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Steam Generator Chemistry

and Turbine/Condenser
E ciency: (Not) Separated
at Birth
03/01/2012

By Brad Buecker, Contributing Editor

Steam turbine and surface condenser performance is just as important as ever, and is intimately tied in
with chemistry control on both the steam side and cooling water side. In this article, we examine these
issues, plus revisit a straightforward method to monitor condenser performance.

A Turbine Discussion First


Utility steam turbines typically consist of thr
ee stages, high-, intermediate-, and low-pressure. A
question for the readers is, "Have you ever considered how much power is produced by each?" Let's
look into this topic.

The gure on pg. 53 is from Babcock & Wilcox's book, Steam, now in its 41st Edition. The drawing
outlines a realistic heat balance from a 2,400 psig drum unit with a 593 MW generator output.

Figure 1 Drum Unit Heat Balance


Source: Babcock & Wilcox
While a thermodynamic analysis of this system could seem quite daunting, in actuality the First Law of
Thermodynamics can be utilized to reasonably determine the work output of each turbine section. or F
steady state operation, the turbine work (WT) can be calculated by mass ow rate (m) multiplied by the
enthalpy drop (Dh) through the turbine.

WT = m(hin hout)

Of course, in the steam generator outlined in the gure, a number of steam extractions are utilized for
feedwater heating. However, the work done by the steam from all processes can be calculated by the
straightforward application of the formula outlined above. An analysis of Figure 1 shows that the output
of the three turbine sections (and in which author's calculations suggest a moisture content of the low-
pressure exhaust at 6.5 percent) is as follows.

HP turbine 166 MW
IP turbine 138 MW
LP turbine 289 MW
Although each turbine generates a signicant portion of the total power, the LP turbine has the largest
capacity.

Each turbine section can be affected by operational and steam chemistry factors that reduce efciency.
We will consider several of the most important. Please note that these principles also apply to heat
recovery steam generators (HRSGs), and thus are universal across the utility steam-generating industry.

First, in drum units some moisture always entrains with the steam as it leaves the water surface in the
drum. Thus, drums are equipped with internal steam separators to remove most entrained moisture and
return it to the boiler water. However, complete removal of droplets is impossible, and thus trace
amounts of solids will carry over to the superheater and main steam. These im purities include
chlorides, sulfates, silica, phosphates (in phosphate-tr
eated units) and other compounds. A number of
factors can cause carryover to be excessive. These include poor drum design, failed steam separators,
high dissolved solids in the boiler water, and excessive ramp rates during startup, among others.

Carryover can also be vaporous, in which certain compounds will volatilize on their own and transport
to steam. Silica and copper (in units with copper-allo
y feedwater heater tubes) are two notorious agents
for vaporous carryover.

Not to be forgotten is steam attemperation, where the common process is to control main and reheat
steam temperatures by direct injection of feedwater. Impurities that enter the condensate via a
condenser tube leak, makeup water treatment system upset, or other source will be directly introduced
to the steam.

Both mechanical and vaporous carryover become more pronounced with increasing pressure, thus
boiler water chemistry guidelines are increasingly stringent at higher pressures. But how do these
impurities affect turbine operation? The list below outlines many of the most important issues.

Silica solubility decreases as steam pressure decreases through the turbine.


Thus, silica will deposit on turbine blades, particularly in the HP section.
Chloride and sulfate salts will deposit, commonly in the LP turbine. These
impurities, and chloride in particular, may cause pitting and stress corrosion
cracking (SCC) of turbine blades and rotors. The most susceptible locations
are the last stages, L-1 and L-0, where early condensate forms. During times
of low load operation, early condensate formation may move backwards a
bit in the LP turbine.
Sodium hydroxide (NaOH) can also cause SCC of turbine blades.
In units with copper alloy feedwater heaters that operate at or above 2,400
psig, copper carryover can be quite detrimental. For the most part, copper
precipitates in the HP turbine, where even a few pounds of deposition will
reduce capacity by perhaps 10 MW or more. This capacity loss can be critical
during periods of high power demand.

The allowable concentration of contaminants in boiler water to prevent carryover is variable from unit to
unit, and also obviously is a function ofpressure. The Electric Power Research Institute (EPRI) has
published many guidelines on this issue, but the details ar e much too expansive to be presented here,
although I have included an example to highlight this issue. At 600 psia, the guideline for boiler water
silica concentration is 6 ppm to ensure no greater than 10 ppb in the main steam from mechanical and
vaporous carryover combined. Of course, this is a general guideline, and each steam generating unit
needs to be evaluated separately. Regardless, the recommended boiler water silica concentration at
2400 psia is 0.2 ppm! [3] This example illustr ates the large inuence unit pressure has on carryover.
Current limits for main/reheat steam sodium, chloride, and sulfate concentr ation are all 2 parts-per-
billion (ppb), with, as we have seen, a silica guideline of 10 ppb. Saturated steam sampling can be a
valuable tool to determine the level of mechanical carryover from drum units. I have seen excess
mechanical carryover due to incorrect drum size, and also have observed contamination of boiler water
and main steam by organics that produced foam. Excessive ring rates can also inuence carryover.
The Condenser: Money Made or Lost Due to Heat Transfer
After the steam generator, the condenser is the largest heat exchanger in the power plant. Although air-
cooled condensers are becoming more popular as a water conservation measure, steam surface
condensers still dominate this technology . Condenser tube fouling or scaling, or air binding dueot
excess air in-leakage will reduce efciency. Any of these mechanisms can cost a plant hundr eds to
thousands of dollars per day in lost performance. So, what are major issues of concern?

Often the most troublesome cooling water issue is microbiological fouling of condenser tubes, auxiliar y
heat exchangers, and, where cooling towers are utilized, cooling tower ll. Cooling systems provide an
ideal environment, warm and wet, for microbes. Bacteria will grow in condensers and cooling tower ll,
fungi on and in cooling tower wood, and algae on wetted cooling ower
t components exposed o t
sunlight. Biocide treatment is absolutely essential to maintain cooling systemperformance and
integrity.

A problem with microbes, particularly bacteria, is that once they settle on a surface the organisms
secrete a polysaccharide layer for protection. This lm then collects silt from the water, thus growing
even thicker and further reducing heat transfer. Even though the bacteria at the surface may be aerobic,
the secretion layer allows anaerobic bacteria underneath to ourish. These bugs in turn can generate
acids and other harmful compounds that dir ectly attack the metal. Microbial deposits also establish
oxygen concentration cells, where the lack of oxygen underneath the deposit causes the locationsot
become anodic to other areas of exposed metal. Pitting is often a result, which can cause tube failure
well before the expected lifetime of the material.

Fungi will attack cooling tower wood in an irreversible manner, which can eventually lead to structural
failure. Algae will foul cooling tower spray decks, potentially leading to reduced performance and
unsafe working locations.

The core of the microbiological treatment program is feed of an oxidizing biocide to kill organisms
before they can settle on condenser tube walls, cooling tower ll, and other locations. Chlorine was the
workhorse for many years, where when gaseous chlorine is added to water the following reaction
occurs.

Cl2 + H2O HOCl + HCl


HOCl, hypochlorous acid, is the killing agent. The functionality and killing powe
r of this compound are
greatly affected by pH due to the equilibrium nature of HOCl in water.

HOCl H+ + OCl-
OCl- is a much weaker biocide than HOCl, probably due to the fact that the charge on the OCl- ion does
not allow it to penetrate cell walls. The killing efciency of chlorine dramatically declines as the pH goes
above 7.5. Thus, for the common alkaline scale/corrosion treatment programs, chlorine chemistry may
not be efcient.
Due to safety concerns, liquid bleach (NaOCl) ef ed has replaced gaseous chlorine at many facilities.
The major difculty with bleach is that the product contains a low concentration of sodium hydroxide,
thus when it is injected into the cooling water stream it raises the pH, if by only a small amount.

A popular alternative is bromine chemistry, where a chlorine oxidizer and a bromide salt, typically
sodium bromide (NaBr), are blended in a makeup water stream and injected into the cooling water. The
chemistry produces hypobromous acid (HOBr), which has similar killing powers ot HOCl, but functions
more effectively at alkaline pH.

The primary disadvantages are that an extra chemical is needed and feed systems are a bit more
complex than for bleach alone.

Chlorine dioxide (ClO2) has found some application as an oxidant for two primary reasons. Its killing
power is not affected by pH, and it does not form halogenated organic compounds. Also, chlorine
dioxide is more effective in attacking established bio-deposits. New techniques for pr
oducing ClO2 are
making this option more attractive.

An oxidizer that appears to offer a potentially effective alternative is monochloramine (NH2Cl). This
chemical has been widely used in potable water systems, as itemainsr in solution much longer than
free chlorine, and thus can be effective in large distribution systems. However, chloramines are less
potent than free chlorine towards planktonic microbes in the bulk water. The potential benet in cooling
systems appears to stem from the fact that NH2Cl is much better at penetrating the slime layer of
bacterial colonies to kill the sessile microbes underneath. A full-scale test at an anonymous utility
indicated that the chemical removed previously formed microbial deposits and restored condenser
performance during the summer of 2011. [4] The plant utilizes once-through cooling.

Space limitations prevent a full-blown discussion of scale prevention in cooling water systems, but the
topic is of great importance, especially because restrictions on once-through cooling may force more
plants to install cooling towers. Long ago, chemists and engineers disco vered that without treatment,
calcium and bicarbonate ions (Ca+2 and HCO3-, respectively), when subjected to heat in a condenser
or when cycled up in concentration in a cooling tower would form a hard calcium carbonate (CaCO3)
scale on condenser tube surfaces. The following equation outlines this process.

Ca+2 + 2HCO3- + heat CaCO3 + CO2 + H2O


Unlike many salts, calcium carbonate is inversely soluble with temperature, thus as temperatures rise in
a heat exchanger, the potential for CaCO3 scaling increases. For once-through systems, feed of simple
polyacrylate is often sufcient to prevent scaling. Programs for systems with cooling ot wers are much
more complicated. In the "Good Old Days" of water treatment, a common technique consisted of
sulfuric acid feed to the cooling tower makeup to convert bicarbonate alkalinity to CO2 gas, with feed of

chromate (CrO4-2) to the recirculating water to provide corrosion protection for metal surfaces.
However, chromate use has essentiallybeen banned due to the toxic characteristics of hexavalent
chromium (Cr+6). Most towers now are operated on an alkaline regime to minimize corrosion, and
where to this point in time inorganic and especially organic phosphates have been used for scale
prevention and additional corrosion protection. These programs are not foolproof, as poor chemistry
control can lead to scale formation from phosphate compounds. An important note is that
phosphorous-based treatment programs are losing favor due to phosphate's nutrient effect in natural
waters. Phosphate in cooling water discharge can lead to algae blooms in surface waters and
difculties thereby. All-polymer programs are gaining popularity as the technology improves. [5]

The Thermodynamics of Condenser Fouling


Let's go back to the example outlined at the beginning of this document and inv estigate the effects of
condenser tube fouling or scaling. We will examine the LP turbine, and for simplicity's sake will ignore
the extraction ows. The diagram shows that 2,744,971 lb/hr of saturated steam exits the LP turbine. At
the design condition of 2.5" Hg pressure and a calculated 6.5 percent moisture level, the enthalpy of the
exhaust is 1043.1 Btu/lbm. So the work done in the LP turbine, excluding that from the extraction
streams, is,

2,744,971lb/hr * [(1386.7 1043.1) Btu/lbm] 3,413,654.6 Btu/MW = 271.4 MW

Now consider if condenser fouling causes the absolute backpressure to increase by 1" (Hg) to a level of
3.5" (Hg) absolute. Thermodynamic calculations show that the exhaust enthalpy increases to 1090.1
Btu/lbm. The work from the low-pressure turbine decreases to 238.5 MW. This is a loss of nearly 33
MW! This example illustrates the importance of maintaining condenser cleanliness.

Condenser performance can also be affected by excess air in-leakage. If the vacuum system is not
capable of removing all of the air, the remainder will coat tubes and form pockets within condenser
tubes. Air is a very good insulator, and air binding can cause efciency lossesas great as those induced
by fouling or scaling.

Condenser Performance Monitoring


In 1992, I wrote about condenser performance monitoring for Power Engineering . In the 20 years
since, many power plant engineers, chemists and oper
ators have retired from utility life and have been
replaced by new personnel.

The technique for condenser performance monitoring about which I wrote in 1992 is still just as valid
today, and indeed I have discovered the calculations in sophisticated programs installed on plant
distributed control systems (DCS). However, I have also learned that the datamay be overlooked in the
complexity of hundreds of other readouts, and that plant operators may not recognize condenser
performance problems as they rst arise. Prompt detection is often vital ot prevent small difculties
from becoming large. Via the followingstraightforward process, plant engineers and chemists can
monitor condenser performance and be prepared to react if problems are detected. Much of the
following text is adapted from my 1992 article.

At that time, some of my former co-workers from City Water, Light & Power had attended the General
Physics (www.gpworldwide.com ) course, "Fundamentals of Power Plant Performance for Utility
Engineers."
This excellent course included calculations for determining condenser cleanli ness factors. With
personal computers still being somewhat in their infancy , we rst put the calculations in BASIC
language and used them to monitor condenser performance. Of course, nowadays spreadsheet format
is an excellent method to track condenser performance, and for any interested readers I have the
calculations in Excel. The program utilizes the process variables of cooling water inlet temperature,
outlet temperature, and hotwell temperature, along with xed constants to calculate a condenser
cleanliness factor. The xed constants are,

Circulating water ow rate (gpm)


Number of condenser tubes
Inside tube diameter
Outside tube diameter
Tube length
Number of passes

Also necessary are two variables known as the circulating water correction factor and condenser tube
correction factor, which exist in table format. These values, which were originally compiled by the Heat
Exchange Institute (http://www.heatexchange.org">www.heatexchange.org) are easy to input
into a spreadsheet.

A general rule-of-thumb regarding the program output, i.e., the cleanliness factor, is that a clean
condenser will exhibit a reading of 85 percent. I found this to be true with some condensers, but for
others came up with readings that exceeded 100 percent. The latter was due to design factors.
However, the strength of this program is its ability to monitor trends. Using a clean condenser as a
baseline, a factor above 100 percent is not an issue. The key is detecting a decline in condenser
cleanliness factors, which the program will do without inuence from seasonal changes in cooling
water inlet and outlet temperatures. These changes can otherwise mask true problems.

I successfully used the program for over 15 years to track performance of a number of condensers and
alert operations and maintenance personnel to problems. Both microbiological fouling and scaling
typically manifest themselves as a gradual decline in cleanliness factor. Often, these problems arise
due to a malfunction of chemical feed equipment. It is very important to catch such problems early.

In one instance, a summer drought had reduced the volume of the cooling water surface supply by a
factor of four, and correspondingly increased the dissolved solids concentration by the same factor.
Two once-through condensers that hadnever encountered fouling or scaling difculties in the past
began to exhibit gradually declining performance, as determined by the program. As it turned out, the
drought-induced increase in dissolved solids coupled with summer temperatures initiated calcium
carbonate scaling in the tubes. A mechanical contr actor came in to scrape the tubes during autumn
outages on both units.

The program is excellent for detecting excess air in-leakage, which occurs quite commonly. The strong
vacuum in a condenser naturally will pull in air from any leaks in the condenser shell or the many lines
that penetrate the condenser shell. In one case, the program showed a precipitous drop in condenser
cleanliness factor from 75 percent to 45 percent in a single day on a 200 MW unit.

An inspection revealed that a crack had developed in the condenser shell where a heater drips line
penetrated. The maintenance crew pad-welded the leak, and cleanliness factors returned to normal.

Approximately three months later, the readings once again dropped dramatically the weld had failed.
Maintenance personnel then welded a steel collar voer the spot, which solved the problem permanently.
On another unit, a malfunctioning trap on the condensate return line of a gland steam exhauster
allowed outside air to enter the condenser. The problem was unique in that theair in-leakage was not
evident at high loads, but certainly was at reduced load. Cleanliness factors sometimes uctuated
between 65 percent and 28 percent within the same day as load changed. These wild uctuations ruled
out tube fouling as the problem. After an extensive search, plant operators found the defective trap and
it was repaired. The difculty might have gone on for months without detection from this excellent
program.

References

B. Buecker, "Computer Program Predicts Condenser Performance Monitoring"; Power


Engineering, June 1992.

Kitto, J.B., and S.C. Stultz, Steam/its generation and use, 41st edition, 2005, the Babcock &
Wilcox Company, Barberton, Ohio.

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

Personal conversation with Darrell Rose, Buckman Laboratories, Power-Gen 2011, and
subsequent follow-up with personnel at the utility where the test was performed.

Buecker, B., Post, R., and R. Aull, "Chemical Treatment and Fill Selection Methods to Minimize
Scaling/Fouling in Cooling Towers"; the 71st International Water Conference, Orlando, Florida,
November 13-17, 2011.

Brad Buecker is a contributing editor for Power Engineering and also serves as a process
specialist with Kiewit Power Engineers, in Lenexa, Kan. He has over 30 years of experience in,
or afliated with, the power industry, much of it in chemistry, water treatment, air quality
control, and results engineering positions with City Water, Light & Power in Springeld, Ill.,
and Kansas City Power & Light Company's La Cygne, Kan., station. He has written many
articles and three books for PennWell on steam generation topics. He is a member of the
ACS, AIChE, ASME, and NACE. He is also a member of the ASME Research Committee on
Power Plant & Environmental Chemistry, the program planning committee for the Electric
Utility Chemistry Workshop, and the program planning committee for Coal-Gen.
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