makes cation conductivity monitoring so valuable is that contamination of feedwater or steam
is rarely due to a single contaminant. When a condenser tube springs a leak, chloride, sulfate,
carbonate, and many other anions contaminate condensate and feedwater. The combined effect will
significantly raise cation conductivity and provide the desired early warning even when the individual
contamination levels are small. Of course, if there is a large contribution from CO2 or organic acids,
the problem may not be detected until it is too late. Carbon dioxide in steam is too volatile to create a
low-pH environment for turbine blades and therefore cannot cause corrosion. Whether or not organic
acids can damage a turbine is an area of active research.

Turbine manufacturers are very aware of the long-term damage that can be caused by even low
levels of chloride and sulfate. The simplest, most reliable way to detect such contamination in real
time has been cation conductivity. Therefore, turbine OEMs have set cation conductivity limits where
a significant contribution from CO2 or organic acids cannot be tolerated.

During plant commissioning, for example, CO2 and other organic chemicals in first steam can raise
the cation conductivity level so high that meeting the warranty limits specified by the turbine
manufacturer(s) seems impossible. This leaves the plant two unpalatable options: invest in
additional water treatment equipment to remove the offending organic chemicals, or use a more
sophisticated tool—such as ion chromatography—to prove the absence of chloride and sulfate in the
steam. Turbine original equipment manufacturers often require that, during routine start-ups, the
cation conductivity of steam be less than 1 µS/cm before it can be admitted into the prime mover.
Sampling problems and CO2 in the condensate can result in levels higher than that, unnecessarily
delaying start-ups.

“New and improved” cation conductivity

Because cation conductivity is so simple and reliable, significant efforts continue to be made to
improve the technique by removing interferences from carbon dioxide, in particular. The new
parameter to be monitored and analyzed goes by the name of degassed cation conductivity.
Because the pH of the sample following the strong acid cation resin is acidic, most, if not all, of the
CO2 in the sample is in the form of a dissolved gas. The most common way to remove it is to drive it
off with heat using a reboiler. After the sample is passed through the strong acid cation resin, it is
heated to near boiling, cooled to 77F, and then sent to a conductivity meter.

The most common complaint about reboiler-style degassed cation conductivity is unreliability. The
temperature control of the reboiler is critical—too low or too high produces unreliable results. What’s
more, the temperature of the sample after the reboiler can affect the result.
The CO2 also can be removed by sparging it out with nitrogen gas through an empty or packed
column. Nitrogen purge systems are typically only used during start-ups until the regular cation
conductivity value drops to a normal level. The systems’ nitrogen consumption rate makes them
impractical for continuous use. For units that only experience high cation conductivity during start-
ups, nitrogen sparging may be all that is required.

A relatively new technique uses a spinning-disk reactor and CO2-free air as the purge gas. The air is
first passed through a molecular sieve to remove all the CO2. The water sample passes through the
cation column and then is mixed with the CO2-free air and put through the reactor, whose large
surface area creates air bubbles that strip the CO2 from the sample. The reactor removes about 70%
of the CO2, so it does not completely remove the interference. But the results are good enough to get
within the desired limits. This method does not require heating or cooling the sample.

Seeing differently

Because some plant operators and chemists have had problems with degassed cation conductivity
monitoring, they have looked for other ways to detect parts-per-billion levels of contamination in
condensate. Here are three that we have seen used successfully.

Sodium. On-line sodium analyzers have become more reliable and simpler to maintain. A number of
manufacturers—including Swan Analytical Instruments (www.swan.ch), Thermo Fisher Scientific Inc.
(www.thermo.com), and Hach (www.hach.com)—make sodium analyzers that can reliably detect 0.1
ppb of sodium. Swan’s Soditrace model claims the industry’s lowest detection limit for sodium ion
concentrations of 1 part per trillion (0.001 ppb). Figure 2 shows Hach’s unit.
2. How low can you go? Hach’s Polymetron 9245 sodium analyzer boasts a sensitivity of 0.01 ppb.
To maintain an optimum response time in low-sodium solutions, the analyzer automatically
reactivates the electrode using nonhazardous chemicals. Courtesy: Hach Company

Most cooling water contains sodium concentrations of the same order of magnitude as those for
chloride or sulfate. Therefore, sodium detection in condensate, even at the 0.1 ppb level, becomes
an excellent early warning system for condenser tube leaks or sodium leakage from water
pretreatment systems. However, sodium analysis doesn’t address chloride or sulfate concentrations
directly. For that reason, M&M strongly recommends using both cation conductivity and sodium
monitors not only on the main steam sample but also at the hotwell or condensate pump discharge
(or, if there are condensate polishers, downstream of them). Sodium monitoring is the only way to
detect caustic contamination.

Chloride. As part of its Orion line, Thermo Fisher Scientific offers a chloride monitor that can detect
levels as low as 0.1 ppm (Figure 3). Though this sensitivity level is insufficient to detect
contamination of feedwater, it has been used very successfully to continuously monitor chloride
levels in boilers and HRSGs. Because contamination quickly concentrates in steam generators, this
instrument can provide the desired early warning.

3. No moving parts. According to the manufacturer, the Orion 2117XP chloride monitor holds
calibration up to 60 days between reagent changes. The instrument can measure chloride
concentrations as low as 0.1 ppm. Courtesy: Thermo Fisher Scientific Inc.
Ion chromatography. The only technique that can directly analyze for chloride, sulfate, and
phosphate with a single sample injection is ion chromatography. If desired, an ion chromatograph
can even be configured to analyze for organic acids such as formic and acetic acid. Great strides
have been made in simplifying the technique. However, it still requires significant dedication to set
up and maintain calibration on an ion chromatograph—particularly one that is detecting ppb levels of
contamination.

Those who make that commitment usually end up feeling it was worth the effort. For example, lab
techs at a large coal-fired plant that for years has used an on-line ion chromatograph from Dionex
Corp. (www.dionex.com) have been very pleased with the results. By the way, the plant’s control
room operators still use cation conductivity analyzers to monitor feedwater purity. Why? Ion
chromatography analysis of a single sample for chloride, phosphate, and sulfate can take quite a few
minutes. And if you’re measuring multiple sample points, you may only get one analysis per point
per hour. Cation conductivity measurement, on the other hand, is essentially continuous.

Don’t drive blind

Whether you monitor cation conductivity or degassed cation conductivity alone or in combination
with other analytical techniques, it is essential that your instruments be reliable, on-line continuously,
and sensitive enough to detect contamination early enough to take corrective action to prevent
corrosion.

You would never think of operating your car at night without headlights. Don’t operate your steam
turbines and HRSGs without the tools to see what’s coming down the road soon enough to steer
away from problems. Like driving in the dark, the risks of operating a plant ―blind‖ are far too great.

—David G. Daniels (david_daniels@mmengineering.com) is a principal of M&M Engineering

Associates and a contributing editor to POWER.
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Inclusion in New Products does not imply endorsement by POWER magazine.

|
October 2011 POWER www.powermag.com 85
How to Measure Corrosion Processes Faster
and More Accurately
05/01/2009 | Daniel C. Sampson and Peter D. Hicks, Nalco

Maintaining reliable and efficient plant operations requires good control of corrosion and corrosion
product transport in power plant water systems. The Electric Power Research Institute recommends
oxidation-reduction potential for passivator control in feedwater systems, as do many industry
experts. Here’s how to turn that recommendation into a robust feedwater monitoring program.

The Electric Power Research Institute (EPRI) has for some time advocated the use of online room-
temperature (RT) oxidation-reduction potential (ORP) measurements to monitor boiler feedwater
corrosion chemistry and thereby minimize corrosion and reduce the frequency of boiler tube and
other steam cycle failures. Unfortunately, current corrosion control and monitoring methods located
upstream of a boiler can be unreliable, unpredictable, and impractical. The right instrument,
improperly installed and operated, will return poor or misleading results.

Most plants attempt to monitor dissolved oxygen (DO), ORP, and reductant residuals (if reductant is
used). Their monitoring programs, however, are often deployed in few locations with poor or little
corrosion product transport monitoring, which can leave large portions of a plant unprotected. Even
when corrosion product monitoring is performed, there are often questions related to the validity and
interpretation of the numbers produced.

Fortunately, new, more accurate and responsive ORP measurement instruments are available that
enable plant operators to significantly reduce steam cycle corrosion.

Dynamic Corrosion Effects

Power plant operators and chemists tend to perceive ORP as analogous to conductivity — a
relatively static measurement that, taken in one location, provides a good indication of conductivity
throughout the steam cycle. In fact, ORP is much more analogous to temperature, which is dynamic
and varies widely throughout the steam cycle. ORP is really an ever-changing kinetic indicator of
system health at both the point of measurement and throughout the steam cycle.

Corrosion stress, both general and localized, occurs often in a power plant, but traditional monitoring
programs often fail to detect or react to such events. Local damage may cause failure, and corrosion
product transport provides a secondary failure mechanism where corrosion deposits accumulate.
Detecting these events may require major upgrades to the monitoring tools available at most plants.
DO, reductant feed and consumption, and corrosion product transport would have to be monitored at
multiple locations and with great accuracy. In most plants, this isn’t practical (because of
instrumentation cost and the lack of installed sample points) or possible (given limitations in real-time
corrosion product transport measurements, data validity, and interpretation, as well as the plant’s
use for direct control).

Many plants focus control of corrosion stress at a single location (EPRI recommended the
economizer inlet in earlier work and the deaerator inlet in its later recommendations), with the
assumption that control at a single point provides protection throughout a circuit. This approach is
relatively straightforward and can be effective in stable systems or when the location of the corrosion
(reduction/oxidation) stress site is known or is close to the point of measurement.

Most systems, however, are not stable, and potential corrosion stress is widespread and often
dynamic. The corrosion "space" changes, and single-point monitoring with slow response can miss
short-lived changes in chemical demand or the corrosion environment. Traditional corrosion
monitoring and control programs miss the dynamic stresses by assuming that slow response is
"good" and a "good" measurement in one location indicates adequate protection in all locations.

The ever-changing ORP space requires a rapidly responding, real-time monitoring and diagnostic
measurement that reacts immediately to the changing corrosivity of the system. Such a tool gives
operators and controllers time to respond to the cause of the variation, thus minimizing any of its
negative impacts.

Establish an ORP Reference

ORP is the electrical potential of a liquid at a specific temperature. As such, ORP represents the net
sum of redox potentials/reactions in a sample stream as measured on noble metals (usually
platinum or gold). Measurements are usually made against some standard reference electrode such
as silver/silver chloride or copper/copper sulfate. ORP is the difference in voltage between these two
electrodes.

It’s important to quote the temperature and other conditions at which the reading was taken when an
ORP number is quoted and the reference electrode is used to measure the potential difference. For
example, consider an ORP sample taken at 400F when an ORP number is simply quoted as "–0.6
V." This value is essentially meaningless. There’s no way of knowing if the voltage measured is –0.6
V against the standard hydrogen electrode (SHE) at 400F, –0.6 V against the SHE at 77F, –0.6 V
against some other reference electrode at 400F, or –0.6 V against some other reference electrode at
77F. The plant chemist should be aware of the importance of temperature when investigating and
comparing competing ORP claims.

For the purposes of this article, we use the ORP value versus the reference electrode with
temperature. For example, an ORP measurement of –0.6 V obtained with the SHE at 400F is
reported as –0.6 V vs. SHE (400F).

At-Temperature ORP

The at-temperature (AT) ORP program continuously monitors the corrosion stress in a hot water
system such as boiler feedwater. It provides a window into the process that’s not available from the
traditional room-temperature measurements such as DO, ORP, or reductant residuals tests. The
measurement also allows real-time analysis of the corrosion kinetic continuum rather than providing
a postulated measurement that assumes thermodynamic stability and equilibrium, allowing operators
to take rapid action to control and/or identify corrosion stress to minimize corrosion and subsequent
corrosion product transport. In essence, AT ORP is a paradigm shift in corrosion stress management
and control for the power industry.

AT ORP enables in-situ measurement of ORP in feedwater at the elevated temperatures where
sensing electrodes are actually in contact with high-temperature water. Traditional ORP
measurements utilize a nonrepresentative sample (cooled feedwater) that moves through long
sample lines (increasing lag time) to a non-optimum device (RT ORP). AT ORP takes a
representative sample (hot feedwater) to a much more sensitive device (Figure 1).

1. At-temperature oxidation-reduction potential (AT ORP) measurement. These are the

components of Nalco’s AT ORP cell. Courtesy: Nalco

The Nalco Co.’s AT ORP assembly consists of a sample inlet and outlet, connections for an integral
resistance temperature detector (RTD), platinum electrode, and a separate external pressure-
balanced reference electrode (EPBRE). This apparatus has been used in high-temperature water
environments up to 500F and 3,000 psi (20.68 MPa).

The potentials measured by the AT ORP platinum probe are measured against the external,
pressure-balanced, silver/silver chloride reference electrode. The temperature of the water flowing
through the probe is recorded. All of the data collected by the probe can be archived and recovered
on the plant data-logging system with suitable electrical signal conditioning. The signals can be used
to control any species affecting the ORP space (typically reductant feed) and for advanced
diagnostics.

Particle Analysis

Traditional monitoring of metal transport and generation in the steam cycle relies primarily on
periodic wet tests such as "patch" tests or photometric analysis. This approach, though valuable,
leaves significant holes in the data history. Every thermal, chemical, or hydraulic event liberates or
generates metal oxides in the steam cycle called a "crud burst," and these events occur frequently
yet randomly.
Time-based testing (iron sampling at a specific frequency, for example) is important, but it cannot
detect the majority of these events. Thus, plants are flying blind during normal operation. The only
reliable method for determining metal transport is periodic inspections and tube deposit weight
density measurements. These methods are important and must continue, but they can only detect a
metal transport problem after it has occurred. What’s missing is an intermediate step where plant
operations can be tuned to minimize metal transport before damage is done.

Particle analysis provides a near-real-time measurement of metal liberation and transport. Two
different technologies can be used: particle size analysis and particle counts.

The particle monitor, such as that sold by Chemtrac Systems Inc., detects particulate contamination
in a flowing, liquid sample by dynamic light obscuration (DLO). As particles pass through the
illuminated sensing area, they obstruct a portion of the transmitted light. A sensitive photodetector
converts these light fluctuations into a root mean square signal representative of particulate size and
concentration. The online flow-through sensor eliminates sampling/testing variances encountered in
the more-familiar manual Millipore analyses used to count particles. Multiplexed sensors provide
complete, real-time monitoring of individual condensate streams or any other component of the
boiler system.

Use the AT Tools

An ideal monitoring program would correlate the interplay of the oxidizing environment with all of the
possible corrosion stressors across the ORP space and relate that data to corrosion product
transport. Combining particle counts with AT ORP technology closes the loop on steam cycle metal
transport. This combination offers two windows into the process: an extremely accurate
measurement of the oxidizing environment (AT ORP technology) with control capabilities and a
measurement of the impact of that operating environment (particle counts and metal transport). AT
ORP technology and particle analysis also can provide visibility into previously undetectable events.
The two technologies can be used to correlate particle counts with metal (iron and copper) transport
test results and operating environment (AT ORP technology).

It is possible to generate a set of plant-specific corrosion product transport curves using particle
analysis and traditional monitoring techniques. Once that relationship has been established, then the
particle counter output can be scaled to match the text results. Thus, particle analysis could
generate an output proportional to the actual concentration of particulate metal oxides in ppb levels.

The next step is to use the particle counter and AT ORP technology to evaluate the impact of metal
liberation and transport. Event analysis can be used to identify those plant evolutions that result in
the greatest metal transport and the greatest change in the oxidizing environment. With this list,
plants can then tune operation to minimize metal transport during these events. The monitoring
program can then be used for real-time metal transport and oxidizing environment monitoring once
the initial metal transport mitigation system has been implemented. Plants can use these monitoring
tools to detect any significant increase in metal transport, identify the cause, and take corrective
action.

Where to Sample?

Most coal-fired plants monitor and control the oxidizing environment at two or three locations,
typically at the condensate pump discharge, deaerator inlet and outlet, and economizer inlet (Figure
2). Combined-cycle plants usually monitor and control the oxidizing environment at just two
locations: the condensate pump discharge (usually after chemical feed) and the deaerator or low-
pressure (LP) drum outlet. The sample locations themselves might be appropriate, but the AT ORP
sampling should be made as close as possible to the actual sample take-off point.

2. Popular sample points. These are typical steam cycle water and steam sample point
locations. Source: Nalco

It’s important to remember that steam cycle corrosion occurs at temperature and pressure. Any
measurement taken to estimate corrosion should be made as close as possible to the conditions at
which the critical corrosion processes are occurring. The following are additional suggestions for
improving the quality of your samples.

Don’t Quench the Sample. The active species in your sample will be quenched in your sample
cooler. That means you forfeit the opportunity to observe any correlations that exist at actual
operating temperatures and pressures. In some cases, the wrong conclusions are reached by
measuring ORP at temperatures that are unrepresentative of actual operating temperatures.

Minimize Sample Lag Time. Sample water often travels hundreds of feet from the sample connection
to the steam sample panel. Sample water often passes through large-volume coolers and filters at
the sample panel before contacting the panel’s low-temperature probes. This circuitous path adds to
sampling lag time and dilutes real system effects. Also, further corrosion reactions can occur as the
sample passes through the long sample lines and large coolers before it contacts the room-
temperature probes.
Accurately Measure Reductant Activity. Like corrosion stressors and corrosivity, reductants (oxygen
scavengers/passivators) are more active at temperature. This is particularly true of many of the
passivating scavengers such as hydrazine, carbohydrazide, diethylhydroxylamine, and the like. The
reductant impact on corrosion stressors is enhanced at temperature, so control based on reductant
residual is more sensitive and realistic at temperature. A cooled sample might not show how much
"power" (in reductant) is present in the system, but an at-temperature sample (AT ORP) will show
this.

Figure 3 illustrates the impact of reductant feed on both RT ORP and AT ORP. Reductant was
added to a solution initially containing 140 ppb DO. More reductant was added over time, and DO
declined. The range of ORP movement increases significantly with the AT ORP measurement. The
AT ORP probe is more responsive to changes in DO and/or reductant. This increased sensitivity has
important implications for system control based on an ORP setpoint. Greater sensitivity provides
better response to changes in the corrosion environment. RT ORP probes are completely insensitive
to some of the macro corrosion changes occurring at temperature.

3. Some like it hot. The at-temperature oxidation-reduction potential (ORP) probe, with water
samples at operating temperatures and pressures, produces superior results. Source: Nalco

Carefully Measure Dissolved Oxygen. RT ORP can correlate with DO, but it tends to be a poorer
indicator of reductant excess in boiler feedwater systems. However, even as a DO "indicator," the AT
ORP probe response and magnitude of movement to DO upsets is far superior to that of RT ORP.

Figure 4 presents laboratory data showing ORP response as measured after making short-term
changes in DO concentration in a system. The immediate, relative, and greater magnitude of the AT
ORP response is evident. It’s especially important to note the resolution of the AT ORP response at
extremely low (<10 ppb) DO concentrations. RT ORP response is especially poor at low dissolved
oxygen concentrations, yet this is the very zone where power plants typically operate.
4. At-temperature measurements are more responsive. Note the difference between at-
temperature (AT) ORP and room temperature (RT) ORP response to adding various amounts of air-
saturated water at 400F. Source: Nalco

The greater response of AT ORP technology to changes in the oxidizing environment makes it an
excellent tool for plants that do not feed reductant but that remain justifiably concerned about
corrosion stress. The extremely sensitive response of the AT ORP probe to low-level DO
concentrations indicates that this technology can be used in both reducing (AVT-R) and oxidizing
(AVT-O) regimes.

Correctly Measure Corrosion. AT ORP technology will also respond to any species present in the
water that will affect the corrosion space and is not limited to DO and oxygen scavenger feed. Figure
5 illustrates the AT ORP probe response as compared to the RT ORP probe as a result of corrosion
processes occurring within a feedwater heater. The additional soluble corrosion products, such as
iron and/or copper, are sensed by the AT ORP probe but go unnoticed by the RT ORP probe.
5. AT ORP sees more. AT ORP is much more responsive than RT ORP to corrosion occurring in
the outlet of a feedwater heater. Source: Nalco

Case Study #1: A Small Problem with Reductant Feed?

The following example concerns a common occurrence at many power plants: a relatively small
increase in DO concentration. Most plants might consider this a minor "blip" that can be ignored, but
the corrosion environment at temperature tells a different story.

In this system (Figure 6), scavenger chemical feed rate was slaved to steam flow off a primary
boiler. A secondary boiler was brought online, which placed a higher load on the single deaerator.
Oxygen scavenger was added to the deaerator for the primary boiler, but the feed of scavenger was
not adjusted during this event because its control was from the primary boiler steam flow only.
6. Peak performance. A corrosion stress event illustrates that a relatively small increase in DO
can lead to large corrosion stresses. Source: Nalco

Note the conductivity decrease during the event, signifying the lower scavenger concentrations in
the DO as more makeup water was added but scavenger feed was not adjusted upward. Also,
notice that AT ORP data show the lack of feedwater corrosion stress and corrosivity control.

The AT ORP sensor response clearly shows that returning the system to a lower ORP space (lower
corrosivity) can take a considerable amount of time and that some resulting damage might not be
reparable. Note that AT ORP level does not decline with DO but remains elevated longer as ongoing
system oxidation (corrosion) keeps the ORP elevated. This is an indication that the effects of active
corrosion are still being sensed even though DO has decreased.

This example demonstrates the need to minimize the magnitude and duration of feedwater corrosion
stress excursions because even relatively small events can have a large impact on corrosivity. An
inline AT ORP sensor identifies such problems more rapidly and helps manage the impact of such
problems automatically.

Case Study #2: A Tale of Two Events

This example illustrates another problem common in power plants: air inleakage through condensate
pump seals. In this example, the AT ORP technology initially monitors the event (the "monitoring
phase" of the study). Later, the AT ORP system attempts to control corrosion stress in the face of
this same corrosion stress event.
The unit has two condenser hotwell pumps (pump A and pump B). During the AT ORP monitoring
phase, it was clear that the pumps had different implications for corrosion stress creation in the
feedwater system. Figure 7 shows the low-pressure heater #3 (LP#3) and the gland steam
condenser (GSC) AT ORP and DO values with the use of two condensate pumps. Figure 8 includes
data taken from the two RT ORP probes during the same time period.

7. Leaking air. AT ORP and dissolved oxygen (DO) values on switching condensate pumps
indicate that Pump A has a seal that allows air in-leakage. Source: Nalco
8. Pump preference. AT ORP and RT ORP values on switching condensate pumps indicate that
Pump A air in-leakage significantly increases the corrosion potential in the condensate
system. Source: Nalco

The AT ORP probes reacted immediately to the change in feedwater corrosion conditions as soon
as the switch to pump A was made. Some of the corrosion stress was caused by the increase in
feedwater DO due to air in-leakage from condensate hotwell pump A.

The passivator consumed some of the DO inventory, but some of the DO was involved in corroding
the metallurgy of the feedwater heaters. As mentioned before, the AT ORP probe also picks up the
production of soluble corrosion species.

The AT ORP readings indicated that operating with pump A was more damaging to the LP heaters
than pump B. The AT ORP probe was more sensitive and responsive to this pump change and was
able to detect and react to the real feedwater corrosion stress events better than an RT ORP probe.
The RT ORP probes were found to be significantly less sensitive or unresponsive in detecting real-
time feedwater corrosion stress events.

Also note that the LP#3 feedwater heater exit AT ORP level was higher than the AT ORP level at the
GSC with pump A, even though DO was lower at the LP#3 sample point. The reason for this is that
extra scavenger had been consumed (raising AT ORP levels) across the feedwater heaters, and
soluble, oxidized corrosion products had been released, thereby raising the AT ORP level as well.
Figure 9 illustrates control of the AT ORP levels at the LP#3 sample point to –350 mV versus the
EPBRE (271F) when the different condensate pumps were in operation. Note the increase in
feedwater corrosion stress when condensate pump A was operated with its air in-leakage problem.
With current scavenger feed limitations at this plant, even controlled feed of carbohydrazide at 100%
pump speed could not reach and maintain the AT ORP setpoint of –350 mV versus the EPBRE
when the plant was operating with condensate pump A. When the plant operated under constant
load (195 MW) using condensate pump A, the lowest AT ORP reading that could be achieved and
maintained under current plant operating conditions was –325 mV versus the EPBRE.

9. Pick your pump. Controlling an AT ORP setpoint of –350 mV levels in pump A that was
experiencing air in-leakage wasn’t possible even when adding carohydrazide at 100% scavenger
pump speed. Source: Nalco

The LP#3 AT ORP probe sensed a change in feedwater corrosion stress and adjusted the
carbohydrazide pump speed when the plant switched from condensate hotwell pump A to pump B.
AT ORP controlled feed of carbohydrazide was then able to maintain the –350 mV setpoint when
condensate pump B was operating. AT ORP readings indicated that operating with condensate
hotwell pump A was more damaging to the LP heaters than using Pump B.

Case Study #3: Obtain and Maintain Low Corrosion

This example illustrates how the AT ORP level varied during the monitoring phase and how it was
controlled during the control phase. Prior to installation of the AT ORP system, operators at this plant
were unaware of the dramatic variations in the corrosion space of their feedwater heater system,
even though they had RT ORP monitors.
The goal of this particular program was to obtain and maintain reduced conditions to limit feedwater
corrosion in the boiler. AT ORP monitoring at the low-pressure feedwater heater outlet showed how
the AT ORP level varied greatly, and there were many excursions to the elevated, more oxidizing
regimes.

In Figure 10, the percentile plots show that during the monitoring phase, 90% of the AT ORP data
fell within the blue rectangular box. However, when the system switched to controlling the AT ORP
space, the average AT ORP level was reduced and then maintained in a much tighter control range,
thereby significantly reducing feedwater corrosion and lowering corrosion product transport. The
plant now has far greater confidence that its boiler assets are much better protected than they were
prior to the AT ORP program introduction.

10. Tight process control. Percentile plots showing how the AT ORP space was controlled after
switching from monitoring mode to control mode with AT ORP technology. Source: Nalco

—Daniel C. Sampson (dcsampson@nalco.com) is a power industry technical consultant and Peter

D. Hicks (phicks@nalco.com) is a research scientist for Nalco Co.
More Strategies for Inspecting HRSGs in Two-
Shift and Low-Load Service
08/01/2014 | Peter S. Jackson, PE, David S. Moelling, PE, and James W. Malloy

This supplement to “Strategies for Inspecting HRSGs in Two-Shift and Low- Load Service” in the
August issue includes additional discussion of the heat recovery steam generator (HRSG)
Inspectors Toolkit and HRSG Inspection Guide sections of the main article plus additional photos of
damage caused by rapid startups and two-shifting of units over time.

More Tools for the HRSG Inspectors Toolkit

Many combined cycle plants have aggressively pursued periodic inspections of HRSG component
integrity during scheduled combustion turbine (CT) maintenance outages, even though the plants in
general have operated significantly few hours than originally assumed. A thorough HRSG inspection
provides important information on existing pressure-part condition prior to a transition to either low-
load operations, faster starts (high-pressure [HP] drum ramp rates), or from baseload to two-shift
cycling.

Inspections alone do not provide sufficient basis for transitions from two-shifting to low-load
operation. Engineering evaluations of the HRSG design capability to accommodate the specific load
being marketed are essential to confirm that the pressure parts will operate in compliance with
ASME Code requirements. One concern is the maximum metal temperature that pressure parts are
subjected to during low-load operations.

Upgrades such as GE’s IGP and OpFlex control strategies (see “Managing the Changing Profile of a
combined Cycle Plant” in the June 2014 issue) can yield CT exhaust temperatures that are higher
than the original plant design. Thermal analysis of pressure part components using a design
simulation tool such as KED’s Power Plant Simulator & Designer or proprietary HRSG original
equipment manufacturer (OEM) tools is essential to confirm the metal temperatures in HP
superheater and reheat (RH) tube panels and related conditions, such as HP evaporator
circulation/buoyancy and the implications of duct firing at low load. Inspections of high-temperature
components for low-load operations will need to identify increases in the rate of damage so that
corrective actions and schedules can be planned.

Such assessments will often include comparison of predicted temperatures with plant data historian
archives or temperatures from temporary thermocouples. Operation at higher temperature in Grade
91 components in the HP superheater and RH increase creep damage accumulation while low-load
operation means substantially lower pressure, which reduces the operating stresses that propagate
creep cracks.

One estimate of these effects is that an increase of 20F may reduce creep life by 50% while a
reduction of operating stress by 20% may double creep life. The net effect for a specific HRSG can
be determined by an engineering assessment of the proposed low-load operation on high-
temperature component life using the methods endorsed by ASME in the FFS-1 Fitness-for-Service
Standard, first published in 2007.
Borescope inspections were relatively uncommon in the past for new, large HRSGs due to limited
access and the expectation that there was little accumulation of water-side deposits early in life. Ten
years ago, borescope inspection was principally applied for steam plant components to conduct
inspections of attemperator spray liners for HP steam and RH steam piping.

Today, articulating borescope/videoscope inspections are standard inspection practice for mid-life
two-shifting HRSGs. It is an important tool to assess the early accumulation of waterside deposits in
HP evaporators before the development of under-deposit corrosion and extensive damage to
affected tube panels (Figures 1 and 2). A number of plants, particularly those in cogeneration
service, have required panel replacements that might have been avoided had borescope inspections
been part of scheduled HRSG inspections.

1. Under-deposit damage of a high-pressure (HP) evaporator tube is illustrated. Courtesy: Tetra

Engineering Group, Inc.
2. A macro-section of the HP evaporator tube shown in Figure 1 is shown. Courtesy: Tetra
Engineering Group, Inc.

HRSG Inspection Guide

Following are areas of potential trouble that should be checked.

Grade 91 Components. Grade 91 creep-strength enhanced ferritic (CSEF) steel has been
susceptible to weld cracking in two-shift cycling plants over time (Figures 3 and 4).
3. A Grade 91 hot reheat bypass piping weld cracked in this two-shifting unit. Courtesy: Tetra
Engineering Group, Inc.

4. This 3×1 combined cycle plant operated on a two-shifting schedule experienced a steam leak due
to a weld crack in its 18-inch-diamater main steam pipe. Courtesy: Tetra Engineering Group, Inc.

High-Temperature Tube Leaks and Failures. Tube failures are less common, but have occurred in
many large reheat HRSGs. The root causes of these failures varies and depends on many factors,
such as material type, thermal/stress conditions during operations, and water hammer. One common
cause is tube exposure to high gas temperatures during startup followed by a rapid quenching
(resulting in a tensile overload failure) from condensate accumulation or excess attemperation spray
(Figures 5 and 6).

5. A grade 91 hot reheat wye (“laterolet”) cracked during use in this two-shifting HRSG. Courtesy:
Tetra Engineering Group, Inc.

6. A Grade 91 reheater tube failed and separated from its header in this two-shifting plant. Courtesy:
Tetra Engineering Group, Inc.

Another well-known cause is corrosion fatigue, which occurs when aggressive water chemistry
combines with an inadequate vibration restraint, and a corrosion site rapidly propagates through-wall
as a corrosion-fatigue crack.
Casing, Liner, and Gas Baffle Damage. Casing and liner plate damage were common in early large
HRSGs, with hot spots typically evident on the casing surface, particularly around doors and
anywhere there is insufficient insulation. Liner plates are generally damaged by thermal buckling,
usually by caused by the bolting/welding design, overheating in firing ducts (due to radiant heat
transfer from burner flames) or from the use of materials with an inadequate temperature rating
(Figures 7–9). More recent designs by most HRSG OEMs have significantly reduced the incidence
of this type of damage. Most plants with extensive damage have repaired or replaced the affected
components.

7. This supplemental firing duct liner in a two-shifting plant experienced damage from radiant heat
transfer and the use of an inadequate material. Courtesy: Tetra Engineering Group, Inc.
8. The seal below the reheater outlet was damaged and replaced in this two-shifting plant. Courtesy:
Tetra Engineering Group, Inc.

9. A central baffle in this two-shifting unit failed. Courtesy: Tetra Engineering Group, Inc.

Duct Burners. Duct burners can adversely impact the integrity of downstream tubes if flame
impingement occurs. This typically happens when the firing duct is not sufficiently long to
accommodate the length of the burner flame. When flame impingement occurs, the end of the flame
is actually in the downstream tube panel. In this case, the burners need to be turned down to prevent
this damage. Duct firing also has advantages during certain low-load operations where the increased
steam flow helps “cool” high-temperature components and mitigate the increases in temperature
which might otherwise occur (Figure 10).
10. Duct burner flame impingement on the reheater first pass is illustrated. Courtesy: Tetra
Engineering Group, Inc.

Quench Damage. All HRSG OEMs assume a temperature variation in their panel design
calculations, and temporary thermocouples can assess whether the assumed variation is bounded
by the OEM’s assumptions. Some plants have also installed thermocouples to determine whether
steam binding is occurring in poorly vented HP economizers, although this issue is less common
with new design HRSGs. Water hammer caused by poor drainage or a leaking attemperator can
cause extensive damage, particularly steam piping (Figure 11).

11. Water hammer damaged this unit’s cold reheat piping and supports. Courtesy: Tetra Engineering
Group, Inc.

Attemperator sprays continue to be a significant problem for a variety of reasons, such as poor
engineering designs of spray line layout and control by manufacturers, premature failure of some
spray valve components in the field due to manufacturing/QC causes, and a demand for high spray
flow rates in order to control downstream metal temperatures to below design values.

Cold End Corrosion. Cold end corrosion is heightened in many merchant plants because they are
operating for more time at part load than anticipated by design. At part load, component surface
temperatures (principally the low-pressure economizer or feedwater heater) may operate below the
acid dewpoint temperature, which provides the environment in which acids will condense on tube
surfaces, causing corrosion damage.

Calculation of the acid dew point based on fuel gas constituents, emissions controls equipment
factors, and the specific thermal conditions for low-load operation can assess the expected severity
of the problem for a specific HRSG design. This problem is aggravated by greater than anticipated
sulfur content in fuel gas in some locations. Older units have employed CO2 blasting to remove some
of the deposits, but the effectiveness is limited if the affected section has many (deep) tube rows.
Those units with cold end corrosion problems generally have a combination of design and fuel gas
quality issues and are often characterized by frequent exposure of susceptible surfaces to high
ambient humidity with long periods of layup (Figure 12).

12. Deposits often form on low-pressure economizer or feedwater heater tubes when the metal
temperature is less than the dew point temperature of the exhaust gas. On this tube, the sticky
deposit has a pH of 3 and will soon cause cold end corrosion of the fins and tubes. Courtesy: Tetra
Engineering Group, Inc.

—Peter S. Jackson, PE (peter.jackson@tetra-eng.com) is director, field services, David S. Moelling,

PE (david.moelling@tetra-eng.com) is chief engineer, and James W. Malloy (james.malloy@tetra-
eng.com) is managing director (Europe) for Tetra Engineering Group, Inc.
 WATER TREATMENT
Microbial Control in Cooling Water
Improves Plant Performance
Microbial inhibition, as part of a robust cooling water treatment program, pres-
ents a special challenge because of the variability in makeup water sourc-
es, plant processes, and discharge permits. Failure to maintain a proper
microbial inhibition program will affect your bottom line as a result of
heat rate degradation.
By Ryan Forbes, AEP and Kevin Boundreaux and Aaron Haines, Nalco Chemical Co.
A
EP’s Conesville Station, located in
Conesville, Ohio, is a coal-fired con-
ventional steam plant rated at 1,695
MW. The plant consists of six units, three of
which (Units 4, 5, and 6) remain in service.
The three active units were commissioned
between 1973 and 1978. Like many plants of
this vintage, the chemical feed systems are
not as reliable as in the past and require addi-
tional maintenance. A loss in plant efficiency
and output often results from a loss in chemi-
cal feed system reliability, particularly the
plant’s biocide program. For example, loss in
condenser performance is directly related to
microbial growth on condenser tubes.
Units 4, 5, and 6 each use a closed cool-
ing water system for their steam surface con-
denser, with makeup water coming from the
nearby Muskingum River. Units 5 and 6 have
separate cooling towers, but their basins are
interconnected, making the two towers es-
sentially one system. Unit 4 uses a separate
cooling tower and recirculating system that is
completely independent of the other units.
The plant had been struggling with main-
taining its oxidizing biocide program for many
years because of equipment deficiencies, as
well as a dated chemistry application strategy.
Consequently, the plant staff struggled with
poor condenser performance that resulted in a
higher-than-design plant heat rate.
The staff of Conesville recently performed
a trial of ways to optimize the plant’s use of its
current biocides to determine the cost savings
of any improved microbial inhibition practic-
es. The microbial control tests were conducted
on the 780-MW Unit 4 cooling water system.
The results of the trial, as well as how those
results were used to justify the costs for new
feed equipment, are discussed below.
Perform Pretrial Research
Pretrial investigation revealed that the plant’s
poor microbial inhibition was caused by two
principal factors:
80
■ The chemical feed system was inadequate.
The biocide feed system consisted of two
pumps for each chemical that fed all three
cooling towers via a common header. This
configuration of cooling water piping did
not allow for proportional, consistent feed
of the biocide to each cooling tower. Con-
sequently, it was nearly impossible to feed
the appropriate amount of biocide to each
tower.
■ The water permits were restrictive. The
original interpretation of the discharge
permit suggested that the plant is only al-
lowed to chlorinate 2 hours per day. Dur-
ing that time, the total residual chlorine
(TRC) level in the outfall must be less than
0.2 ppm. At this feed rate and duration, the
result was a gross underfeed of biocide,
during which time the system was ripe for
microbial growth.
Further review of the permit indicated that
continuous chlorination was allowed, but the
outfall TRC residual was decreased to 0.038
ppm. This meant that a dechlorination system
on the outfall was a must.
Establish Trial Goals
The goals for the cooling water treatment tri-
al included completing three specific tasks:
■ Determine the efficacy of feeding oxidiz-
ing biocide continuously at low oxidant
residuals. This approach will minimize the
need for dechlorination at the outfall and
protect the cooling system from corrosion
due to elevated oxidant levels.
■ Determine the lowest, continuous residual
TRC necessary to maintain biological
counts within the industry standard of
<105 colony forming units (CFU)/ml.
■ Design a chemical delivery system ca-
pable of consistently supplying the nec-
essary amount of oxidizing biocide, both
bleach and CB70, to all three towers.
www.powermag.com
Trial Preparation
The plant staff installed a bisulfite feed skid
before the trial began so that continuous
chlorination was possible while complying
with the discharge permit TRC requirement.
The bisulfite was fed into the blowdown
stream whenever Unit 4’s blowdown was op-
erating. The feed rate was manually adjusted
because the concentration of the bisulfite did
not track the blowdown flow rate. Rather,
it was set to neutralize 1.0 ppm TRC at the
maximum possible blowdown rate.
The operating experience along the Musk-
ingum River suggested a daily usage of bleach
in the Unit 4 cooling tower of approximately
300 to 600 gallons per day, which has a re-
circulation rate of 305,000 gpm and a system
volume of 2 million gallons. The amount of
bleach added also fluctuates with tempera-
ture, organic loading, and plant power setting.
However, this range of expected bleach usage
was a good starting point for estimating the
theoretical size of the chemical feed systems.
Also recall that this biocide program uses a
bleach and stabilized bromine blend (CB70),
so the actual amount of bleach used would be
considerably less.
Testing and Data Collection
The trial period began July 12, 2012, and ran
until August 20, a total of 45 days. The chem-
icals were manually fed with adjustments
made based on the results of free chlorine
testing because the existing feed system was
incapable of continuously feeding the neces-
sary amount of bleach and CB70 to maintain
a target residual of 0.3–0.5 ppm. The tempo-
rary setup was sufficient to determine the ef-
ficacy of the proposed program and allowed
the close monitoring of biocide inventories,
which in turn aided in designing the ideal
feed system for the application.
For chlorine measurements, the plant be-
gan using the standard Hach DPD method, as
is typical in many applications. However, the
|
POWER May 2013
 WATER TREATMENT
fluctuating manganese in the makeup water
1. Free chlorine in water discharge. The chemical feed rate to maintain permitted
source, which is known to contribute to in- residual chlorine levels in the discharge was established during the 45-day testing period, July
terferences in the DPD method test results, 12 through August 20. Source: Nalco Chemical Co.
produced inaccurate results. The decision
was made to use the Hach amperometric test 1.0
method (Hach AutoCAT 9000 Method) to
0.9
ensure that there was no discharge of TRC
beyond the permit limits. Along with free 0.8
chlorine and TRC testing, microbial dipslide
0.7

Free chlorine (ppm)

tests (to test for the presence of microorgan-
isms in liquids) were performed weekly to 0.6
track the effectiveness of the biocide treat-
ment system. 0.5
Data collection consisted of downloading
0.4
and aggregating plant historian data plus data
from manual field tests. This historian data is 0.3
critical, as it contains important information
0.2
regarding overall plant operation, specifical-
ly condenser and cooling tower performance. 0.1
Once the data is compiled and analyzed, the
effectiveness of the biocide program can 0
7/
7/ 201
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01
mance of the very systems the program was

designed to protect.
Review Water Chemistry
The target TRC was set as 0.35–0.5 ppm
prior to the trial. However, biological mon-
2
itoring using dipslides determined that a
constant 0.15–0.2 ppm TRC maintained
the bulk water biocounts well below the
industry standard of less than 104 CFU/
ml (Figure 1). Meeting the biocount stan-
dard is particularly challenging because
the organically loaded makeup water from
the Muskingum River can rapidly change,

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|
May 2013 POWER www.powermag.com 81
 WATER TREATMENT
ide, NaOCl + H2O HOCl + NaOH. The are derivatives of ammonia by substitution of
2. Bleach and bromine dissocia-
tion are very dependent on pH. hypochlorous acid further dissociates into one, two, or three hydrogen atoms with chlo-
Source: Preventive Macrofouling Strategies hydrogen and hypochlorite ion, HOCl H+ rine atoms. The possible reactions proceed as
for Nuclear and Fossil Fired Power Plants, Ed- +OCl–, which is highly dependent on the pH follows:
ward W. Ekis, Jr., and Michael G. Trulear, Nalco of the water. According to the FILMTEC Re- HOCl + NH3– NH2Cl + H2O
Chemical Co. verse Osmosis Membrane Technical Manual HOCl + NH2Cl NHCl2 + H2O
published by Dow Water & Process Solu- HOCl + NHCl2 NCl3 + H2O
HOCI HOBr tions, “The germicidal efficiency of free On the other hand, bromine chemistry is
residual chlorine is directly related to the appreciably different than bleach. Because
concentration of undissociated HOCl. Hy- bromine is typically used in conjunction with
80 20 pochlorous acid is 100 times more effective bleach, HOCl + NaBr HOBr + NaCl.
than the hypochlorite ion OCl–. The fraction As with hypochlorous acid, the hypobro-
Un-ionized acid (%)

60 40 Ionized acid (%) of undissociated HOCl increases with de-
creasing pH” (Figure 2).
In practical terms, this means that as the
40 60
pH increases, the amount of free available
HOCl decreases. For example, a pH of 8.0,
20 80 which is typical for cooling tower applica-
tions, leaves approximately 20% HOCl, with
0 100 80% as OCl–. Therefore, it takes considerably
4 5 6 7 8 9 10 11 more bleach at elevated water pH to main-
pH
tain a specified TRC. Said another way, the
particularly during the hottest months of amount of bleach needed to control micro-
the year. biological activity increases as the water pH
Understanding how the bleach and bro- increases.
mine chemistry control organics is impor- Furthermore, when bleach reacts with or-
tant. As bleach is fed to water, it dissociates ganics, considerably less-effective biocides
into hypochlorous acid and sodium hydrox- called chloramines are formed. Chloramines
mous acid (HOBr) will dissociate into the hy-
pobromite ion (OBr–), which, as with bleach,
is also pH dependent: HOBr H+ + OBr–.
However, the percentage of available
HOBr is much higher at elevated pH rela-
tive to available HOCl. Recall in the previ-
ous example, that at a pH of 8.0, there is
approximately 20% HOCl, with 80% as the
less-biocidal OCl–. At that same pH, there
is approximately 80% HOBr, with 20% as
OBr–, a marked improvement.
In addition to dissociation advantages,
there are also two other notable benefits to
using bromine chemistry: The short-term
biocidal activity of OBr– is very similar to
HOBr, and any bromamines formed have

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82 www.powermag.com |
POWER May 2013
 WATER TREATMENT
viewing the data that follows. First, Unit
3. Low-pressure condenser TTD. Note the trend to lower condenser TTD during the
4 has a two-pressure, two-compartment,
trial, which indicates reduced microbial growth. Source: Nalco Chemical Co.
single-pass condenser, which means the
LP TTD (F) LP design TTD (F) cooling water flows first into the low-pres-
20 sure (LP) condenser compartment and then
through the high-pressure (HP) condenser
18 compartment.
Also, around July 8 the cooling tower
16
Low-pressure condenser TTD (F)

fan performance improved, which in turn

14 improved the vacuum pump and air remov-
al operation due to lower vacuum pump
12 seal water temperature. This explains the
sharp performance improvement a few
10
days before the biocide trial began. Finally,
8 as the biocide test began, Unit 4 was oper-
ating at less than 85% of rated capacity. It’s
6 best to run these tests at rated capacity so
the condenser is operating at design tem-
4
peratures, vacuum conditions, and steam
2 and water flow rates. When full rated load
Prior to trial Trial period isn’t possible, it is common practice to use
0 performance data when operating at 85%
6/10/12 6/20/12 6/30/12 7/10/12 7/20/12 7/30/12 8/9/12 8/19/12 8/29/12
of rated load and higher, which reflects the
data collected during the trial and used to
4. High-pressure condenser TTD. Source: Nalco Chemical Co. prepare the following figures.
The figures of merit selected to present the
LP TTD (F) LP design TTD (F) performance improvement are the terminal
20 temperature difference (TTD) and backpres-
sure penalty (BP penalty), arguably the most
18 important plant parameters when monitoring
condenser performance. The TTD reflects the
High-pressure condenser TTD (F)

16
heat transfer efficiency across the condenser
14 tube bundle and is usually affected by air in-
leakage, scale, and microbiological growth.
12 The BP penalty represents the steam turbine
performance loss caused by poor condenser
10
performance.
8 The historian data collected during the
45-day trial was processed using a special-
6 ly developed condenser performance moni-
toring tool (CPMT) program. The CPMT
4
takes the raw historian data and uses in-
2 dustry-accepted calculations to thoroughly
Prior to trial Trial period analyze the condenser performance. The
0 results of those calculations determine the
6/10/12 6/20/12 6/30/12 7/10/12 7/20/12 7/30/12 8/9/12 8/19/12 8/29/12 actual cost of condenser performance deg-
radation.
the same biocide effect as HOBr. These key at a pH between 8.4 and 8.8 (refer to Figure The split condenser requires care-
factors make bromine a much more effective 2), and the Muskingum River organic load- ful consideration of the performance loss
and persistent biocide. Using bromine allows ing can vary between 2 and 25 ppm. At this (TTD and BP penalty) imposed by scaling,
the plant to maintain a much lower oxidant elevated pH and organic loading, it would air in-leakage, and microbial formation in
residual while maintaining an effective mi- take a considerable amount of bleach to re- each compartment. The losses can then be
crobial inhibition program. duce bio-populations given the amount of summed to produce the final lost steam
Years prior to this particular trial, plant chloramines and OCl– that would be gener- turbine performance. There is also another
staff and Nalco consultants performed a ated. Therefore, a bromine-based chemistry important value in using these two metrics:
study that compared the performance of program was identified as the best choice to They are calculated independent of each
“bleach only” and “bleach/CB70 blend” op- control microbial activity and produce a con- other. The TTD is calculated using actual
tions. The study concluded that the blended tinuous, low TRC residual. measured parameters, while the BP penalty
biocide program provided a more effective is calculated using different measured pa-
microbial kill at a much lower TRC residual. First-Rate Results rameters as well as design data. This ap-
Based on the bleach and bromine chemistry Conducting a plant performance test when proach reduces the possibility of hidden
discussed above, this should be expected, control of the unit isn’t possible can be interactions where common data sources
because the cooling towers typically operate tricky. Consider the following when re- are used.

84 www.powermag.com |
POWER May 2013
 WATER TREATMENT

5. Low-pressure condenser BP penalty. Again, the trend to low backpressure (BP) Table 1. The economics of im-
during the trial indicates reduced microbial growth. Source: Nalco Chemical Co. proved biocide use. The biocide tests
delivered improved condenser performance
1.4 and therefore improved plant heat rate, or
reduced fuel consumption for a specified out-
1.2 put. Source: Nalco Chemical Co.

1.0 LP turbine HP turbine

Condenser vacuum (in HgA)

(Btu/kWh) (Btu/kWh)
0.8
Pretrial (July 1–11) 54.8 32.9
0.6 During trial 5.9 12.5
(July 13–14)
0.4 Improvement 48.9 20.4

0.2 Fuel savings calculation

Heat rate 69.3 Btu/kWh
0.0 improvement
Generation during 855,192 MWh
–0.2 trial
Prior to trial Trial period
–0.4 Coal heat value 11,577 Btu/lb
6/10/12 6/20/12 6/30/12 7/10/12 7/20/12 7/30/12 8/9/12 8/19/12 8/29/12 Coal cost $84/ton
Savings during trial $215,006
6. High-pressure condenser BP penalty. Source: Nalco Chemical Co. Cost of chemicals $12,000
Net saving during $203,000
1.6 trial

1.4 Net annual savings $1,650,000

1.2 Show Me the Money

The table illustrates the summary data col-
1.0
Condenser vacuum (in HgA)

lected and processed during the test pe-

0.8
0.6
0.4
0.2
0.0
–0.2
–0.4
6/10/12 6/20/12
The data shows that the TTD began to
improve shortly after implementing the
biocide program (Figures 3 and 4). The
design TTD is shown as a horizontal red
line, and data above the line reflect a loss
of condenser performance. During the trial
period, confidence is high that scale con-
trol was maintained at normal conditions
and there was no change in plant air in-
leakage. Therefore, the improved TTD is a
good representation of improved microbial
control. More specifically, the data reflects
effective removal and control of biofilm
production. Also, both the LP and the HP
compartments show TTD improvement,
indicating that both compartments were
experiencing significant microbial growth
prior to the trial.
Prior to trial Trial period
6/30/12 7/10/12 7/20/12 7/30/12 8/9/12 8/19/12 8/29/12
The BP penalty is calculated from many
parameters, including condenser water inlet
temperature, condenser heat duty, condenser
tube characteristics, design cooling water
flow, and the design condenser cleanliness
factor. In other words, the design backpres-
sure is determined assuming the condensers
are clean, with no air in-leakage, and are
operating under design conditions. The dif-
ference between the actual turbine backpres-
sure and the backpressure corrected to design
conditions is the BP penalty, or performance
lost due to heat transfer degradation. Figures
5 and 6 illustrate the BP penalty trends dur-
ing the trial. Note that these trends mirror the
TTD results, thus confirming the improved
performance can accurately be attributed to
the biocide trial.
riod, as well as the calculation procedure
used to estimate cost savings. Based on
the plant’s data and calculations, during
the trial period of 45 days, the plant real-
ized savings of $215,000 in reduced fuel
consumption simply by improving cooling
water biocide control. During this same
45-day trial period, costs for the biocide
program were estimated to be approxi-
mately $12,000, producing a net savings
of $203,000 during that 45-day trial pe-
riod, or about $1,650,000 for a full year,
assuming constant plant operations.
The impressive trial results enabled plant
staff to obtain approval for installation of a
new biocide feed system. In addition, the
chemical feed configuration will be upgraded
so that there are separate, redundant bleach
and CB70 feed pumps for each cooling tow-
er. The installed cost of the new system is ap-
proximately $106,000, which is less than the
$203,000 cost savings enjoyed by only Unit
4 during the short 45-day trial period. ■
—Ryan Forbes (rjforbes@aep.com) is
environmental and chemistry supervisor
at AEP’s Conesville Station. Kevin Bou-
dreaux (kjboudreaux@nalco.com) is an
industry technical consultant for Nalco’s
Power Business Unit. Aaron Haines
(aahaines@nalco.com) is a Nalco district
representative.

86 www.powermag.com |
POWER May 2013
Selecting a Combined Cycle Water Chemistry
Program

03/01/2013 | Colleen M. Layman, HDR Inc.

The lifeblood of the combined cycle plant is its water chemistry program. This is particularly true for
plants designed for high pressures and temperatures as well as fast starts and cycling. Even though
such plants are increasingly common, no universal chemistry program can be used for all of them.

In 1957, just a little more than 50 years ago, the first heat recovery steam generator (HRSG) was
connected to a gas turbine and the combined cycle power plant was born. However, it was not until
the mid-1970s that advances in high-temperature materials and air-cooling of gas turbine blades
made the combined cycle power plant commercially attractive. Development of the combined cycle
power plant design has rapidly improved, and today a variety of both simple and complex plant
configurations exist.

As designers strive to optimize cycle efficiency and heat recovery, the designs grow more intricate,
involving multiple pressure circuits, complex piping arrangements, and exotic materials. These
increases in cycle complexity and efficiency have also been associated with increases in the number
of HRSG tube failures. Data compiled by the Electric Power Research Institute (EPRI) indicated that
of the top five modes of HRSG tube failure, four (flow-accelerated corrosion, corrosion fatigue,
under-deposit corrosion, and pitting) had links to or could be influenced by cycle chemistry. (See the
sidebar for additional resources on these subjects.)

In the past, many attempted to apply the same guidelines established for industrial water tube drum-
type boilers to combined cycle power plants. For instance, in 1994 the ASME Research Committee
on Water and Steam in Thermal Systems published a ―Consensus on Operating Practices for the
Control of Feedwater and Boiler Water Chemistry in Modern Industrial Boilers‖ (ASME Publication
CRTD-34), but in 2001 it issued errata excluding HRSGs used in combined cycle power plants from
this original consensus document.

As the volume of operating experience on HRSG and combined cycle power plants grew, it became
clear that this class of power generating equipment had unique chemistry considerations that
needed to be addressed in a different fashion than typical water-tube drum-type industrial or power
boilers. In fact, last year the ASME Research Committee on Water and Steam in Thermal Systems
issued recommendations specific to combined cycle power plants.

What Makes Combined Cycle Plants Special?

There are so many different design configurations that selecting the proper chemistry plan and
establishing optimal chemistry operating limits can be challenging. Therefore, it is impossible to
develop universal guidelines.
Unlike most conventional fossil or nuclear power units, combined cycle power plants generally
operate at several temperatures and pressures. Multi-pressure HRSG circuits (low pressure [LP],
intermediate pressure [IP], and high pressure [HP]) within a common HRSG casing are the norm
rather than the exception, and these different circuits may be drum circuits, once-through circuits, or
a combination of both styles.

Combined cycle plants also are designed with complex flow patterns; during startup, some tubes in
the HRSG may sit stagnant or even flow in the opposite direction from operation. IP steam may be
utilized for combustion turbine cooling. The unit may be designed for fast starts or rapid cycling,
which can strain a chemistry program by restricting the plant’s ability to tolerate chemistry holds,
which have been standard fare in traditional fossil units. A whole host of design and operation
variations can exist and may affect the choice of chemistry program and limits.

By carefully considering each specific unit’s design and operational parameters, however, a solid
chemical treatment plan can be developed that balances the top concerns of plant operators today:
flexibility, cycling service, economics, and ease of use coupled with the need to protect and maintain
plant assets.

Today’s Treatment Programs

Four basic types of cycle chemistry programs are described by EPRI, ASME, the International
Association for the Properties of Steam and Water, and other entities. They are phosphate
treatment, caustic treatment, all-volatile treatment, and oxygenated treatment programs. Phosphate
and caustic treatment programs are only applicable to drum-style units, while oxygenated and all-
volatile programs can be implemented on once-through or drum-style units.

Phosphate Treatment Programs. Phosphate treatment programs for boiler waters have been
around for nearly 70 years and are probably the most commonly utilized treatment programs in
drum-style units. Coordinated phosphate chemistry was first introduced in the 1940s by Whirl and
Purcell and was based on the addition of trisodium phosphate (TSP) to the drum water.

In the 1950s, congruent phosphate treatment was introduced. This program, which was based on
maintaining a sodium-to-phosphate ratio in the range of 2.2 to 2.8, was designed to combat the
problem of caustic gouging that many plants operating on coordinated phosphate programs were
experiencing. Despite the successes that many plants experienced operating on the congruent
phosphate program, some units, particularly those operating at higher pressures (greater than 2,000
psi) and with higher heat fluxes, developed problems with phosphate hideout.

The 1990s brought another phosphate treatment program in response to those units that were
having difficulty with phosphate hideout: equilibrium phosphate treatment. The theory behind
equilibrium phosphate treatment was that each unit must independently determine its own
equilibrium point for phosphate. This approach considers the different operating conditions of each
boiler, such as boiler firing rate, unit cleanliness, heat flux, and fuel variations, all of which can affect
the maximum concentration of phosphate that a unit can tolerate without scale building up on boiler
surfaces.

The shift to equilibrium phosphate treatment was a positive step for many operators dealing with
phosphate hideout issues; however, implementation of this program was sometimes confusing, and
some of the units operating on equilibrium chemistry still experienced failures, but now the failures
were linked to hydrogen damage.
The latest revision to this long history of phosphate drum water treatment programs is the phosphate
continuum (PC) treatment program introduced by EPRI in 2004. Two forms of phosphate treatment
are provided for under the PC program—phosphate continuum low (PC(L)) and phosphate
continuum high (PC(H))—but there is no distinct boundary distinguishing the two treatments,
necessitating the term ―continuum‖ to describe the program. PC(L) treatment is designed for units
using high-quality demineralized makeup water using low levels (0.2 to 3 mg/l) of phosphate to deal
with low-level impurities in the cycle. PC(H) treatment is designed for units using lower-quality
makeup water and increased amounts (approximately 3 to 10 mg/l) of phosphate to deal with
impurities in the cycle.

PC chemistry requires the addition of TSP and sodium hydroxide (NaOH) to the steam
drums/evaporators, ammonia and/or an amine to the condensate/feedwater system to control the pH
of these streams, and possibly an oxygen scavenger to the condensate/feedwater system for
dissolved oxygen control. The operating ranges of pH and phosphate in the steam
drums/evaporators are bounded by the ratio of sodium (Na) to phosphate (PO4) = 3 and TSP + 1
mg/l NaOH (Figure 1).

1. Phosphate continuum control chart. The chart provides a visual interpretation of the phosphate continuum

operating ranges illustrating target pH and phosphate concentrations. Source: Derived from “EPRI Cycle

Chemistry Guidelines for Combined Cycle/Heat Recovery Steam Generators,” Technical Report 1010438, March

2006

Caustic Treatment Programs. Caustic treatment (CT) programs have been used successfully in
drum-style units where difficulties with phosphate hideout have been experienced. CT programs
have been historically more popular in European countries than in the U.S.; many U.S. units
abandoned the use of these treatment programs in the 1960s due to caustic gouging problems in
higher-pressure units. Recently, however, this type of treatment program has been regaining
popularity in the U.S. as plants investigate solutions to deal with the challenges encountered in
utilizing phosphate treatment programs.

In CT programs, a low concentration of sodium hydroxide is added to the drum/evaporator water to

achieve the recommended pH in the drum and provide protection against corrosion. As in phosphate
treatment programs, ammonia and/or an amine is also added to the condensate/feedwater system
for controlling the pH of these streams, and an oxygen scavenger may be added to the
condensate/feedwater system for dissolved oxygen control.

The sodium hydroxide dosage rate is determined based on drum operating pressure to control the
amount of sodium carryover in the steam to a target of less than 2 µg/l. As drum pressure increases,
the dosage rate of sodium hydroxide decreases along with the protection level that this treatment
program provides. Therefore, CT programs are impractical for implementation in units operating
above 2,400 psi (Figure 2).

2. Caustic injection control chart. This is a visual interpretation of the

sodium hydroxide dosing rates recommended by EPRI. Source: Derived

from “EPRI Cycle Chemistry Guidelines for Combined Cycle/Heat

Recovery Steam Generators,” Technical Report 1010438, March 2006

All-Volatile Treatment Programs. All-volatile treatment (AVT) programs have a long history of
successful application in conventional fossil units and are applicable to combined cycle power plants
that operate with high-quality demineralized water and very good feedwater quality. There are two
basic variations of AVT programs utilized in plants today: oxidizing all-volatile treatment AVT(O) and
reducing all-volatile treatment AVT(R). Full-flow condensate polishing is strongly recommended for
units designed to operate using either AVT(O) or AVT(R) chemistries due to the extremely limited
ability of units operating under these chemistry regimes to tolerate contaminant ingress. Polishers
are especially necessary for units designed with seawater or high total dissolved solids (TDS)
circulating cooling water.

AVT(O) is only applicable to units designed with all-ferrous metallurgy and utilizes ammonia or a
neutralizing amine to elevate the pH of the condensate and feedwater to maintain a pH greater than
9.4 in the LP drum, thus minimizing flow accelerated corrosion (FAC). This typically requires that the
pH of the condensate/feedwater be controlled to a minimum level of 9.6. A pH adjustment chemical
is the only additive for the cycle in this treatment scheme. The dissolved oxygen concentration in the
system is controlled solely through mechanical means, creating a slightly oxidizing environment and
a slightly positive oxidization reduction potential (ORP).

AVT(R) is recommended for units designed with copper alloys in the system and units with steam
hosts. Like AVT(O), this program utilizes ammonia or a neutralizing amine to elevate the pH of the
condensate and feedwater. However, the pH under this treatment scenario is limited to a maximum
of 9.1 in order to minimize copper transport in the system. An oxygen scavenger such as hydrazine
or carbohydrazide is also added to the condensate/feedwater to control dissolved oxygen in the
system and provide protection of the copper-based alloys. The addition of the oxygen scavenger
creates a reducing environment and a corresponding negative ORP.

Oxygenated Treatment Programs. Oxygenated treatment (OT) programs are not commonly
utilized in combined cycle power plants due to the cycling nature of most plant designs, but these
treatment programs may be applicable for some baseloaded plants or for plant designs that include
once-through HRSG pressure circuits.

OT programs, also sometimes called combined water treatment (CWT) programs, use oxygenated
high-purity water to minimize corrosion and FAC in the feedwater system. This type of chemistry is
only suitable for units that contain all-ferrous metallurgy in the cycle and that do not experience
routine cyclic operation. Full-flow condensate polishers are required in the design to maintain the
feedwater purity required to employ these treatment regimes.

OT utilizes ammonia or a neutralizing amine to elevate the pH of the condensate and feedwater.
Copper alloys in the cycle, downstream of the condensate polisher, are not compatible with OT
programs, as the presence of oxygenated water will result in dissolution of those alloys at an
accelerated pace. In a drum-style circuit, the pH is maintained within the range of 9.0 to 9.4; in a
once-through style circuit, a lower pH range is frequently permitted, approximately 8.0 to 8.5.

The optimal pH of the circuit must be determined in the field and should be based on minimization of
iron transport in the cycle. An oxidant is also fed to the condensate/feedwater to create the oxidizing
conditions in the cycle that promote formation of the protective cover layer on the ferrous materials.
The most commonly used oxidant is oxygen gas. Air and liquid oxygen are also utilized in some
plants. Air, however, contains undesirable contaminants such as carbon dioxide and, therefore, its
use is generally discouraged.

Chemistry Selection Recommendations

Ideally, selection of the proper chemistry protocol should be done early in a project’s design phase,
and material selection and component specification should be performed with the specific chemistry-
monitoring and control requirements in mind. Design parameters for the unit and the chemistry
program need to go hand-in-hand; there is no one-size-fits-all chemistry program, and even the best
treatment program cannot compensate for improper material selection or poorly designed system
components.

The process of selecting the chemistry treatment program needs to keep the uniqueness of the
combined cycle plant in mind and should consider many plant parameters, including steam purity
requirements, condenser cooling system design, presence and type of condensate polishers,
potential for condensate contamination, condensate and feedwater system metallurgy, cycle design,
operating pressure, the use of duct burners, cycling service or quick-start requirements, and the
availability of a chemist to quickly implement corrective action—should it be required.

HRSG and Steam Turbine. In selecting the best cycle chemistry treatment program and deriving
operational chemistry limits specific to a given unit, one should begin by compiling and analyzing the
steam turbine, HRSG, and combustion turbine original equipment manufacturers’ (OEM) specified
chemistry limits. The easiest way to do this, in general, is to begin with the steam turbine OEM limits
and work backwards through the cycle to calculate the chemistry required in the HRSG and
condensate/feedwater to meet these limits, considering the manner in which the plant is designed to
operate.

In some instances, however, the HRSG or combustion turbine components may have limits based
on their design or operation that are more stringent than the chemistry requirements dictated by the
steam turbine limits. One specific example is a combustion turbine design where IP steam is utilized
for cooling. In this instance, the purity of the IP steam to meet the combustion turbine requirements
is more stringent than the purity that would normally be required based on steam turbine OEM limits.
This is why it is important to collect and review all chemistry guidelines supplied by the OEMs for all
major pieces of equipment.

The addition of multiple separate pressure circuits to the HRSG to supply IP or LP steam for
services such as deaeration and feedwater heating has been an important improvement in the
steam cycle efficiency and has been applied to most combined cycle power plant designs. Steam
from these IP and/or LP circuits replaces the steam extraction regenerative feedwater heating
design used in conventional steam power cycles. This design combines separate HRSG circuits with
varying operating pressures within a common HRSG casing but typically utilizes a common
condensate/feedwater system to supply water to all of the circuits.

It’s true that IP and LP circuits may have less-stringent chemistry requirements than the HP circuit
strictly based on operating pressure under standard water tube boiler guidelines. But the
intermingling of condensate, feedwater, and steam systems within the combined cycle power plant
generally requires all HRSG circuits to be restricted to the same chemistry limits as the highest
pressure circuit.

Although originally intended to improve simple cycle plant efficiency by absorbing and utilizing the
waste heat from a gas turbine or turbines in a steam turbine, many HRSGs are now designed to
incorporate the routine use of duct burners. The use of duct burners can significantly increase the
operating pressures of all HRSG circuits and considerably increase the unit’s steaming rate. When
choosing operating chemistry limits and the appropriate treatment for the HRSG, operators and
designers need to consider these higher operating pressures as limiting design conditions.
Operating experience has shown that the most prevalent cause of phosphate hideout in a HRSG is
operation of the duct burners. The degree of hideout experienced generally varies with the firing
capacity of the duct burners: The greater the rate at which a unit is duct fired, the more severe the
hideout issues experienced generally are. Frequency of duct burner use should be factored into the
chemistry selection process, and unit testing during duct burner operation should be performed to
determine how a given unit will respond if a phosphate treatment program is selected for application
at the facility. If phosphate hideout is severe and maintenance of proper drum chemistry becomes a
challenge, the operator may be better served by implementing a caustic or AVT program at the
plant.

Several once-through HRSG designs are available that do not include a steam drum in one or more
of the various HRSG pressure circuits. Drum-type units utilize a steam drum not only for water/steam
separation but also for concentration and removal of impurities in the system. Once-through units, on
the other hand, are designed such that feedwater is pumped into the HRSG in the liquid phase and
is converted to steam as it passes through the heat exchangers in the HRSG. No provisions are
provided in this design for concentration and mechanical removal of impurities. Whatever
contaminants are present in the feedwater are transported to the turbine in the steam. Therefore,
condensate and feedwater must be maintained very pure and must match the steam turbine OEM’s
steam purity requirements. Condensate polishing is crucial to establishing and maintaining this high
level of purity in the cycle, and chemistry choices are limited to OT and AVT programs.

At drum pressures of 2,400 psi or higher, contaminants such as sodium and chloride present in the
boiler water easily vaporize with the steam and carry over to the steam turbine. This is due to the
―partition coefficient,‖ or the ratio of the concentration of these contaminants in the steam versus in
the water, which begins to increase rapidly at pressures above 2,400 psi. Due to concerns with
carryover, phosphate and/or sodium hydroxide addition is not recommended for HRSG drums
operating 2,400 psi or higher drum pressures.

Condensate/Feedwater System. Selection of a cycle chemistry treatment program is significantly

simplified when the system metallurgy is all ferrous and no copper alloys are present in the cycle.
This includes the condenser tubes, feedwater heater tubes, condensate and feedwater pumps, and
any heat exchangers belonging to a host that receives steam supply from the plant. Copper alloys
possess excellent heat transfer characteristics but are susceptible to ammonia attack and, therefore,
the presence of these alloys in the system limits operating pH in the condensate and feedwater to
approximately 9.1. Operation at this lower pH does also increase the system’s risk of FAC. Systems
with copper alloy components can not operate on AVT(O) or OT. Chemistry treatment programs for
these units are limited to AVT(R), phosphate, or caustic.

For all-ferrous units, all four types of treatment programs are applicable. However, it is strongly
recommended that oxygen scavengers not be utilized in all-ferrous systems due to the potential link
between a reducing environment in the condensate/feedwater and single-phase FAC. Two-phase
FAC, on the other hand, which is common in many HRSG LP evaporator circuits, is not impacted by
reducing or oxidizing chemistry (the addition or absence of an oxygen scavenger). To protect against
two-phase FAC, boosting the pH of the LP evaporator by adding sufficient ammonia (in AVT
programs), TSP (in phosphate treatment programs), or sodium hydroxide (in phosphate and/or
caustic programs) directly to the LP drum to increase the pH of the drum water above 9.6 is
recommended.

Adding phosphate or caustic, however, is not always possible in the LP evaporator. The chemical
treatment of the LP drum varies depending on HRSG arrangement. In some configurations, each of
the HRSG drums receives feedwater in parallel from the condensate/feedwater system. In other
configurations, some of the drums are in series with drum water from one drum (usually the LP)
providing feedwater to other steam drums (usually IP and HP drums). In configurations where the LP
drum is the feedwater source for higher-pressure (IP and HP) drums, phosphate or sodium
hydroxide cannot be added to the LP drum to provide protection against two-phase FAC. The same
challenge exists in designs where water from the LP drum is used for steam attemperation. In
designs where water from the LP drum is used for steam attemperation, the LP drum water must
meet the same purity requirements as the steam itself and, therefore, the addition of caustic or
phosphate to the LP steam water is not permitted.

Whether or not the condensate system is designed to include condensate polishers has a big impact
on the selection of the cycle chemistry program. The design of any unit must include a means to
handle the ingress of any impurities that may enter the system via condenser tube leaks, air in-
leakage, makeup demineralizer operational issues, and the like. If condensate polishers are included
as part of the plant design to remove any impurities that find their way into the system, AVT and OT
chemistry programs can be utilized. If no condensate polishers are included in the plant design,
phosphate or caustic treatment programs should be employed to buffer or neutralize any ingress of
impurities and minimize corrosion and deposition in the system.

Looking for More HRSG Water Chemistry Resources?

The POWER online archives are an excellent resource for those researching plant water chemistry
topics, as well as other plant design, operation, and maintenance issues. For example, the following
are 10 related articles, in alphabetical order, that discuss real-world experience with plant water
chemistry and tube corrosion.

 ―Condensate Polishers Add Operating Reliability and Flexibility,‖ August 2008

 ―Reconsider Startup Controls to Avoid Boiler Deposits and Underdeposit Corrosion,‖ May 2009
 ―Cycle Chemistry Commissioning Deserves Its Own Strategy,‖ September 2012
 ―Designing HRSGs for Cycling,‖ March 2006
 ―Designing Steam Cycles to Avoid Corrosion,‖ April 2006
 ―Make Your Plant Ready for Cycling Operations,‖ August 2011
 ―Organics in the Boiler and Steam: Good or Bad?‖ September 2006
 ―Put a Lid on Rising Chemical Costs,‖ September 2008
 ―Ten Years of Experience with FAC in HRSGs,‖ September 2010
 ―Water Chemistry an Important Factor to Consider for Cycling HRSGs,‖ May 2007
You can search the archives by issue (at the Archives link) or by keyword, using the Search box in
the upper right corner of our homepage, http://www.powermag.com. The updated search feature
now automatically searches POWER and all sister publications— COAL POWER, GAS POWER,
MANAGING POWER, and POWERnews.

Plant Operating Regimes Must Be Considered

The proper water treatment process must be selected for the operating conditions and type of
equipment, as just discussed. How the equipment is operated is equally important, as the water
treatment process may be remarkably different at a baseload plant, a cycling plant, and one of the
new generation of fast-start plants.
Cycling Service Considerations. Although phosphate treatment programs are designed to provide
good buffering capability for drum units, cycling operation while utilizing these treatment regimes has
been linked historically with phosphate hideout problems, where the concentration of the phosphate
in the boiler/HRSG seems to ―disappear and reappear‖ as the unit makes significant load changes.
When the phosphate ―disappears,‖ operations staff typically try to correct the situation by adding
more chemical, which usually results in an overfeed situation when load changes again and the
phosphate ―reappears.‖

Any drum-level control problems that result as part of the load swings can also result in mechanical
carryover of phosphate and sodium from the drum to the superheater sections and the steam
turbine, leading to potential deposition and corrosion. Oxygenated treatment programs are also best
suited for steady load–type operations, whether the unit is a drum or once-through type boiler.

Boilers operating in a cycling mode are best served chemistry-wise by employing an AVT program
coupled with full-flow condensate polishing to remove any contaminants that may enter the cycle.
Units with copper-bearing alloys in the steam system should employ AVT(R) chemistry, where
ammonia/amine is added to the condensate/feedwater to control pH and an oxygen scavenger is
also added to the condensate/feedwater to minimize dissolved oxygen concentration. Ferrous-only
units are best served by implementing an AVT(O) chemistry program where ammonia/amine only is
added to the condensate/feedwater. It is recommended that inorganic chemicals (such as
ammonium hydroxide and hydrazine) be used as the pH adjuster and oxygen scavenger, but there
are numerous organic substitutions on the market today that will also yield good results when
properly applied under the advice of a water treatment expert.

Fast-Start or Rapid-Response Designs. Several ―fast-start‖ or ―rapid-response‖ HRSG designs

have made their way into the combined cycle market in recent years. These units—developed
usually through collaborative efforts among the steam turbine, gas turbine, and HRSG OEMs—
feature combined cycle power plant designs that are intended for quick startups and/or very quick
and frequent load swings. These designs, while providing the swift reaction to the electric grid needs
that today’s power market demands, also complicate steam cycle chemistry issues.

Chemistry, like the HRSG and steam turbine equipment, must now also be flexible enough to
respond to fast startups and/or very quick and frequent load swings. These plants cannot tolerate
chemistry holds that have been standard in traditional fossil units and still meet their startup time or
load swing guarantees. Therefore, use of high-quality makeup and maintenance of
condensate/feedwater purity are primary concerns for projects that utilize a fast-start or rapid-
response design.

Such plants should ideally include permanent condensate polishers as part of their standard design
to maintain condensate and feedwater purity and minimize chemistry holds. For Siemens’ once-
through Benson boiler design, for instance, condensate polishers are required because the HP
portion of the HRSG is designed to operate on OT chemistry, and therefore condensate polishers
are a key part of this chemistry treatment program. For other fast-start designs, AVT chemistry
programs coupled with a condensate polisher are generally the best choice to maintain a clean cycle
and respond rapidly to changes.

Other Water Chemistry Issues

Plants incorporating an air-cooled condenser (ACC) for condensation of the steam turbine exhaust
have unique requirements for their cycle chemistry treatment program.
The ACC design consists of a very large surface area for condensation of the exhaust steam.
Though this large surface area works well for heat transfer purposes, it can upset the steam-water
cycle chemistry. Newly erected ACCs are difficult to completely clean and tend to contribute a
substantial amount of contaminants to the cycle during initial startup and even during unit restart if
vacuum has been broken. The large surface area also increases the likelihood of iron transport in
the system, particularly during initial startup and during unit restarts, and the potential for air in-
leakage in the system. Owners should seriously consider including a condensate polisher when
using an ACC.

FAC concerns are also common in the ACC. In order to minimize FAC in an ACC, the pH in the early
condensate must be increased above that required for an equivalent water-cooled condenser. HP
feedwater pH should be maintained in the range of 9.6 to 9.8 to minimize FAC in the ACC. This may
require supplemental chemical injection for the HP steam drum or HP feedwater.

Steam from auxiliary boilers is frequently utilized in combined cycle power plants for purposes such
as pegging the deaerator during startup, holding vacuum overnight, or hotwell sparging. The purity of
the steam coming from the auxiliary boiler must be the same as the steam produced in the main
cycle. Therefore, the chemical treatment program utilized for the auxiliary boiler must be compatible
with the operating pressure and temperatures of the main cycle, even though the auxiliary boiler
typically operates at lower pressures and temperatures.

For instance, nonvolatile oxygen scavengers are frequently used in industrial boilers operating at low
pressures (less than 800 psi). However, if the industrial boiler is serving as an auxiliary boiler that is
supplying steam to an HRSG with a HP pressure of over 800 psi, volatile oxygen scavengers such
as hydrazine or carbohydrazide must be used in treating the auxiliary boiler, just as in the main
steam cycle.

Consider Plant Staffing

The plant staffing plan and operating experience level of the team may also affect the choice of
chemistry treatment for a unit. Managing a high-performance chemistry program (AVT or OT)
requires tighter operating controls, more supervision of plant makeup water treatment systems and
chemical additions, and a higher-level knowledge of steam cycle chemistry practices. An operations
team supported by a dedicated on-site plant chemist or chemistry technician specifically trained in
these practices is preferable. If the facility is unable to provide this level of support and supervision
of steam cycle chemistry, the better option is to use a phosphate chemical treatment program, which
can be more forgiving when system upsets occur.

— Colleen M. Layman (colleenlayman@hdrinc.com) is the energy-water management practice

director for HDR Inc.
Battling White Rust
Does your power plant use a chiller for combustion turbine in-
let air cooling or other processes that reject heat? If so, there
is a good chance you also have an auxiliary cooling tower
(Figure 1) or a wet surface air cooler (WSAC, Figure 2) to cool
these systems. (See POWER, September 2008, “Wet Surface
Air Coolers Minimize Water Use by Maximizing Heat Transfer
Efficiency.”) Galvanized steel has been commonly used in the
construction of smaller, package-type cooling tower systems
because it is relatively inexpensive. These cooling towers are
popular in many different industries and will increase in use
in power applications.
Those of us who work in the water treatment industry are
familiar with the smaller, package-type cooling towers from
our experience in the food and beverage, institutional, and
manufacturing business units. These units are typically con-
structed using galvanized and stainless metallurgies. How-
ever, many in the power industry are only familiar with wood
or fiberglass-reinforced plastic (FRP) because these are the
materials most commonly used in the construction of field-
erected cooling towers at central station power plants.
1. Cool breeze. This is a typical auxiliary evaporative cooling tower.
Courtesy: Nalco Power ITC
2. Go with the flow. The co-current flow of air and water (both
flow downward) in a wet surface air cooler increases the system’s heat
transfer efficiency. Courtesy: Nalco Power ITC
14 www.powermag.com
A cooling water treatment program must consider not just
the galvanized, wood, or FRP but also all the materials that
the water will come into contact with throughout the plant,
such as titanium, stainless steel, and copper-based alloys
used in the condenser and possibly other balance-of-plant
heat exchangers.
The question of acceptable chloride levels in the bulk cool-
ing water always comes up anytime stainless steel alloys are
used. Typically, the engineering firm responsible for the plant
design will select appropriate materials and a water chemistry
program that ensure chloride levels in the cooling water are
kept at acceptable levels, depending on the grade of stain-
less. When stainless steel is used, developing an acceptable
water treatment program is straightforward.
Galvanized cooling towers are a much different story. Al-
though rare in the power industry, towers using galvanized
steel components are becoming more popular with the in-
creased use of chillers for inlet air-cooling combustion
turbines in combined cycle plants, as well as WSACs in the
air-cooled configuration.
In general, all cooling towers are very sensitive to wa-
ter chemistry, particularly chlorides, sulfates, and alkalinity.
These constituents are often overlooked when designing a
cooling water treatment program. (See POWER March 2013,
“Selecting a Combined Cycle Water Chemistry Program” and
September 2009, “Avoid These 10 Mistakes When Selecting
Your New Water Treatment System.”) Even so, using galva-
nized parts within a cooling tower makes the problem of wa-
ter treatment even more difficult—the water is tough on the
galvanized parts, and the power industry operates cooling
towers at much higher cycles of concentration than other
industries.
Finally, the propensity for white rust formation in galva-
nized systems is not very well known in the power industry.
The remainder of this article will define white rust, how it
is formed, its potential impacts on equipment integrity, and
how to control its formation.
Galvanized Steel and White Rust
Galvanized steel is carbon steel with a coating of zinc metal
on its surface. Either a hot-dip or electroplating process can
produce a zinc layer that is a protective surface coating as
well as a sacrificial anode. Because zinc is less noble than
carbon steel, it will corrode sacrificially to protect the under-
lying base metal. If the protective zinc layer should corrode
through, the base-layer steel will corrode at the same rate as
unprotected carbon steel. It is important to note that gal-
vanized steel will always have some small amount of general
corrosion occurring, just as with mild steel. The key is to
minimize those general corrosion rates while minimizing the
potential for localized corrosion.
When a galvanized steel system is operated under nonag-
gressive conditions such as a neutral pH and moderately hard
water, a protective layer of nonporous zinc carbonate and
zinc hydroxide forms to prevent further corrosion of the zinc
coating. However, if the system is operated under aggressive
conditions such as high pH, low hardness, or high chloride or
sulfate levels, rapid corrosion of the protective zinc layer can
occur. If the corrosion is severe, all the galvanized coating
|
POWER April 2013

3. Corrosion begins. White rust on a galvanized panel is caused
when the protective zinc coating is attacked. When the galvanized sur-
face is penetrated, the steel base metal will begin to corrode. Cour-
tesy: Nalco Power ITC
will be removed, exposing the unprotected steel, producing
the familiar rusty-brown or black appearance. In less-severe
cases, the zinc coating can be corroded to form what is known
as “white rust” (Figure 3).
Both the protective oxide film and white rust are forms of
CIRCLE 9 ON READER SERVICE CARD
|
April 2013 POWER www.powermag.com
zinc carbonate and zinc hydroxide. The difference between
the two is the rate of formation and the density of the layer.
Rapid formation of an oxide film produces a porous deposit
that allows continued corrosion of the nonpassive surface, if
left unchecked. A slower formation of the zinc layer provides
a nonporous, protective layer.
A common misconception is that once the layer of white
rust has formed, no further corrosion can take place. Not only
is this not true, but the corrosion byproduct also can create
an oxygen concentration cell, creating an accelerated local-
ized corrosion reaction. This situation is further complicated
with the addition of high levels of sulfates and chlorides.
As stated in the Nalco Guide to Cooling Water System Failure
Analysis (1993), “Once the zinc layer is breached, the un-
derlying steel becomes susceptible to attack and is severely
wasted locally” (Chapter 5, p. 108). The reference book also
notes: “On galvanized steel, tubercles may develop rapidly at
breaches in the zinc layer. Attack is frequently highly local-
ized if aggressive ions such as chloride or sulfate concentrate
beneath deposits” (Chapter 4, p. 72).
White rust has a porous, soft, gelatinous, or waxy appear-
ance and is relatively easy to identify. The galvanized zinc
coating can be severely damaged when white rust is formed,
which in turn can shorten the life of the cooling tower. Also,
because white rust formation can be highly localized, once
the zinc layer has been consumed, corrosion of the mild steel
may progress rapidly, as with any penetration of a metal coat-
ing. White rust is typically caused when operating outside of
the typical guidelines for the cooling water pH and alkalinity.
17
However, many cases of white rust have been attributed to for slow formation of the protective layer. Second, the passi-
improper passivation of a new or newly cleaned system, which vation process can and should be repeated periodically if the
is typically caused by compressed commissioning schedules tower is operated outside the manufacturer’s guidelines dur-
and short-circuited cleaning steps. ing normal operation. This is not to say the normal operating
White rust can quickly become a very costly problem. Not chemistry can be significantly outside the guidelines and
only does it cause heat exchanger degradation across the still be reconditioned. Reconditioning does not restore the
tube bundle during normal operation, but also cleaning and lost galvanized surface when severe damage to the zinc coat-
remediating a system with white rust can be a costly ven- ing has occurred. Frequent visual inspection is recommended
ture. Remediation typically requires mechanical brushing of to ensure damage to the zinc coating caused by white rust
the affected area, painting with an aluminum paint or epoxy formation is not taking place.
coating, followed by a repassivation of the system. These Coat the Galvanized Steel. If galvanized steel is to be
steps may need to be repeated, depending on the severity used with an aggressive water treatment program, then coat-
of the white rust (BAC Technical Resource Document - RLD ing the metallurgy may be an option to consider. For instance,
1069–9/2010). BAC uses Baltibond, a special hybrid polymer that is imperme-
able to fluids. This material is applied by electrostatic spray
Preventing White Rust Formation to G-235 (Z700 metric) hot-dip galvanized steel surfaces. The
A better strategy for battling white rust is to take steps to pre- initial and periodic seasoning of the system is not needed
vent its formation in the first place. There are five preventive when this coating is applied. Although the coating will pro-
steps you should consider. tect the structural surfaces, “hot-dip galvanized coils must
Choose a Different Metallurgy. The obvious first option use the water quality guidelines for galvanized steel units,”
would be to select a different alloy—one chosen specifically
with the makeup water chemistry in mind. As more plants
become reliant upon relatively aggressive makeup water from Table 1. Typical cooling tower chemistry guidelines.
Source: Cooling Tower Institute
nonstandard sources such as high-conductivity well waters
and municipal gray waters, the use of galvanized steel for Parameter Range
cooling tower construction should start to diminish. How-
ever, one of the attractions to using galvanized steel towers pH 7.0–8.0
is the often lower first cost, which may drive the purchase Chloride as Cl- <450 ppm
decision. If that is your situation, then other solutions must Sulfates as SO42- <1,200 ppm
be explored.
Alkalinity as CaCO3 50–300 ppm
Operate Under Manufacturer’s Guidelines. Though not
popular in the power industry, galvanized cooling systems Hardness as CaCO3 >50 ppm
have been used extensively in other industries with very good
success. The difference between success and failure can be
as simple as following the manufacturer’s guidelines. Our ex- Table 2. Galvanized cooling tower chemistry guide-
perience has been that when users follow the manufacturer’s lines. Source: White Rust Prevention—An Industry Update and Guide
guidelines to the letter, they tend to not have white rust (2012), Association of Water Technologies
formation on their galvanized towers. However, those who
deviate from the guidelines tend to suffer with either white Parameter BAC Evapco Marley
rust in the wetted areas or sulfate and chloride attack in the Reference Operating manual Engineering Manual 92-114B
wet-dry areas. This is particularly true of those users who bulletin 036A
operate with very high cycles of concentration. Passivation 4 to 8 weeks 4 to 12 weeks Minimum of 8
Those in the power industry often overlook the fact that duration weeks
these package cooling towers tend to have a greater per- pH during >7.0 to <8.2 >7.0 to <8.0 >6.5 to <8.0
centage of drift than field-erected cooling towers. When drift passivation
occurs in galvanized systems, the evaporated salts can ac-
pH for routine 6.5 to 9.0 >6.0 to <9.0 None found
cumulate on the external structure and attack the galvanized
service suggested
surfaces. The tube-bundle will appear very well protected, but
the structure of the cooling tower is deteriorating. Hardness as >30 ppm >50ppm 100 to 300 ppm
CaCO3
Discovering the acceptable chemistry limits for white rust
prevention can be a bit complicated. As Table 1 shows, the Alkalinity as <500 ppm <300 ppm 100 to 300 ppm
Cooling Tower Institute guidelines have a much higher limit CaCO3
for sulfates and chlorides than the three leading manufactur- Chlorides as Cl- <250 ppm <250 ppm None found
ers of galvanized cooling towers (Table 2). Following the con- Sulfates as SO42- <250ppm <250 ppm None found
servative, manufacturer guideline for your particular tower is
Conductivity <2,400 microS <2,400 microS None found
the most prudent approach.
Complicating the decision, however, is the presence of two Chlorine as free <1.0 ppm as a <0.5 ppm as a None found
competing pH guidelines: operating pH for the passivation Cl2 routine routine
process as well as the manufacturer’s recommended operat- Comments BAC offers Critical to have a Chromate rinse
ing pH for routine service (Table 2). The former guideline removal and passivation plan used for heavy
is important for two reasons. First, the initial passivation treatment and assigned mill galvanized
process seasons the galvanized steel, making it ready for recommendations responsibility prior steel sheet
for white rust to startup
normal service. The initial passivation is designed to allow

18 www.powermag.com |
POWER April 2013
according to BAC Series V operating and maintenance instruc- have been no water chemistry offerings to inhibit the forma-
tions. In other words, the coating may prevent white rust tion of white rust. However, Nalco researchers have devel-
formation on structural surfaces, but it will not prevent cor- oped a chemical program that has proven to provide good
rosion of the tube bundle. Therefore, the chemistry guidelines protection for galvanized steel systems. Nalco 73801WR is
in Table 3 must still be followed. a synergistic blend of passivation agents that can minimize
Use Chemical Corrosion Inhibition. Until recently, there white rust corrosion. Because NALCO 73801WR is specifically
intended to inhibit white rust formation, it is designed to
supplement other treatment programs such as mild steel cor-
Table 3. BAC chemistry guidelines. Source: BAC Series V rosion inhibition and scale inhibition (Figure 4).
and Low Profile V—Cooling Towers, Closed Circuit Cooling Towers, and The corrosion rates for galvanized systems dropped signifi-
Evaporative Condensers Operating and Maintenance Instructions
cantly, from 0.75 mils per year (mpy) to 0.1 mpy after the ini-
Parameter Baltibond Galvanized steel
tial feed of Nalco 73801WR on a test cooling tower. Although
the corrosion rate rises and levels off at 0.25 mpy, that still
pH 6.5 to 9.0 7.0 to 9.0
translates into a 67% reduction in corrosion rate.
Hardness as CaCO3 30–500 ppm 30–500 ppm Another example involves a plant using a makeup water
Alkalinity as CaCO3 500 ppm max 500 ppm max source high in conductivity, alkalinity, sulfates, and chlo-
ride, while operating at relatively high cycles of concen-
Total dissolved solids 1,200 ppm max 1,000 ppm max
tration for a galvanized cooling tower. This tower is also
Chloride as Cl- 250 ppm max 250 ppm max experiencing promising results using Nalco 73801WR (Table
4). This is a fairly new trial, so corrosion rates are not avail-
able yet. However, photos show excellent protection of the
4. Good results. The initial test results of Nalco 73801WR have system (Figure 5).
been excellent. This figure shows the results of a trial performed in a Determine the Dose Rate. The typical dose rate for Nalco
power plant closed-loop system. Source: Nalco Power ITC 73801WR is 50 ppm. However, halogen use rates and water
conditions may dictate higher dose rates. Because there is
1.2 no Trasar component in this chemistry, the additive dose rate
1.1
Galvanized steel probe (mpy)

1.0
must be slaved to the other chemicals used in the program.
0.9 The efficacy of the program will be, as with any corro-
0.8
0.7 sion-inhibition program, determined by monitoring corrosion
0.6 rates. Monitoring for corrosion rates can be achieved via the
0.5
0.4 following methods:
0.3
0.2
0.1 ■ Galvanized steel corrators measure current flow across two
0 identical electrodes to which a small current is applied and
11/4/2010 12/5/2010 1/5/2011 2/5/2011 3/8/2011 4/8/2011
measured. From the current flow, corrosion rates can be
calculated and displayed online, from which trend lines can
also be produced.
Table 4. The chemistry of the makeup water and
cooling tower bulk water are compared with the As- ■ Galvanized coupons of the same metallurgy can be used to
sociation of Water Technologies guidelines summa- produce absolute corrosion rates and the most accurate mea-
rized in Table 2. Source: AWT, Nalco Power ITC surement of metal loss.
■ Visual inspections may be subjective, but frequent inspections
Parameter Makeup source Circulating water Guideline can prove to be very valuable in identifying problems before
pH 8.7 9.3 6.5 to 9.0 they become severe.
■ Zinc coating testing is critical, as the coating is what you
Hardness as CaCO3 4.6 39 >30 ppm
are protecting. Trend data collection is also important to
Alkalinity as CaCO3 210 1,000 <500 ppm help determine if the zinc coating is leaching into the sys-
Chlorides as Cl- 120 460 <250 ppm tem. A baseline should be developed for zinc levels in the
Sulfates as SO42- 110 390 <250 ppm
system prior to introducing the program. Once the program
is established, zinc levels should decrease if the program is
Conductivity 1,000 4,000 <2,400 micromhos working effectively.

Increased awareness of the potential pitfalls of using gal-

5. Tube protection. Surface corrosion on galvanized tubes was
prevented during recent testing. Courtesy: Nalco Power ITC
vanized components in cooling towers is needed in the power
industry. Though it is relatively inexpensive when compared
to stainless steel, galvanized steel demands a certain dili-
gence when developing a cooling water treatment program.
Specifically, end users need to be aware of the makeup water
source and the desired cycles of concentration in the cooling
tower. Only then can they make an informed decision about
a comprehensive water treatment regimen, including a corro-
sion inhibition plan, prior to startup. ■
—Kevin Boudreaux (kjboudreaux@nalco.com) is a power indus-
try technical consultant for Nalco Co.’s Power Group.

20 www.powermag.com |
POWER April 2013
Cycle Chemistry Commissioning Deserves
Its Own Strategy
09/24/2012 | By Dr. Otakar Jonas, PE and Lee Machemer, PE

Delayed startups and damage to plant equipment due to inadequate water cycle chemistry
commissioning are thought to be major problems for half of all new generating units, as well as for
older units that have been upgraded or had their operation or chemistry changed. Fortunately, most
of these problems are avoidable. There’s no shortage of knowledge or experience related to water
chemistry and corrosion. It’s the inability to access and apply the correct resources that usually
causes problems.

During the commissioning of a plant, the risk of water chemistry–related delays is at its highest,
while the ability to analyze and control water cycle chemistry is at its lowest level in the life of the
unit. Typically, delays are the result of a lack of readiness of cycle chemistry–related equipment, an
accumulation of corrosion products, the use of the wrong water treatment chemicals, and/or
inattention to cycle chemistry and corrosion. Many water treatment–related problems can be avoided
simply by taking the proper steps throughout the design, construction, and commissioning of the
unit.

A proven way to reduce the incidence of cycle chemistry–related delays is to develop and implement
cycle chemistry commissioning guidelines at new plants, at plants that have had major equipment
upgrades, and at plants whose water chemistry or operating mode has been changed. An example
of the latter is a plant that switches from baseload to cycling service. This article explains the topics
such guidelines should address and includes a number of case histories that illustrate how
implementation of cycle chemistry commissioning guidelines could have prevented problems and
saved millions of dollars.

A Guide to the Guidelines

Cycle chemistry commissioning guidelines are a mix of action items and checklists for verifying that
all cycle chemistry–related equipment is operational and in good condition, that personnel are
properly trained, and that procedures are in place for sampling, analyzing, and controlling water
cycle chemistry parameters. To be most effective, the guidelines must be customized for each plant
as a function of its water cycle design and operating mode.

Cycle chemistry guidelines have two purposes: to avoid delays in commissioning a plant and to
prevent short- and long-term cycle chemistry and corrosion problems. To achieve both goals, they
must address all the steps that must be taken to ensure that all waterside and steamside equipment
is as clean as possible, so the plant’s cycle chemistry can be brought within recommended limits
quickly. Implementing the guidelines also ensures that water and steam sampling and analysis
systems are prepared to do their job at the first fire.

Cycle chemistry guidelines are most effective when they include a cycle design review, address the
materials selection process, and verify that the chemistry of plant water can be controlled by
treatment and monitoring. Accordingly, putting together the guidelines requires the cooperation of
the plant’s architect/engineer, owner, operator, and equipment suppliers.
Following is a list of topics that all cycle chemistry commissioning guidelines should include or
address:

 A review of the plant’s water and steam cycle designs, including a review of the design of all
water-related equipment. Issues and subjects that are typically addressed here include
corrosion of various types, impurity transport, heat flux, and stresses.
 A set of plant-specific water chemistry control and management guidelines.
 Procedures for protecting equipment during manufacture, transport, storage, erection, and
layup, and procedures for removing preservatives.
 Training of operators and chemists prior to plant commissioning.
 Operating and maintenance procedures and manuals.
 Scheduling inspections of cycle chemistry–related equipment.
 Pre-operational cleaning (acid, steam/air blow) and hydrotesting.
 Pre-steaming checks of the boiler, turbine, and condenser, as well as condensate polishing.
 Performance testing for steam purity/carryover, boiler hideout, iron transport, and the like.
 Water and steam sampling system design and operation.
 The plant’s cooling water system.
 Discharges and disposal of water treatment chemicals.
 The plant’s chemical laboratory.
 Safety issues.
 A water cycle commissioning schedule.

Each issue should have its own action items and a checklist of tasks to be signed off on at different
times during the plant’s design, construction, and commissioning processes. Individual checklist
items should be assigned either to the plant’s developer, contractor, or representatives of its owner,
and the timing of the checks should be coordinated with the plant’s erection and commissioning
schedule. Finally, plant management must take responsibility for ensuring that all pertinent checklist
items are signed off before proceeding. Cycle chemistry guidelines should not be used as a
substitute for other commissioning and operation documents.

Two of the listed topics are worth mentioning in greater detail:

 Design reviews. The purpose of the steam cycle design review is to establish the cycle’s basic
characteristics. They should quantify its ability to transport and remove products of corrosion,
its deaeration characteristics, the effects of condenser leaks and air inleakage, and the cycle’s
ability to decompose and transport organics. The design review of water-related equipment
should focus on concentration of impurities on component surfaces (such as boiler tubes and
turbines) and on the effects of heat transfer and stress on corrosion, stress corrosion, and
corrosion fatigue.
 Performance testing. This procedure should include an experimental determination of the cycle
chemistry’s transport characteristics, in particular boiler carryover and steam purity, boiler
hideout, deaeration, makeup and polisher performance, and iron transport. The testing may
require intensive two-week monitoring of water and steam chemistry under anticipated
operating conditions. Additional chemists and consultants may be needed. Performance
 testing need not be done during water cycle commissioning, but it should be done within the
first two months of the plant’s normal operation.

A Case Study and a Summary of Problems

Many commissioning delays and later problems are the result of cycle chemistry–related problems
that should have been detected and solved during water cycle commissioning. But there are just as
many instances where implementation of cycle chemistry commissioning guidelines have prevented
delays or nipped problems in the bud.

Consider, for example, how such guidelines—which were implemented from design through plant
commissioning—facilitated the startup of an 800-MW, three-pressure, combined-cycle unit with a
1,920-psig high-pressure (HP) boiler, an air-cooled condenser, and a powdered resin condensate
polisher. With the exception of its low-pressure (LP) boilers, where congruent phosphate treatment is
employed, the unit uses all-volatile water treatment with ammonia and hydrazine. Pre-operational
cleaning of the heat-recovery steam generator (HRSG) was via citric acid, and steam piping was
cleaned using extensive air blowing. The commissioning of this unit, whose water and steam
chemistry are summarized in Table 1, was not delayed by water chemistry–related problems
because all of its cycle chemistry commissioning guidelines were met.

Table 1. Summary of water and steam chemistry during and after startup of a combined-cycle
unit for which water chemistry commissioning guidelines were used. Source: Jonas Inc.

Obviously, not all plant owners have been implementing such guidelines. The consequences of
failing to do so are detailed in Table 2, which lists 15 examples of commissioning-related problems
experienced by combined-cycle and conventional fossil-fired units. Illustrations of selected problems
are shown in Figures 1 through 5. Among the problems listed are:

 Cycle contamination because of undetected condenser leaks.

 Corrosion of equipment during unprotected storage.
 High cation conductivity of steam because of decomposition of organic water treatment
chemicals.
 Poor performance of condensate polishers and subsequent turbine corrosion.
 High boiler carry-over, leading to turbine deposits and stress corrosion cracking.
 Flow-accelerated corrosion.
Table 2. Examples of problems experienced during commissioning. Source: Jonas Inc.
1. Heavy deposit in HP superheater tube after cycle contamination with brackish
water.Courtesy: Jonas Inc.

2. Scanning electron microscopy and elemental analysis of the black tarry deposit that
formed after unsuccessful chemical cleaning. Courtesy: Jonas Inc.
3. Flow-accelerated corrosion of carbon steel channel separators in the LP drum. Courtesy:
Jonas Inc.

4. Severe stress corrosion cracking of an L-1 LP turbine disk caused by high concentration of
sodium hydroxide in steam. Courtesy: Jonas Inc.

5. Corroded waterwall tube from a high-pressure drum boiler after one year operation at
maximum continuous rating. Courtesy: Jonas Inc.
Nuclear Plants Are Not Exempt

Many U.S. pressurized water reactors (PWRs) have suffered severe corrosion damage during
commissioning or their first few fuel cycles. In many cases, the damage has been caused by a
combination of a poor design, wrong water chemistry guidelines, and/or cycle contamination by
condenser leaks, air inleakage, or malfunctioning condensate polishers.

6. Chloride concentration in steam generator water throughout several fuel cycles of a

pressurized water reactor. Courtesy: Jonas Inc.

The costly consequences of corrosion damage at nuclear plants have included dents in steam
generator tubes that required a multi-million-dollar replacement of the generator; turbine stress
corrosion cracking that necessitated replacement of an entire turbine or rotor; and flow-accelerated
corrosion of feedwater and wet steam piping and turbine casings. Figure 6 is an example of steam
generator water chemistry for a PWR unit using seawater condenser cooling. It illustrates the degree
of noncompliance with specified chloride limits during early operation.

This article was originally published in the April 2004 issue of POWER. The consultancy Jonas Inc.,
established by the late Dr. Otakar Jonas in 1983, is now managed by Lee Machemer, PE. Edited by
Dr. Robert Peltier, PE.
 WATER TREATMENT
ORP as a Predictor of WFGD Chem-
istry and Wastewater Treatment
Recent studies have shown that system oxidation-reduction potential (ORP)
is not only an important factor for predicting wet flue gas desulfurization
(WFGD) absorber chemistry but also may be a predictor of process equip-
ment corrosion and wastewater treatment requirements.
By S.R. Brown, R.F. DeVault, and D.B. Johnson, Babcock & Wilcox Power Generation Group Inc.
P
urge streams of wet flue gas desulfur-
ization (WFGD) units, which are one
byproduct of controlling SO2 emis-
sions from coal combustion, are being in-
creasingly subjected to stricter wastewater
regulations. Consequently, coal-fired power
generators need a method for controlling the
operational chemistry of these WFGD units.
Upon implementation of a suitable control
method, WFGD bleed stream chemistry and
flow rate may be optimized, thereby result-
ing in improved performance of one or more
downstream unit operations. A further ben-
efit is reduced reagent and additive costs in
various devicies, including the WFGD unit.
One control parameter of interest is the
oxidation-reduction potential (ORP) of the
bleed stream. Much like pH, the measure-
ment of ORP can be taken in real time and
integrated with other plant-monitoring
data. By incorporating ORP measurements
into a process control scheme for limestone
forced-oxidized WFGD absorbers—along
with various other control variables such
as SO2 removal, absorber pH, reagent flow
rate and/or one or more reaction stoichiom-
etries, and/or gypsum purity—generators
are able to manage the oxidation states of
various dissolved metals in the slurry and
the potential reemission of mercury. (Also
see “How to Measure Corrosion Processes
Faster and More Accurately,” May 2009 in
the POWER archives and “Mercury Control:
Capturing Mercury in Wet Scrubbers, Parts
I and II,” July and September 2007, respec-
tively, in the COAL POWER archives—both
available at powermag.com.)
A further benefit is control of the corro-
sion rate of the absorber recirculation tank
(ART) and other alloy parts within the sys-
tem. Many utilities have had ORP excur-
sion events in WFGD wastewater discharge
where the ORP readings changed from 150
millivolts (mV) to 300 mV to a reading
above 500 mV. Previously, these fluctua-
40
tions have gone largely unexplained. We
have determined that this magnitude of
change in ORP, in an ART, due to coal
composition and upstream air quality con-
trol system (AQCS) effects on WFGD ab-
sorber chemistry, can accelerate corrosion.
One potential solution to fluctuating ORP
readings is to use integrated process con-
trols designed to tune the upstream opera-
tion of the AQCS train to produce consistent
inlet flow parameters to the WFGD tower,
rather than operating each as an indepen-
dent process. The control of the ORP level
in a WFGD system may produce improved
plant operations by reducing the amount of
wastewater treatment necessary and helping
mitigate mercury reemission.
Fundamentals of ORP
ORP is a measure of the potential for a
chemical species either to acquire or re-
lease electrons. The potential is common-
ly measured by an ORP probe in units of
millivolts, which can be measured in real
time under online plant process conditions.
Positive readings are indicative of a system
operating in oxidizing conditions; negative
readings indicate a system operating in re-
ducing conditions. If a material comes into
contact with a solution that has a higher
oxidative potential, then a chemical reac-
tion may occur in which the solution is re-
duced and the material is oxidized.
The ORP of WFGD slurry and effluent is
driven by the presence or absence of strong
oxidizers. Many WFGD units operate at a
moderate ORP range of about 100 mV to
300 mV, thereby achieving, or yielding, a
rather stable voltage reading over time. The
range of 100 mV to 300 mV is referred to
as “low” ORP in this article. Such WFGD
units often have oxidizer concentrations
within the slurry below 200 ppm. Other
WFGD units operate at higher ORP values,
often above 500 mV. Slurries with high
www.powermag.com
ORP almost always contain a high concen-
tration of at least one strong oxidizer such
as persulfate (S2O8-2), peroxymonosulfate
(HSO5-), or hypochlorite (OCl-).
Persulfate has been identified and quanti-
fied using ion chromatography on absorber
slurry samples collected at several sites. This
anion is the most powerful oxidant of the
peroxygen family of compounds, and it be-
comes a more effective oxidizer at scrubber
process temperatures above about 120F due
to free radical formation. In several instances,
strong oxidizers were measured at total resid-
ual concentrations over 1,000 ppm in WFGD
absorber slurry samples exhibiting high ORP
after the samples were removed from the sys-
tem and analyzed in the laboratory. Operating
WFGD units are observed to swing from one
process condition to the other (high to low
ORP), but few, if any, hold at an intermedi-
ate value for an extended period of time. The
rate and magnitude of these changes in slurry
chemistry are indicative of upstream process
changes affecting absorber chemistry.
Once you determine the WFGD slurry
ORP, you can predict the dominant oxida-
tion state for the various constituents that
may be present in the absorber slurry. For
many metals, solubility is a function of the
oxidation state. Therefore, once the ORP of
a solution has been determined, a predic-
tion can be made of the preferred oxidation
state for a given chemical species in a so-
lution. The predominant species of various
metals, and other compounds or ions, can
thus be determined. Using this knowledge,
the ORP in WFGD slurry can then be con-
trolled in order to control the speciation of
various metal ions, as well as other com-
pounds and ions.
The range of potential electrochemical
states of a given material can be found with-
in a Pourbaix diagram for a given chemical
species and presented as a function of pH
and electrochemical potential versus pH.
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POWER July 2013

For example, a variety of general predic-
tions about the various phases of mercury,
selenium, and manganese based upon ORP
and pH can be made (see the table).
Dynamic Chemical Processes
By monitoring the ORP of WFGD absorber
process slurry, changes within the system
process and chemistry can be determined.
Estimations of various parameters of WFGD
absorber chemistry can also be determined,
including the dominant oxidation states and
phases of metals within the slurry, the po-
tential reemission of mercury, and the risk
of accelerated corrosion of the alloy vessel.
Measurement of the system ORP also alerts
operators to the likelihood of problems in
downstream wastewater treatment (WWT)
systems, especially the ratio and concentra-
tion of selenate ions to selenite ions within
an effluent stream.
The chemistry inside a WFGD absorber
is a complex system of hundreds of poten-
tially changing ionic species and distinct
compounds existing simultaneously through-
out the slurry. The modeling of WFGD ab-
sorber slurries has been based on equilibrium
thermodynamics to date. However, we have
determined that in operating units, WFGD
absorber slurry chemistry is more likely to
be kinetically controlled. Most absorbers are
operating at an unsteady state. Due to kinetic
interaction, mercury could become reduced
to the elemental state, thereby becoming va-
porous and exiting the system boundaries in
what is called mercury re-emission.
Another important aspect of ORP with
relation to WFGD process chemistry is the
reaction of any of the one or more strong oxi-
dizers present with one or more halide ions
present in solution, thereby resulting in in-
creased demand for reagent in the absorber
and a possible lowering of pH in the purge
stream after the solids have been removed.
Because persulfate is a powerful oxidant, it
has the ability to convert some halide anions
to their respective elemental state. Specifi-
cally, some chloride may convert to chlorine
under high-ORP conditions:
Similar reactions occur between the
oxidizer(s) and other halide species pres-
ent (for example, bromide, iodide, and the
like). Thus, the concentration of chlorine in
absorber slurry is present as three species
in equilibrium within the aqueous phase:
dissolved gas (Cl2), hypochlorous acid, and
ionic hypochlorite:
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July 2013 POWER
Dominant forms of mercury, selenium, and manganese for approximate
ORP levels. Source: Babcock & Wilcox Power Generation Group Inc.
ORP Level Mercury
<0 (mV) Vapor
0-300 mV Aqueous ion, with the solids
300-500 mV Aqueous ion, with the solids
>500 mV Aqueous ion, with the solids
Within the typical WFGD operating range,
equilibrium favors HOCl. The formation of
H+ ions associated with this chemical reac-
tion will cause a decrease in pH as halogen-
containing species are liberated from the
scrubber. In WFGD systems that are oper-
ating in pH control mode, the reagent feed
controls will respond to the lower pH by add-
ing more reagent. In systems with high ORP
levels, gypsum formation may occur without
the addition of oxidation air when sulfite re-
acts with strong oxygen containing oxidizing
agents. Higher gypsum purity can result as
excess limestone, normally an impurity with-
in the gypsum product, is reacted to buffer
the system from dropping pH.
Due to the electro-reactive nature of mer-
cury, ORP levels are a main driver in control-
ling reemission, dissolution into the slurry,
and solid phase retention. Higher ORP values
in the ART are favored in order to maintain
dissolved mercury. ORP levels above 500 mV
often favor an increase in the dissolved mer-
cury, with constant total mercury content in
the slurry. A decrease in the ORP in an ART
is an indication of a less-oxidizing environ-
ment, leading to elemental mercury forma-
tion and potentially release (or reemission).
A possible chemical pathway for mercury
reemission to occur is shown in Equation 3:
Swings in ORP value may also cause mer-
cury to enter the elemental state and be re-
emitted from a WFGD tower.
Staying in Compliance
WWT systems are tuned to control metals
present in influents and to produce effluents
within a certain concentration range. Changes
in the influx of these metals to WWT may
disrupt performance if controls and opera-
tional parameters cannot respond quickly. As
swings in WFGD and/or WWT process occur,
ORP may ultimately produce changes in the
dominant state of regulated metals, thus per-
mitting the WFGD effluent flow rate to affect
the mass flux of each species. In this situation,
detrimental fluctuations in ORP may result in
minimal removal of some metals and poten-
tially result in out-of-compliance operation.
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WATER TREATMENT
Selenium Manganese
Selenite Aqueous ion
Selenite Aqueous ion
Selenate Aqueous ion
Selenate MnO2 solid
Controlling process ORP can lead to im-
proved efficiency of WWT systems related
to selenium removal. WFGD effluent ORP
controls the precipitation of many regulated
metals, particularly selenium. At low ORP, se-
lenium exists mainly as selenite (SeO3-2) and
can be removed by many WWT methods in-
cluding chemical precipitation. At higher ORP
levels (greater than about 300 mV,) selenium
will predominantly occur as selenate (SeO4-2),
which passes through many WWT systems.
The combined effects of over 1,000 ppm of
total oxidizers and low pH potentially associ-
ated with high-ORP WFGD effluent streams
can result in damage to bioreactor stock and/
or increased reagent costs in WWT systems.
Strong oxidizers present within WFGD effluent
have the potential to upset biological processes.
During high-ORP conditions, the WFGD would
essentially be feeding bleach (hypochlorite),
peroxide, and stronger oxidizers to downstream
systems; such oxidizers can damage microbial
health when fed to biological treatment units.
Furthermore, high ORP in a WFGD effluent
can result in low pH of WWT influent. As de-
scribed earlier, oxidizers will continue to react
with halide ions in solution, thereby liberating
a hydronium ion and thus lowering pH. When
excess carbonate is available, it may buffer such
impacts. Once unreacted limestone is removed
from the slurry filtrate during dewatering, the
pH buffering capacity of the system rapidly de-
creases while oxidizer and halide ion concentra-
tions remain and are fed to WWT.
Materials Must Resist Corrosion
Materials coming into contact with WFGD
slurry and effluent should be selected with care-
ful consideration to the corrosive potential of
high-ORP slurries containing ionic manganese.
Strong oxidative content is present in high-ORP
slurry leaving the scrubber, and very low pH
levels may be seen downstream in conjunction
with high ORP. While industry focus has been
given to WFGD ART corrosion, the potential
exists for similar corrosion to occur in process
pumps, dewatering operations, vacuum systems
for gypsum production, as well as in process
piping and WWT equipment.
Alloy 2205 duplex stainless steel (UNS
S32205) is proving susceptible to accelerated
corrosion from slurries that contain precipi-
41
 WATER TREATMENT
tated, or non-solubilized, manganese species
and/or high ORP levels. Within the WFGD
absorber, the majority of the corrosive attack
is observed below the slurry level in the ART.
Under high-ORP conditions, the rate of cor-
rosion can accelerate. When the ORP of op-
erating WFGD slurries is pushed above about
500 mV, manganese normally soluble as ionic
Mn+2 will oxidize and precipitate out as MnO2.
When this precipitate contacts metal as part of
a deposit, it serves as a galvanic cathode to ex-
acerbate the fluoride and chloride driven un-
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der-deposit corrosion mechanism. Corrosion
thus accelerated by manganese precipitation
can be rapid and severe.
In many applications ceramic tile and lin-
ings are considered as alternatives to alloy.
Wall-papering with UNS N10276 (Hastelloy
C-276) has been performed in some installa-
tions. Some plastics and resins may also be
susceptible to attack from high ORP levels.
Strong oxidizers within the slurry effluent
may react with and thereby degrade some
polymer bonds, because high-ORP filtrate
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samples were observed to weaken and dis-
color HDPE bottles in a laboratory setting.
Within substances such as fiberglass-rein-
forced plastic, such a reaction with resins
could potentially cause some dissolution of
the resin and/or lead to fiber delamination.
Plantwide Impact
The WFGD ART ORP and the WWT influent
process ORP both need to be controlled. Cur-
rently, studies are being performed to define
techniques to maintain steady ORP and to allow
for greater fuel flexibility. Such control would
afford utilities the option to obtain the most
cost-effective fuel, maintain a constant effluent
for wastewater, and provide a better treatment
scheme. Coal yard and boiler operators will
need to work in conjunction with the plant’s
continuous emission monitoring systems, the
WFGD system, and WWT plant operators to
implement improvements that integrate the en-
tire process. Learning how a parameter change
upstream affects the WFGD and WWT systems
is quickly becoming crucial. With full control
of the AQCS process train and dewatering sys-
tems, control of WWT influent is expected.
The effects of blending coals, staging com-
bustion, and swinging load can create issues
with AQCS equipment, especially in environ-
ments where WFGD units are employed. The
WFGD system serves as the catch basin for
all flue gas byproducts as well as any fine ash
not captured in an electrostatic precipitator or
pulse jet fabric filter. Undesired ORP levels,
or undesired fluctuations therein, can cause
problems ranging from mercury reemission to
increased corrosion and improper treatment of
WFGD effluent. Adjustments to combustion
processes may affect operating parameters of
the WFGD environment as well as the WWT
systems. Combustion systems need tuning to
allow for efficient power generation, compli-
ance with existing regulations, and flexibility
to comply with anticipated, tighter water and
solid discharge regulations.
Due to the potential for aggressive or ac-
celerated corrosion of some alloy material in
high-ORP environments, care should be taken
on selection of alloys or materials in the WFGD
slurry and filtrate contact zones. Constituents of
the WFGD slurry will include limestone, gyp-
sum, halide ions, and metals from the burned
coal as well as silica from the ash and other
up-stream constituents. The ORP levels in the
tank can cause the metals to undergo phase
partitioning or to change their solubility due to
changes in their oxidation state. ■
—S.R. Brown (srbrown@babcock.com) is
AQCS engineer, R.F. DeVault (rfdevault@
babcock.com) is research chemist, and
D.B. Johnson (dbjohnson@babcock.com)
is field service engineer for Babcock &
Wilcox Power Generation Group Inc.
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POWER July 2013