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3/16/2017 Combined-Cycle Water/Steam Monitoring - Power Engineering

Combined-Cycle
Water/Steam Monitoring
11/14/2013

By Brad Buecker, Contributing Editor

Earlier in this series, I wrote about modern techniques to minimize impurity ingress, scaling, and
corrosion in heat recovery steam generators (HRSG). But without accurate sampling and good data
collection, the conditions within an HRSG may be or become harmful without the knowledge of operators
or other technical personnel.

This is another of those cases where an "ounce of prevention is worth a pound of cure." This article
outlines important samples required for successful HRSG operation.

Monitoring the Entire System


Organizations such as the Electric Power Research Institute (EPRI) have written entire manuals
regarding HRSG sampling [2], so obviously a complete overview is not possible in a single technical
article. However, it is possible to discuss the most important samples and the benefits derived thereby.

HRSGs come in many different designs, but a common general arrangement is shown in Figure 1. We
will use it for this discussion.

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Let's begin at the condenser and condensate pump discharge (CPD), with the note that many HRSGs
are not equipped with condensate polishers. For units with water-cooled condensers, the condenser is
the primary source within the system for impurity ingress. Even a minor leak from one condenser tube
can introduce enough impurities to cause significant damage in the evaporator circuits. In the opinion of
many, the CPD sample point is the most important of any within the entire water/steam network.

Where the condensate is treated by a polisher, the effects of a condenser tube leak are dampened.
However, it is still important that any leak be detected as quickly as possible to prevent premature
exhaustion of the polisher and subsequent carryover of contaminants to the boiler.

Recommended on-line analyses include:

Cation Conductivity (or becoming popular, degassed cation conductivity)


Sodium
Dissolved Oxygen

The name for cation conductivity has undergone an evolution, and research groups have now begun
referring to the technique as conductivity after cation exchange (CACE). For this article, we will continue
to use cation conductivity. The technique has been adopted at most plants for detecting impurity in-
leakage. If a condenser tube fails or impurities enter from another source (a makeup water treatment
system failure is the next most likely source), the sodium, calcium, and magnesium salts in the water are
converted to their respective acids, primarily dilute sulfuric and hydrochloric acids, by the cation
exchange column.

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The dilute acids that emerge (HCl and H2SO4, primarily) are more conductive than their respective salts
and have an immediate influence on conductivity, thus providing a quick indication of upsets. The cation
column also removes ammonium ions (NH4+), which are formed by conditioning chemicals added to the
feedwater. If ammonium ions are not removed from the sample, they can mask impurities. In general,
the cation conductivity of a clean condensate sample should be less than 0.2 micromhos
(microsiemens) per centimeter (S). This limit is mandatory for systems that operate on all-volatile
treatment oxidizing [AVT(O)], which has been developed to minimize flow-accelerated corrosion in
economizers and evaporator tubes. [3]

So, how does degassed cation conductivity improve upon the method? Air that leaks into condensers of
course contains a small percentage of carbon dioxide. At significant air in-leakage rates, the CO2 that
enters can increase the condensate conductivity and mask other impurity ingress. Degassed cation
conductivity utilizes either a reboiler or purge vessel (with nitrogen gas feed) to remove carbon dioxide.

Direct sodium monitoring of the CPD is also very effective for detecting condenser leaks and other
impurity ingress. With a tight condenser, sodium levels in the condensate should be very low (<3 parts-
per-billion [ppb]), and in many cases less than 1 ppb. On-line sodium analyses in conjunction with
cation conductivity are very useful. A combination of the two instruments provides backup readings in
the event of an instrument malfunction.

Dissolved oxygen (D.O.) analyses are quite important for monitoring air in-leakage to the condenser
from the steam-side. Ideally, if the condenser air removal system is operating at maximum efficiency,
dissolved oxygen levels should be below 10 ppb. A sudden increase in dissolved oxygen indicates a
problem below the waterline in the condenser. Leaks above the waterline, if severe, may cause
significantly decreased condenser performance. [4]

Deaerator Outlet
The deaerator (D.A.) in multi-pressure combined-cycle units may be integral or separate to the LP
drum, but in either case the D.A. should maintain D.O. concentrations below 10 ppb. Deaerator outlet
sampling for dissolved oxygen (grab sampling is most common) helps the plant operator or chemist

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monitor deaerator performance. An increase in D.O. levels over normal concentrations could indicate
problems with the internal deaerator components. Trays may become misaligned. Or, the deaerator
vents may not be adjusted properly.

Feedwater/ Economizer Inlet


This sample is very important, as it is the last checkpoint before the evaporator circuits. Feedwater
chemistry can have a significant impact on boiler operation for several reasons. First, excessive
feedwater contamination will reduce the boiler cycles of concentration and require increased blowdown.
Second, improper control of feedwater chemistry may cause corrosion of feedwater piping and heat
exchanger tubes, which will introduce corrosion products to the boiler. Third, feedwater is often utilized
for main and reheat steam attemperation. Contaminated feedwater introduces impurities directly to the
steam.

Recommended on-line analyses include:

pH
Dissolved Oxygen
Speci c Conductivity
Cation Conductivity
Sodium

Suggested grab sample analysis:

Ammonia
Silica

Ammonia or in some cases an amine (see final paragraph of this article) is typically utilized to adjust
feedwater pH to minimize general corrosion. The optimum feedwater pH for systems with all-ferrous
metallurgy is 9.2 to 9.6. Ammonia monitoring via grab sample analyses can be quite useful, but most
common is to monitor the dosage based on continuous specific conductivity. Cation conductivity and
sodium analyses perform the same function as for the condensate pump discharge, but also indicate if
contaminated feedwater is being sent to the attemperators.

Continuous dissolved oxygen readings are valuable to confirm that that the deaerator is performing
properly, but except in the rare case where copper alloys exist somewhere in the feedwater network, in
no circumstance should the feedwater D.O. concentration be zero. As much research has shown,
single-phase flow-accelerated corrosion (FAC) is generated by reducing environments where oxygen
has been scavenged by chemicals such as hydrazine or one of its organic alternatives. [5] In general,
single-phase FAC is most pronounced around 300oF, which in HRSGs corresponds to the LP
economizer and evaporator.

Some recommendations call for continuous sodium monitoring of feedwater, but in this author's opinion
such sampling may be redundant if continuous monitoring is provided at the condensate pump
discharge or after the condensate polisher, if one has been installed. Grab sample analyses for silica

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(SiO2) indicate the concentration of this contaminant that is being transported to the LP drum and
beyond, and the attemperators.

An additional technology, particulate monitoring, is becoming more popular for condensate and
feedwater chemistry evaluation, and it can be particularly useful for systems operating with air-cooled
condensers (ACC). An ACC eliminates the potentially catastrophic impurity ingress that can occur from
water-cooled condensers, but ACCs are so very large that a vast surface area of carbon steel is
exposed to flowing steam and condensate. Typically, the bulk of the corrosion products that emerge in
the condensate/feedwater consist of iron oxide particles. Particulate monitoring provides a much better
analysis of carbon steel corrosion than dissolved iron analysis.

Boiler Water
Along with condensate pump discharge, the boiler water sample is the most critical. For drum-type
HRSGs as outlined in this article, the high temperatures and the concentrating effect caused by
recirculation of the boiler water require close monitoring. Furthermore, improperly controlled
concentrations of dissolved solids in the boiler water can introduce excessive contaminants to the
steam, where they may form deposits and/or corrode superheater tubes and turbine components.

Either the drum blowdown line or a downcomer should be utilized for evaporator sampling, although
EPRI recommends the downcomer if the unit is on oxygenated treatment. [3]

Recommended on-line boiler water analyses include:

pH
Speci c Conductivity
Cation Conductivity
Sodium
Phosphate (for those units on phosphate treatment)

Important grab samples include:

Ammonia
Silica

Boiler water pH is one of the few samples where an immediate unit shutdown is required if the chemistry
goes bad. EPRI calls for immediate shutdown if the pH drops below 8.0 although I am aware of at least
one HRSG manufacturer that has set a limit of 7.0. Personally, I feel more comfortable with the 8.0 limit,
as if a condenser tube leak or other serious issue is causing the upset, time is of the essence in taking
action. From a treatment standpoint, many drum units are operated with EPRI's phosphate continuum
program, in which only tri-sodium phosphate (Na3PO4) is utilized for feed with perhaps a small amount
of caustic (NaOH) at start-up. The free caustic concentration should never be higher than 1 ppm to
minimize under-deposit caustic gouging. It must be noted that for HRSGs as outlined in Figure 1, where
the LP circuit provides feedwater to the IP and HP circuits, the LP circuit must rely on the all-volatile
feedwater treatment only with no phosphate addition. Phosphate can cause difficulties in the IP and HP

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economizers that receive feed from the LP circuit.

Specific conductivity is important for monitoring total dissolved solids (TDS) concentration. Excessive
solids will mechanically carry over to the steam, as drum steam-separators are never 100 percent
efficient. This effect is influenced by boiler pressure, thus the allowable dissolved solids concentration
decreases with increasing pressure. Charts are available to determine TDS limits, but every steam
generator is unique and only actual operation provides the exact carryover data. Cation conductivity
provides a method to evaluate the chloride and sulfate concentration in the evaporator circuits.
Research has shown that these contaminants can cause significant corrosion if boiler water chemistry is
not properly maintained.

With regard to silica, carryover is the primary concern where transfer of silica from boiler water to steam
is primarily by vaporous carryover, not mechanical. The mechanism is influenced by pressure, where
the effect becomes dramatic as pressure increases. For example, in a 900 psi boiler the recommended
maximum drum water silica concentration is 2.8 ppm to keep silica below 10 ppb in the steam. In a 2,400
psi boiler the recommended maximum is 0.2 ppm! Again, each boiler will exhibit individual properties in
this regard.

Ammonia sampling is valuable, as at the low phosphate concentration often maintained in boiler circuits
nowadays, ammonia can impart a false pH indication. The operators may think that chemistry is
adequate to prevent under-deposit chloride and sulfate corrosion, and its progeny, hydrogen damage,
when in fact the chemistry is not doing the job. Grab sample ammonia analyses are typically
recommended, where the analyst can utilize charts to evaluate the chemistry effects. Excel programs
are also available that allow these calculations to be made quickly. [6]

Saturated Steam
In the past, main/reheat steam sampling was considered more important than saturated steam
sampling, and indeed the importance of main/reheat sampling has not diminished. However, the
recommended maximum concentrations of sodium, chloride, and silica in steam have all been reduced
to the extremely low limit of 2 ppb. These impurities are now known to cause turbine corrosion at very
low levels. This issue has increased the importance of periodic saturated steam sampling for
mechanical carryover, as that is the primary mechanism for Na, Cl, and SO4 to enter the steam.

Main and Reheat Steam

These samples are quite critical, as they provide a direct indication of steam impurities generated by
drum carryover or by feedwater attemperation. Some substances such as silica exhibit decreasing
solubility with decreasing steam pressure, and will precipitate on turbine blades as pressure lowers
upon steam passage through the turbine. Other contaminants, including sodium, chloride, and sulfate
will come out of steam in the early condensate that begins to form in the LP turbine. These salts can
initiate stress corrosion cracking and corrosion fatigue of blades and rotors.

Recommended continuous analyses include:

Cation Conductivity
Sodium
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An important grab sample analysis is,

Silica

The primary measurement is cation conductivity, and it is typically used as the criteria for performance
evaluation and warranty requirement by turbine manufacturers. The common upper limit is 0.2 S. As in
the earlier discussion, degassed cation conductivity is an alternative to eliminate the influence of CO2
upon the readings. In fact, in some cases degassed cation conductivity may be particularly useful if
amines are used for pH control in the feedwater. The high-temperatures in superheaters and reheaters
induce decomposition of organic compounds to small-chain organic acids and CO2. The compounds
naturally will influence conductivity.

Sodium is another good tool for monitoring steam chemistry, as these instruments are reliable and
provide quick results. Sodium readings above 2 ppb suggest impurity leakage into the steam. Grab
sample silica analyses ensure that the limit of 10 ppb is being maintained in the steam.

Makeup Water Treatment


Space limitations prevent much additional discussion of sampling issues, but briefly, makeup water
treatment system sampling is also important. An increasingly common makeup water treatment scenario
is micro- or ultrafiltration, followed by reverse osmosis, in turn followed by portable ion exchange or
continuous deionization (CEDI) for polishing. A properly designed and operated system should produce
water with a specific conductivity less than 0.1 S, silica less than 10 ppb, and sodium, chloride, and
sulfate less than 3 ppb. Research has also shown that a good makeup system should limit total organic
carbon (TOC) in the effluent to less than 300 ppb. Organic carbon that enters the condensate system
will break down at the high temperatures in the boiler to generate small-chain organic acids that
potentially may influence turbine corrosion. This issue is still being researched intensively, but is the
primary reason why organizations such as EPRI do not recommend the feed of organic pH control
chemicals, or, if necessary, organic metal passivator/oxygen scavengers, to condensate and feedwater.

An Additional Monitoring Tool


In my previous articles and in other literature cited in this article and elsewhere, the severe corrosion
that even minor amounts of chlorides and sulfates, particularly chlorides, can cause in steam
generators, especially if they concentrate under deposits. Chloride and sulfate monitoring is more
difficult than other parameters, and these constituents are often not monitored at all. However, a
technique that can be utilized to detect even part-per-billion (ppb) concentrations of chloride and sulfate
is ion chromatography (IC). The equipment is not inexpensive and it requires a knowledgeable operator,
but for anyone who wishes to closely monitor these harmful constituents, IC is a good method.

Conclusion
Installation of a reliable sampling system and proper monitoring of the data requires effort and
commitment on the part of plant management. This may sometimes be problematic given the somewhat
minimal staffing at combined-cycle plants. However, conscientious monitoring and prompt action during
upset periods can be worth their weight in gold if they prevent system corrosion, boiler tube failures and
unit shutdowns. The ultimate price is loss of life, which has occurred due to flow-accelerated corrosion
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tube and piping failures at a number of utilities during the last 25 years.

A final note about sampling is that sample extraction and conditioning are critical for ensuring accurate
analyses. I will report on these topics in an upcoming issue of Power Engineering.

References
B. Buecker, "Corrosion Control in HRSGs"; Power Engineering, July 2011.

B. Buecker, "Combined-Cycle Water/Steam: The Lifeblood of the Plant"; Power Engineering, June 2012.

Cycle Chemistry Guidelines for Combined Cycle/Heat Recovery Steam Generators (HRSGs), EPRI, Palo
Alto, CA: 2006, 1010438.

B. Buecker, "The Impact of Condenser Performance, Feedwater Heating, and Steam Reheat on Steam
Generator Efficiency"; presentation at the 25th Annual Electric Utility Chemistry Workshop, May 10-12,
2005, Champaign, IL.

Guidelines for Controlling Flow-Accelerated Corrosion in Fossil and Combined Cycle Plants, EPRI, Palo
Alto, CA: 2005, 1008082.

Buecker B. and S. Shulder, "The Basics of Power Plant Cycle Chemistry"; Pre-Conference Seminar of
the 27th Annual Electric Utility Chemistry Workshop, May 15-17, 2007, Champaign, IL.

Author
Brad Buecker is a process specialist with Kiewit Power Engineers in Lenexa, Kan., and a contributing
editor for Power Engineering.

"Boiler water pH is one of the few samples where an immediate unit shutdown is required if the
chemistry goes bad."

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