SWAS AND GAS ANALYSERS

26-03-07

Water plus metal equals corrosion. This reality attacks the bottom line of every steam driven power generation plant
in the world.
In a steam power plant, high purity water is heated and boiled to make steam, which energizes and powers a turbine
to produce electricity.
Water and steam are in constant contact with metal surfaces threatening the integrity of plant equipment like
condensers, heaters, pumps, piping, boilers, and turbines.
Fortunately, water purification and chemical treatment greatly reduce and control the corrosion in the plant.
Ensuring good cycle chemistry to prevent corrosion, however, requires accurate and continuous analytical
measurements in the demineralization train, cooling water, condensate, and boiler feed-water and steam systems.

Corrosion occurs when metal ions transfer from a base metal to water and combine with oxygen to become
hydroxides and solid metal hydroxides. Resultant particles often travel to other parts of the system and are
deposited.

Deposit is a poor conductor

Once a deposit forms, it attracts more suspended solids and the deposit grows. Deposits frequently accumulate on
heat exchange surfaces, boiler tubes, and heaters.
The deposit is a poorer conductor of heat than metal and therefore interferes with heat transfer across the tube. This
lowers the overall cycle efficiency and can cause local tube overheating failures. Deposits can also significantly
lower the efficiency of the turbines and, in turn, become corrosion sites when dissolved solids trapped in the deposit
concentrate as the liquid boils away. Eventually, the concentration reaches highly corrosive levels and severe under-
deposit corrosion occurs.
A tough oxide film that protects the base metal is the best way to defend iron and copper from corrosion. For iron
and carbon steel, the protective film is magnetite.
For copper and copper alloys, the protective film is cuprous oxide. This film works only in the presence of properly
controlled water chemistry.
Proper water chemistry also ensures that the film won't wear away and, if a break occurs, the film quickly repairs
itself.

Controlling water chemistry requires maintaining high purity water, controlling pH, monitoring for trace quantities
of dissolved oxygen, and, if necessary, controlling the feed of a scavenging agent like hydrazine

Better boiler chemistry

A key culprit behind many boiler failures is the accumulation of scale and corrosion brought about by contaminated
water entering the boiler. Even in a well-controlled regime, it is not possible to totally eliminate the presence of
potential contaminants present in boiler feedwater. For example, in a 500 megawatt boiler, 1,500 tons of water is
boiled off per hour – that equates to one million tons per month. Consider that most of the resulting contaminants
that are present in the water will remain in the boiler and the need for close monitoring and control becomes
apparent.

Two areas most likely to introduce contamination into the system are the condenser and the feedwater system. In the
condenser, steam from the turbines is condensed using cooling water from a local source. Although this water is
pretreated to remove mud, silt and any organic matter, problems can still occur if it becomes mixed with the
condensate from the turbine steam. Over time, condenser leaks are almost inevitable, enabling contaminated cooling
water to enter the condensate compartment.

With the feedwater system, de-ionised water is preheated and chemically treated before it enters the boiler. Although
chemical treatment can help to reduce contamination, it can also cause immense damage to the boiler. For example,
certain solid chemicals, such as sodium hydroxide or sodium phosphate, can actually speed up boiler corrosion if
applied in overly high concentrations.

Applications using a boiler drum may also use boiler blowdown to slowly “flush” out feedwater contaminants such
as scale and high chemical concentrations. The level in the drum is maintained by adding make-up water, which is
itself added to the condenser to offset any losses. However, this process can be very wasteful in terms of loss of heat
and high purity water and so should be utilised only when it is essential. If it occurs too frequently, this operation
can become expensive and inefficient.

Why measure boiler chemistry?

The elevated temperatures and pressures inherent in power generation applications greatly increase the speed of the
chemical reactions taking place in the boiler. The result is an aggressive environment that can dramatically reduce
the life of the boiler if not properly controlled. In some cases, boilers with poor water chemistry have been known to
last just six weeks before failure. As further proof, the Electric Power Research Institute (EPRI) estimates that 50%
of forced outages in power plants in the US are due to boiler failures directly attributable to corrosion damage.

By measuring and monitoring not just the boiler chemistry, but also other areas around a power plant, it is possible
to obtain a better overview of current conditions. When incorporated into a planned preventative maintenance
programme, this information can help to substantially reduce the risk of unplanned outages.

Controlling contamination
To keep the steam raising process running at peak efficiency, the following parameters should be monitored
constantly:

Dissolved oxygen: Even small parts per billion concentrations of oxygen dissolved in the feedwater stream can
cause pitting in the boiler, drastically its operating life. The concentration of dissolved oxygen therefore needs to be
checked throughout the feedwater loop, from the extraction pump through to the deaerator and the boiler inlet.

One way to control dissolved oxygen levels is by dosing boiler feedwater with hydrazine. Hydrazine is a colourless
liquid, which is highly soluble in water. It is a powerful reducing agent that reduces oxygen to form nitrogen and
water. At high temperatures and pressure, it will also form ammonia, which increases the feedwater pH level,
reducing the risk of acidic corrosion. As an oxygen scavenger, hydrazine is widely used to remove trace levels of
dissolved oxygen in the boiler feedwater.

Hydrazine is also ideal as it reacts with soft haematite layers on the boiler tubes to create a hard protective magnetite
layer which acts to protect the tubes from further corrosion.

Placing a hydrazine monitor at the feedwater inlet will help check that feedwater is being dosed with the correct
amount of hydrazine. Too much hydrazine is both wasteful and costly, whilst too little will not be able to adequately
control dissolved oxygen levels and will prevent the formation of magnetite. Typically, the most effective dosage of
hydrazine is 3:1 parts hydrazine to the expected level of dissolved oxygen.

pH & Conductivity: pH is an extremely important parameter to measure, as it gives an indication of the degree of
acidity or alkalinity of the feedwater.

Measurement of conductivity in the feedwater and steam loops provides an indication of water and steam purity. By
measuring the electrolytic conductivity of the feedwater (that is, its ability of the feedwater to pass an electrical
current), it is possible to ascertain the level of contamination present, which can then be used to dictate the level or
duration of treatment required. For example, where boiler blowdown is used, conductivity will be one of the main
parameters used to control the frequency of the blowdown process.

Silica: Despite having no direct corrosive effect on plant, silica can form extremely hard and dense scales in the
boiler and turbines, hampering heat transfer efficiency and increasing the risk of mechanical failure such as turbine
blade malfunction. Silica entering a high-pressure boiler can concentrate very quickly.

Just 1ppm of silica in the feedwater for a 500W boiler evaporating 1,500 tonnes of water per hour will result in 1
tonne of silica being deposited in the boiler in just one month.

As dissolved silica is only weakly ionised, it is difficult to detect by conductivity measurement. For this reason,
dedicated silica analysers are necessary if accurate information is to be obtained.

Depending on the type of power plant, typical sampling points for silica monitoring include the water treatment
plant, the boiler drum and the saturated steam.

Sodium: Sodium is one of the most important parameters to measure on a boiler plant. Although conductivity
measurement is typically used to indicate total dissolved solids or chemical conductivity, it lacks adequate
sensitivity. As sodium is present in the critical dissolved compounds, it can be detected with on-line sodium
monitors, which are very sensitive.

Other parameters that operators may also wish to monitor for include phosphate, ammonia and chloride, using
sensors that offer quick response times, are temperature tolerant and require minimal maintenance.

Tips for online monitoring

Tips for maximising the efficiency of online monitoring systems include using instruments that can respond quickly
to changes in boiler chemistry and have self-diagnostic capabilities where possible.

The location of monitoring equipment is a vital component in ensuring the best return on investment in a power
plant. Ideally, monitoring equipment should be situated in an environment that has less potential for damage, has
easy access for maintenance and allows for enhanced measurement accuracy.

Sampling instruments should also be located together, where possible, in a clean and accessible environment. The
conditions for sampling must also be ideal, preferably with samples brought down to 25oC for measurement.

One way to achieve this is to use pre-manufactured packaged monitoring stations. Incorporating a full array of
sampling instruments, including coolers and pressure reducers, these stations can be built to an operator’s
requirements and can simply be connected up to the power plant’s existing sampling lines, greatly reducing the time,
cost and disruption typically associated with installing and commissioning sampling systems.

Summary
The ability to gauge maintenance frequency, coupled with enhanced life cycle costs, offers a golden opportunity to
improve reliability of supply and minimise unscheduled disruptions.

For this reason, it is important to ensure that online monitoring systems are themselves well maintained and that,
where possible, they utilise the latest developments in technology to ensure they deliver maximum benefits.

BOILERS & COOLING TOWERS

Boilers and cooling towers share two major water-related problems: deposits and corrosion. As steam
is generated by a boiler or water evaporates from a cooling tower, dissolved minerals are left behind,
increasing the concentration of these minerals. Additional minerals are introduced via the water added
to makeup the water lost to steam/evaporation. Eventually, the minerals reach a level (or cycle of
concentration) that will cause either loss of efficiency due to scale or damage from corrosion. This
level can be determined by the Ryznar or Langlier indices and correlated to a conductivity or TDS
range. Most people recognize problems associated with corrosion. Effects from scale deposits,
however, are equally important. For example, as little as 1/8" of scale can reduce the efficiency of a
boiler by 18% or a cooling tower heat exchanger by 40%!
A variety of water treatment methods are employed in an effort to control these problems. Even with
water treatment, it is still necessary to regularly blowdown or bleedoff part of the concentrated water
and make up lower salinity water to reduce the overall mineral concentration.
To conserve water and treatment chemicals, it is desirable to allow the dissolved minerals to reach a
maximum cycle of concentration while still avoiding problems. Because feedwater/make-up waters
vary in the types and amounts of minerals present, the allowable cycles of concentration will vary. As
a result, regular testing of boiler and cooling waters is essential to optimize water treatment programs
and blowdown schedules. Tests commonly performed include conductivity or TDS, pH and ORP. Myron
L Company instrumentation provides you with a simple, fast, and accurate means of testing these
parameters.
Many cooling towers and boilers have inline controllers used to release water from the tower or boiler
and feed chemical into the system. The controllers must be calibrated regularly to ensure fouling or
drift of the sensor has not occurred. Our portable instruments in conjunction with NIST traceable
standard solutions provide rapid verification of the accuracy of online controllers. This method reduces
manpower and the likelihood of disturbing or damaging sensors.
CONDUCTIVITY is the measurement of a solution's ability to transmit an electrical current. It is
usually expressed in microsiemens/cm (micromhos/cm). Pure water is actually a poor electrical
conductor (18,200,000 ohms/cm of resistance). It is the amount of ionized substances (or salts)
dissolved in water which determines the conductivity. Because the vast majority of the dissolved
minerals in water are these conductive inorganic impurities, conductivity measurement is an excellent
indicator of mineral concentration. The Myron L Instruments were developed for just this purpose.
Models are available which display conductivity and/or ppm of TDS. For detailed information
regarding the relationship between conductivity and TDS, please see the Myron L Application
Bulletin: Standard Solutions.
pH, the measurement of acidity or basicity, is one of the most important factors affecting scale
formation or corrosion in a boiler or cooling system. The types of impurities comprising the mineral
concentration behave differently at various pHs. Low pH waters have a tendency to cause
corrosion, while high pH waters may cause scale formation.

BOILER WATER requirements can range from very pure to more than 6500 microsiemens, depending on size,
pressure, application, and feedwater. Once the maximum cycles of concentration has been established, a
conductivity instrument can conveniently help you to determine if the blowdown schedule is adequate. Samples
should be cooled to at least 160F (71C) to insure accurate temperature compensated readings.
BOILER CONDENSATE samples are often tested to determine if there is any carryover of boiler water solids or
contaminants entering from outside the system. Condensate is relatively pure water, and values of 2-100
microsiemens are common. Because of these low values, a multiple-range instrument is recommended to
increase the resolution and accuracy of the reading.
COOLING TOWER WATER has become more challenging since the reduced use of acid and the elimination of
chromate. Monitoring conductivity and pH has become imperative to maintain a proper treatment program.
Although many systems have controls on these parameters, the possibility of a system upset is always present.
Even slight upsets can cause rapid scaling of heat exchangers.
BIOLOGICAL GROWTH is another extremely important facet to proper cooling water management. Microbes
can cause corrosion, fouling and disease. Oxidizing biocides (chlorine, bromine & iodine) have been employed
to keep bacteria under control. Monitoring of the ORP (Oxidation Reduction Potential) is very useful in its
ability to correlate millivolt readings to sanitization strength of the water. The new ULTRAMETER line includes
this parameter for quick on-site determinations.