Technical

Paper

Internal Water Treatment For Industrial Steam

Plants
Author: Dennis B. Dyer chloride and sodium sulfate are soluble and usually
do not present a problem in the boiler, but if boiler
A wide variety of fossil-fueled and waste heat boil- water droplets containing these compounds are
ers, turbines, and combined cycle systems are entrained in the steam, deposits can result when
being used in industrial plants. Each plant has spe- the droplets are evaporated in the superheater, or
cific boiler designs, operating pressures, steam load as the steam is expanded through a turbine. Proc-
requirements, quantities of condensate return, and ess feedwater contaminants, such as oil and sugar,
makeup water and condensate qualities. promote foaming and increase steam contamina-
tion. Silica can vaporize with water and add to these
Boiler Feedwater Impurities steam system deposits.
Boiler feedwater impurities, such as calcium, mag- If the steam solids level becomes too high, super-
nesium and iron are well-known threats to boiler heater and/or turbine deposits accumulate. Exces-
reliability. Contamination of feedwater by these sive deposit buildup leads to superheater
elements from makeup and condensate systems overheating and failure, in addition to affecting tur-
has led to many steam generation problems. If not bine efficiency and capacity.
properly controlled, this contamination can deposit
on boiler surfaces, restricting the transfer of heat to Deposit buildup on turbine throttle and stop valves
boiler water and leading to higher tube metal tem- can cause excessive turbine speeds and, subse-
peratures. When the deposit primarily consists of quently, turbine destruction.
iron oxide, it usually has an open pore structure
Dissolved oxygen in boiler feedwater is another
that creates “a boiler within a boiler.” This structure
threat to system operating reliability. Oxygen pit-
concentrates dissolved solids from parts per million
ting can cause metal failures in closed feedwater
(ppm) levels found in the bulk water to percentage
heaters and economizers, requiring expensive
concentrations found within and beneath the
repairs and unscheduled downtime.
deposit. When these under-deposit concentrations
contain dissolved solids, such as sodium hydroxide,
they can corrode the boiler metal. Feedwater Quality Goals
In addition to the more commonly encountered The first step in minimizing potential operating
problems caused by calcium, magnesium and iron, problems associated with feedwater contamination
other feedwater contaminants can also lead to is to minimize contaminant levels in the feedwater.
boiler deposition and generating tube failures. Sil- This can be achieved by efficient external treatment
ica, copper, oil, titanium, barium and many other of the makeup water, by monitoring and (when
compounds can cause unanticipated problems that necessary) by dumping of return condensate.
are often more severe because they are more insu- The level of feedwater quality that must be
lating; consequently, they are more difficult to achieved for successful operation is dependent
remove from the boiler surface. upon individual plant operating conditions. One of
Boiler feedwater contaminants can also lead to the major variables is boiler pressure. The “Consen-
steam system deposits. Sodium carbonate, sodium sus on Operating Practices for the Control of Feed

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©2006, General Electric Company. All rights reserved. TP415EN 0602

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Table A: Suggested water chemistry limits. industrial watertube, high duty, primary fuel-fired, drum-type boilers

Makeup water percentage: Up to 100% of feedwater.

Conditions: Includes superheater, turbine drives, or process restriction on steam purity.
Saturated steam purity target: See tabulated values below.

Drum Operating psig 0-30 301-450 451-600 601-7 751-900 901-1000 1001-1500 1501 -2000
Pressure (1) (11) (MPa) (0-2.07) (2.08-3.10) (3.11-4.14) (4.15-5.17) (5.18-6.21) (6.22-6.89) (6.9010.34) (1Q35-13.79)
Feedwater (7)
Dissolved oxygen, <0 007 <0 007 <0 007 <0 007 <0 007 <0 007 <0 007 <0 007
ppm (mg/L) O2
measured before
chemicaloxygen
scavenger addition (8)

Total iron, =0.1 =0.05 =0.03 =0.025 =0.02 =0.02 =0.01 =0.01
ppm (mg/L) Fe

Total copper, =0.05 =0.025 =0.02 =0.02 =0.015 =0.01 =0.01 =O.01
ppm (mg/L) Cu

Total hardness, =0.3 =0.3 =0.2 =0.2 =0.1 =0.05 ND ND

ppm (mg/L)1

pH @ 77°F (25°C) 8.3–10.0 8.3–10.0 8.3–10.0 8.3–10.0 8.3–10.0 8.8–9.6 8.8–9.6 8.8– 9.6

Chemicals for NS NS NS NS NS VAM VAM VAM

preboiler system
protection

Nonvolatile TOC, <1 <1 <0.5 <0.5 <0.5 <0.2 <0.2 <0.2
ppm (mg/L) C (6)

Oily matter, <1 <1 <0.5 <0.5 <0.5 <0.2 <0.2 <0.2
ppm (mg/L)

Boiler Water
Silica, =150 =90 =40 =30 =20 =8 =2 =1
ppm (mg/L) SiO2

Total alkalinity, <350(3) <300(3) <250(3) <200(3) <150(3) <100(3) NS(4) NS(4)
ppm (mg/L)1

Free OH– alkalinity, ppm (mg/L)* (2)

Specific 5400-1100(5) 4600-900(5) 3800-800(5) 1500-300(5) 1200-200(5) 1000-200(5) =150 =80

conductance (12)
uhos/cm (uS/cm) @ 77°F
(25°C) without neutralization

Total Dissolved Solids (TDS) in Steam (9)

TDS (maximum), 1.0-0.2 1.0-0.2 1.0-0.2 0.5-0.1 0.5-0.1 0.5-0.1 0.1 0.1
ppm (mg/L)

1 as CaCO3
NS = not specified
ND = not detectable
VAM = Use only volatile alkaline materials upstream of attemperation water source. (10)

Page 2 TP415EN 0602

Notes
1. With local treat fluxes >1.5 x 105 Btu/hr/ft2 (>473.2 kW/m2), use values for at least the next higher pressure range.
2. Minimum hydroxide alkalinity concentrations in boilers below 900 psig (6.21 MPa) must be individually specified by qualified
water treatment consultant with regard to silica solubility and other components of internal treatment.
3. Maximum total alkalinity consistent with acceptable steam purity. If necessary, should override conductance as blowdown con-
trol parameter. If makeup is demineralized quality water and boiler operates at less than 1,000 psig (6.89 MPa) drum pressure,
the boiler water conductance should be that in table for 1001-1500 psig (6.9 to 10.34 MPa) range. In this case, the necessary
continuous blowdown will usually keep these parameters below the tabulated maximum values. Alkalinity values in excess of
10% of specific conductance values may cause foaming.
4. Not detectable in these cases refers to free sodium or potassium hydroxide alkalinity. Some small variable amount of total alka-
linity will be present and measurable with the assumed congruent or coordinated phosphate-pH control or volatile treatment
employed at these high pressure ranges.
5. Maximum values are often not achievable without exceeding maximum total alkalinity values, especially in boilers below
900 psig (6.21 MPa) with >20% makeup with total alkalinity >20% of TDS naturally or after pretreatment by lime-soda, or sodium
cycle ion exchange softening. Actual permissible conductance values to achieve any desired steam purity must be established
for each case by careful steam purity measurements. Relationship between conductance and steam purity is affected by too
many variables to allow its reduction to a simple list of tabulated values.
6. Nonvolatile total organic carbon (TOC) is that organic carbon not intentionally added as part of the water treatment regime.
7. Boilers below 900 psig (6.21 MPa) with large furnaces, large steam release space, and internal chelant, polymer, and/or antifoam
treatment can sometimes tolerate higher levels of feedwater impurities than those in the table and still achieve adequate depo-
sition control and steam purity. Removal of these impurities by external pretreatment is always a more positive solution. Alter-
natives must be evaluated as to practicality and economics in each individual case.
8. Values in the table assume existence of a deaerator.
9. Achievable steam purity depends on many variables, including boiler water total alkalinity and specific conductance as well as
design of boiler steam drum internals and operating conditions (Note 5). Since boilers in this category require a relatively high
degree of steam purity for protection of the superheaters and turbines, more stringent steam purity requirements, such as
process steam restrictions on individual chemical species or restrictions more stringent than O.1 ppm (mg/L) TDS turbine steam
purity, must be addressed specifically.
10. As a general rule, the requirements for attemperation spray water quality are the same as those for steam purity. In some
cases, boiler feedwater is suitable; however, frequently additional purification is required. In all cases, the spray water should be
obtained from a source that is free of deposit-forming and corrosive chemicals, such as sodium hydroxide, sodium sulfite,
sodium phosphate, iron, and copper. The suggested limits for spray water quality are <30 ppb (mg/L) TDS maximum, <10 ppb
(mg/L) Na maximum, < 20 ppb (mg/L) SiO2 maximum, and it should be essentially oxygen free.
11. Low pressure boilers frequently use feedwater that is suitable for use in higher pressure boilers. In these cases the boiler water
chemistry limits should be based on the pressure range that is most consistent with feedwater quality. (See Reference 6.)
12. Conversion from ppm (mg/L) TDS values in the ABMA standards (6) used a factor of 0.65.

peak heat fluxes are expected to exceed

water and Boiler Water Quality in Modern Indus-
150,000 BTUs per hour per square foot (Btu/hr/ft2),
trial Boilers,” published by the American Society of
the goal for feedwater contaminant levels should
Mechanical Engineers (ASME), can be used as a
be reduced to that listed for the next highest pres-
guideline in establishing feedwater quality goals
sure range in the ASME table. Conversely, low heat
(refer to Table A).
flux boilers or low load operation may allow re-
Other variables that should be considered include laxation of feedwater quality goals.
boiler heat fluxes, circulation patterns, boiler load
and consistency of control. For example, when
TP415EN 0602 Page 3
Table B: Typical Sampling and Analysis Schedule

to cause a significant deterioration in feedwater

Sample Point Analysis Method Frequency
quality. Continuous conductivity monitoring is
Hardness 2 hours recommended to detect contamination levels that
Treated Makeup require prompt action. Condensate iron levels
Conductivity Silica Continuous
should be monitored during equipment startup
Condensate Conductivity Continuous and at regular intervals to be sure that only
acceptable condensate is being returned. Con-
Iron Daily, equipment densate pH should be monitored at regular inter-
startup
vals to ensure pH of 8.8 to 9.2 is maintained for
pH 8 hours mixed metallurgy systems.
Feedwater pH 8 hours Makeup water quality should also be closely
monitored. Plants with demineralized makeup
Hardness 2 hours
water should monitor conductivity continuously.
Iron Daily Continuous silica monitoring is also recommended
where demineralizers supply makeup to systems
Oxygen Continuous operating above 900 pounds per square inch
gauge (psig) (630 kg/cm2).
Boiler Blowdown Treatment 8 hours
Where sodium zeolite-softened makeup is used,
Alkalinity (or pH) 8 hours
frequent hardness monitoring is recommended.
Silica 8 hours While individual plant experience should be used
as a guide for establishing testing frequency,
Conductivity 8 hours sampling of the main makeup stream once every
two hours is recommended (unless a continuous
Steam Sodium Continuous hardness monitor is used).
A system for the detection and subsequent elimi-
Feedwater Quality Monitoring nation of significant contamination in the makeup
Once feedwater quality goals are established, a should be designed to prevent serious quality
monitoring program, consistent with these goals, deterioration in makeup water storage tanks.
should also be implemented. Feedwater quality
should be monitored downstream of the boiler Boiler Water Treatment
feedwater pumps and any high-pressure feedwa-
There are three general types of chemicals com-
ter heaters. In addition, makeup water and con-
monly used for internal boiler water treatment:
densate should be monitored for contamination
polymers, chelants and phosphates.
prior to their entry into the deaerator. In plants
with makeup and condensate storage tanks,
Polymers
water quality should be monitored ahead of these
tanks. Table B presents a typical sample and Polymers are used to control boiler deposition in
analysis schedule. nearly all industrial boilers. Depending upon the
polymer and feedwater contaminants, the boiler
Quality standards for makeup and condensate
water treatment polymer controls deposition by
streams should be consistent with achieving the
one or more of the following mechanisms:
desired feedwater quality goal. Condensate
streams of generally excellent quality can periodi- • Complexation
cally become contaminated by raw makeup or • Crystal distortion
cooling water as a result of system leaks, or by • Dispersion
iron resulting from a thermal shock to the system
during equipment startup. Provisions should be
made to purify or dump condensate when the
level of contamination becomes sufficiently high
Page 4 TP415EN 0602
Complexation to prevent precipitation of these potentially scale-
forming constituents. EDTA is also successful at
Many of the polymers employed form strong forming complexes with certain forms of feedwa-
complexes with boiler feedwater contaminants, ter iron. Because the precipitation of deposit-
such as calcium. If the polymer-contaminant forming constituents is prevented, boilers are
complex is sufficiently strong to overcome the usually cleaner with chelant treatment than
driving force for precipitation of the contaminant phosphate treatment.
in the boiler water, the contaminant remains solu-
ble and is removed from the boiler by Blowdown. Phosphates
Care needs to be taken in polymer selection, Phosphates are used to control both deposition
because some polymers form insoluble precipi- and corrosion. When fed to control deposition,
tates with calcium when the polymer to calcium inorganic orthophosphate is used to precipitate
ratio becomes too low, because of the underfeed feedwater calcium in the boiler water. In addition,
of chemical or a calcium intrusion. Also, polymers sufficient boiler water alkalinity and silica levels
that form strong complexes with calcium and are maintained to assure the precipitation of
magnesium usually form strong complexes with magnesium.
iron. This can increase erosion-corrosion of the
feedwater system if the polymer is fed there. When proper treatment levels are maintained,
calcium and magnesium are removed from the
Crystal Distortion boiler water, forming a sludge. Consequently, the
boiler water is free of soluble calcium and magne-
In many boiler systems, feedwater contaminants, sium at locations of steam generation so that
such as calcium, are made to precipitate through scale does not form on the steam generating sur-
the addition of phosphate. In these instances, a faces.
polymer is used which adsorbs onto freshly
formed particles, restricting their growth. By limit- When boiler feedwater that is substantially free
ing their size, the polymer aids the formation of from calcium and magnesium is used, such as
particles that move freely with the flow of water, when the makeup water is demineralized, corro-
facilitating their removal through boiler blow- sion control, rather than deposition control, be-
down. comes the main concern. Phosphate is frequently
fed to control corrosion, employing a “coordi-
Dispersion nated” or “congruent” phosphate-pH program. In
these programs, phosphate is fed to buffer the
The boiler polymer employed should be effective boiler water so that neither very high nor low pH
in adsorbing onto particles in the boiler water and conditions develop, even in areas of high boiler
preventing those particles from growing by water concentrations, such as develop beneath
agglomeration with other particles. The polymer porous tube deposits and in areas of poor water
should also prevent particles from attaching to circulation.
boiler surfaces. The polymer should always be
effective on particulate iron oxide that enters all
boilers with the feedwater. In those instances
Treatment Programs
where phosphate is fed to precipitate feedwater Industrial boiler systems are treated with one or a
calcium, the polymer should also be effective at combination of chemicals. Nearly all systems are
dispersing calcium phosphate and magnesium treated with a polymer. Many boilers that receive
silicate. sodium zeolite-softened makeup water are suc-
cessfully treated with only polymer. Others, where
Chelants the demand for deposit control capability is
Chelant treatment of boiler water uses an organic greater, may use chelant and polymer to take ad-
complexing agent, ethylenediaminetetraacetic vantage of the strong calcium, magnesium and
acid (EDTA). EDTA forms complexes with calcium ferrous iron complexes formed by the chelant.
and magnesium in boiler feedwater that are suffi-
ciently stable under most boiler water conditions
TP415EN 0602 Page 5
 blowdown rates be supplemented by monitoring
to assure that stream purity does not deteriorate
and that the internal treatment program is
designed to effectively control deposits under
these conditions.

Steam Purity
To assure both superheater reliability and effi-
cient, reliable steam turbine operation, high steam
levels must be generated consistently. Although
each plant has its own individual requirements,
satisfactory industrial plant operation is usually
Figure 1: Coordinated phosphate-pH program controls free obtained when less than 10 to 20 parts per billion
caustic and resultant corrosion. (ppb) (mg/L) of sodium and 10 to 20 ppb (mg/L) of
silica are present in the steam.
Phosphate is combined with polymer to treat boil-
ers for deposit control whenever high feedwater Steam can become contaminated by either the
hardness is encountered. This treatment is also entrainment of boiler water or the vaporization of
used in many low hardness systems. Both chelant boiler water contaminants. In industrial plants,
and polymer are often combined with phosphate silica is the only common boiler water contami-
to enhance deposit control capability. nant that causes steam contamination due to
vaporization. Silica vaporization is usually con-
Phosphate is used to treat most demineralized trolled by limiting boiler water silica to levels ap-
water systems to control corrosion. A “coordi- propriate for the pressure, pH, and silica
nated” or “congruent” phosphate-pH program to relationship illustrated in Figure 2.
“capture” any alkaline or acidic feedwater con-
tamination is used to prevent tube metal corro- Steam contamination by boiler water entrainment
sion. Figure 1 depicts typical controls used for this is caused by spray mist, leakage, priming or foam-
treatment. ing. Spray mist is the natural entrainment of water
not removed by steam purification equipment.
Boiler Water Quality Control Spray mist contamination increases gradually
with steam load and drum level. It can be reduced
Boiler water control must be established, consis- only by changing the steam drum internals,
tent with plant needs and operating experience. reducing boiler load, changing water level or a
Again, the ASME “Consensus” (Table A) is a place to combination of these actions.
start in establishing control limits. These limits
may be modified, based upon careful considera- Leakage occurs when steam and water bypass
tion of the benefits to be derived and to assure the steam purifying equipment. When leakage is
operating reliability with the design of an internal the main cause of steam contamination, a change
treatment program. For example, it may be nec- in load has little effect on the contamination level.
essary to control specific conductance below the Leakage can be controlled only by the proper
recommended maximum to obtain the steam installation and maintenance of steam purifying
purity necessary for reliable operation. equipment.

For other systems, large amounts of makeup and “Priming” is the term used when large quantities
blowdown water may be saved by exceeding the of water are entering, overloading and passing
ASME recommendations for boiler water conduc- through steam purifying equipment. Priming
tivity and alkalinity, usually through the use of causes large changes in steam purity. It is caused
antifoam additives. This can mean a savings of by rapid losses of header pressure and changes in
tens or even hundreds of thousands of dollars per drum level and steaming rate. Priming can be
year in heat and treated water. However, the sav- controlled only by maintaining consistent pres-
ings could be lost due to a forced boiler or turbine sure and drum level and by limiting the load
outage. Therefore, it is important that reduced change rates.

Page 6 TP415EN 0602

 measuring the sodium content or, if solids greater
than 100 ppb (mg/L) are acceptable, by following
degassed cation conductivity. The installation of
monitoring equipment, such as a sodium-specific
electrode, is recommended to provide a continu-
ous record of steam purity. Periodic sampling for
low-level silica determination is also recom-
mended.

Steam Temperature Control

Steam system deposits often result from problems
with the steam temperature control system.
Plants commonly control steam temperature by
the injection of water into superheated steam.
Sources of this water include the feedwater, a
special evaporator or demineralizer, plant con-
densate, or a sweet water condenser. Any solids
contamination in this water becomes a solid con-
Figure 2: Effect of silica and boiler water pH on the taminant in the steam. Therefore, this water
volatility of silica. should be as pure as the steam itself.

“Foaming” describes the development of stable Regardless of the source of water, operating pro-
bubbles on surface of the boiler water. The bub- cedures can introduce contaminants that cause
bles are closer in density to steam than boiler severe steam system problems. Possibilities
water and, therefore, not as effectively removed in include contamination with condenser cooling
steam purifying equipment. Steam contamination, water, condensate corrosion products, demineral-
resulting from foaming, is usually not easily repli- izer acid, or caustic regenerants. A sodium-
cated, but it often increases with steam load and specific ion electrode provides the most sensitive
boiler level. Percentage increases in boiler water means of monitoring; however, at a minimum,
solids are substantially exceeded by the percent- continuous conductivity monitoring is recom-
age increases in steam solids. Foaming can be mended for this water supply.
controlled by feeding an antifoam additive, Other plants control steam temperature with
increasing boiler blowdown, and, occasionally, by closed heat exchangers. Often a portion of the
reducing boiler water level and operating load. superheated steam passes through one of these
exchangers that are installed in the boiler mud
Steam Purity Monitoring drum. Cracks at the fittings can leak boiler water
into the steam. As a minimum precaution, steam
To help avoid serious problems that can result
purity should be monitored with conductivity
from steam impurities, a steam monitoring pro-
meters to detect boiler water contamination.
gram should be implemented. To assure represen-
tative sampling, nozzles, as prescribed by the
American Society for Testing and Materials (ASTM), Turbine Corrosion
ASME or the Electric Power Research Institute Turbine corrosion is most commonly caused by
(EPRI), should be installed in steam headers, pref- sodium hydroxide deposits, condensation of
erably in a vertical line at sufficient distance from acidic compounds from the steam, and oxygen
elbows or tees to avoid flow effects. and water intrusion when the turbine is out of ser-
If it is necessary to sample superheated steam, it vice.
should be desuperheated at the point of sampling Caustic deposits can cause corrosion and crack-
to prevent “plating out” of steam solids on the ing of expansion joints, diaphragms, seals and
sample line. Steam should be monitored by
TP415EN 0602 Page 7
numerous other components. The problems Bibliography
caused by caustic can best be controlled by main-
taining good steam purity. Additional protection 1. American Society of Mechanical Engineers,
against caustic can and should be obtained by “Consensus on Operating Practices for the
employing a coordinated or congruent phos- Control of Feedwater and Boiler Water Quality
phate-pH program, whenever the boiler feedwater in Modern Industrial Boilers,” ASME, New York,
is of suitable quality. NY (1994).

Volatile acidic compounds, such as low-molecular 2. Betz Laboratories, Inc., Betz Handbook of In-
weight organic acids and carbon dioxide, often dustrial WaterConditioning, 9th ea., Betz Labo-
cause corrosion near the point of initial condensa- ratories Inc., Trevose, PA (1991).
tion. Protection from this corrosion can be pro- 3. Lane, R. W.; Neff, C. H.; Larson, T. E. “A New
vided by a properly selected neutralizing amine. Method for Increasing the Sensitivity of the
The best protection for the turbine is provided by Conductivity Measurement of Steam Purity”,
an amine with a sufficiently low distribution ratio Proceedings of the American Power Confer-
to favor condensate over steam, and adequate ence, Illinois Institute of Technology, Vol. 23. p.
basicity to provide good pH control when fed in
556 (1961),
sufficient quantity.
Out-of-service corrosion protection for the turbine
is accomplished by keeping the turbine dry. The
turbine should be isolated from all steam connec-
tions by a double block-and-bleed arrangement.
Condensation can be avoided by heating with a
continuous supply of warm air to keep the metal
temperature above the dew point.

Summary
Efficient, reliable performance of an industrial
boiler plant requires an effective water treatment
program that includes the following:
• A detailed evaluation of the plant equipment
and the operating requirements
• Establishment of feedwater and boiler water
quality goals, and a chemical treatment tai-
lored to plant operating conditions
• Monitoring of the operation to maintain speci-
fied goals and controls and assure plant per-
formance

Page 8 TP415EN 0602