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PPChem PPChem 101 Fossil Cycle Chemistry

PPChem 1 0 1 FOSSIL CYCLE CHEMISTRY

LESSON 4:

Feedwater Treatment

INTRODUCTION
In Lesson 1, it was explained that chemical measures
focusing on the optimum protection of materials in the
feedwater train (the part of the cycle between the con-
denser and the steam generator) are typically called feed-
water treatment. It was also stated that there are four pos-
sible feedwater treatments:
(1) oxygenated treatment (dosing of oxygen and ammo-
nia);
(2) all-volatile treatment (dosing of ammonia) without an
oxygen scavenger;
(3) all-volatile treatment (dosing of ammonia) with addi-
tional dosing of an oxygen scavenger (typically
hydrazine);
(4) all-volatile treatment based on the use of different
amines and in some cases with the parallel applica-
tion of an oxygen scavenger (hydrazine substitutes).
The oldest treatment is treatment (2), which was already
used in the first half of the last century. Later, this treatment
was modified by the additional (parallel) use of hydrazine
(an oxygen scavenger) treatment (3). Treatment (1) has
been applied (in different forms) since the end of the
1960s. The last treatment, (4), is also relatively new. To be
more precise, it can be subdivided into two different treat-
ment variants:
(4a) all-volatile treatment based on the use of volatile
amines and in some cases with the parallel applica-
tion of an oxygen scavenger (hydrazine substitutes);
(4b) all-volatile treatment based on the use of volatile
amines and polyamines.
The fact that there are several feedwater treatments (not
only one) available already indicates that a responsible
decision has to be made when selecting the optimum
treatment for a particular unit. Very often, the manufacturer
or supplier specifies the feedwater treatment; unfortu-
nately, the specification is not always without fail. In the
case of smaller utilities or industrial steam and power gen-
erators, the operators are not adequately knowledgeable
about plant cycle chemistry and leave the decision to sup-
pliers of conditioning chemicals. In such cases where the
salespersons select the feedwater treatment, the decision
is understandably often a sales-promoting suggestion,
and not a decision based on careful weighing of unit-spe-
cific technical issues.
The goal of this lesson is to help the operator to take an
active part in selecting the feedwater treatment and to
understand the very complex interrelation between the
site-specific conditions and plant cycle chemistry.
WHY ONLY VOLATILE CHEMICALS FOR
FEEDWATER TREATMENT?
An attentive reader has already realized that all the chemi-
cals named in the individual feedwater treatments (oxygen,
ammonia, hydrazine, and amines) are either gases (oxygen
and ammonia) or volatile liquids (hydrazine and amines).
The following question is consistent and appropriate: why
do we exclusively use gaseous or volatile agents for feed-
water treatment?
There are many reasons for not using solids for feedwater
treatment. Let us list some of the most important:
In cycles with once-through boilers, any solid chemicals
present in the feedwater (even in trace concentrations)
would immediately result in either deposition in the
waterwalls of the boiler (with subsequent corrosion
damage to the boiler tubes) or deposition in the turbine
(with subsequent efficiency and/or power reduction and
turbine disc and blade failures).
In cycles with drum boilers, any solid chemicals present
in the feedwater would concentrate in the boiler water.
In most cases, an increased blowdown (with water and
heat losses) would be the awkward consequence of
solid chemical application.

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Feedwater is used for the temperature control of steam
in superheaters and reheaters. For this reason, the
presence of any solids in the feedwater is not accept-
able. Deposition of solids in the superheater or reheater
or their transport into the turbine would result in
inevitable damage to these cycle components.
Volatile alkalis (ammonia, amines) are effective during
the steam condensation. They are to some extent capa-
ble of neutralizing acidic contaminants in condensing
steam. This is very important, in particular at locations
of the first condensation (e.g., in the low-pressure
steam turbine, on the steam/condensate side of feed-
water heaters, or in industrial power plants with steam
sendout in apparatus in which steam condensation
occurs.
FEEDWATER TREATMENT AND PLANT CYCLE
MATERIALS
It is very easy to select the optimum feedwater treatment
for a unit with uniform metallurgy in the feedwater train.
This is the case if the tubing of the feedwater heaters is
made of steel (chemists call this all-ferrous metallurgy).
The operator has a lot of freedom with respect to the feed-
water treatment selection. Of the treatment alternatives
listed in the Introduction, the following may be applied in
cycles with all-ferrous metallurgy:
oxygenated treatment (dosing of oxygen and ammonia);
all-volatile treatment (dosing of ammonia) without an
oxygen scavenger.
Naturally, the decision as to whether the oxygenated treat-
ment (OT) or the all-volatile treatment (AVT) without an oxy-
gen scavenger (oxidizing AVT, AVT-O) represents the opti-
mum for a given unit depends on some additional aspects,
which will be discussed later.
For units with a feedwater train in which steel and copper-
based alloys are applied (mixed metallurgy), there is only
one applicable feedwater treatment: all-volatile treatment
(dosing of ammonia) with additional dosing of an oxygen
scavenger (typically hydrazine) (reducing AVT, AVT-R). In
these cycles, it is indispensable to maintain reducing con-
ditions in the entire plant cycle to minimize copper corro-
sion and transport. This is not only true for steady-state
operation but also for startup, cycling and peaking opera-
tion, shutdown, and layup.
When applying OT and AVT-O, the condensate and feed-
water pH and oxygen content are the decisive parameters
for monitoring the cycle chemistry or the feedwater treat-
ment. In cycles operated on AVT-R (i.e., under reducing
conditions), an additional monitoring parameter has
proven reasonable: the oxidizing reducing potential (ORP).
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A negative ORP at the deaerator inlet (ORP 300 mV to
350 mV) is optimum for cycles with mixed metallurgy.
It has to be mentioned that, in addition to the treatment
alternatives discussed above, treatments using amines are
also in use in both cycles with all-ferrous metallurgy and
cycles with mixed metallurgy. The major plant cycle
chemistry guidelines (e.g., those issued by the Electric
Power Institute (EPRI), U.S.A., or by the VGB PowerTech,
Germany) either do not recommend any amine treatments
at all (EPRI) or only address the application of amines very
briefly (VGB PowerTech). Nevertheless, the application of
some of the amine treatments has proven successful in
utility cycles operating at pressures 12 MPa, in combined
cycle units with heat recovery steam generators, and in
many industrial steam and power generating units.
FEEDWATER TREATMENT AND THE PURITY OF
CONDENSATE AND FEEDWATER
All considerations mentioned above and in the following
are exclusively valid for cycles operated with demineral-
ized water. In power cycle chemistry, it is standard to use
the cation conductivity of the condensate or feedwater as
the most important quality parameter to supply informa-
tion about the purity of the operating fluid.
At this point, for non-chemists, some explanatory lines
seem to be appropriate. Two conductivities are used for
monitoring cycle chemistry:
specific conductivity and
cation conductivity (also called acid conductivity or
conductivity downstream of a cation exchanger).
Specific Conductivity
Specific conductivity is an inexpensive, reliable on-line
method of monitoring the overall level of contaminants and
treatment chemicals. Figure 1 shows the specific conduc-
tivity of pure water as a function of the concentration of
ammonia.
It is obvious that specific conductivity may easily be used
for control of ammonia dosing. However, there is a minor
problem common to both conductivity monitoring tech-
niques: the specific and cation conductivity of pure water
and aqueous solutions changes strongly with temperature.
In Figure 2, the temperature-dependence of the specific
1
conductivity of pure water containing 0.5 mg L ammo-
nia (NH3) is depicted. Figure 3 shows the specific conduc-
tivity of pure water as a function of temperature.
For this reason, it is important either to control the sample
temperature (i.e., to keep the sample temperature constant
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the customary set point is 25 C) or, alternatively, to addi-

tionally measure the sample temperature and correct the
conductivity measured at a temperature different from
25 C to the reference temperature of 25 C. State-of-the-
art instrumentation is capable of performing such calcula-
tions.

Since the ammonia concentration is typically relatively

high compared to the contaminant levels normally present
in the condensate or feedwater, specific conductivity
reflects the ammonia concentration and masks the level of
contaminants (impurities). This is demonstrated in
Figure 4. The solid line shows the specific conductivity of
1
contaminant-free ammonia solution (0.5 mg L NH3); the
solid circles show the specific conductivity of the ammonia
1 1
Figure 1: solution (0.5 mg L NH3) contaminated with 10 g L
Specific conductivity of ammonia solutions. NaCl. It is clear that specific conductivity is inapplicable for
monitoring the purity of the condensate or steam.

Figure 2: Figure 4:
Specific conductivity of an ammonia solution (0.5 mg L1 Specific conductivity of ammoniated feedwater (0.5 mg L1
ammonia) as a function of temperature. ammonia) with and without the presence of contaminants as a
function of temperature.
solid line without contaminants
circles with 10 g L1 NaCl

Figure 3:
Specific conductivity of pure water as a function of temperature.
Cation Conductivity
To solve the problem with the determination of the purity of
plant cycle streams, chemists use a simple trick. The con-
ductivity of the sample is measured downstream of a col-
umn filled with regenerated strong acid cation exchanger
cation conductivity. For this reason, this cation conductiv-
ity can serve as an excellent diagnostic tool for determin-
ing the purity of the condensate or feedwater: ammonia
masking the contaminants is removed from the sample via
ion exchange, as are all other cations. Additionally, the
measurement of cation conductivity is more sensitive than
the specific conductivity measurement since the H + ion

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PPChem 101 Fossil Cycle Chemistry
which replaces all the cations of contaminating salts has a
markedly higher equivalent conductance than all other
cations.
The samples depicted in Figure 4 contaminant-free
ammoniated feedwater (0.5 mg L1 NH3) vs. ammoniated
feedwater (0.5 mg L1 NH3) contaminated with 10 g L1
NaCl (there the specific conductivity measurements) are
analyzed via cation conductivity measurement as shown in
Figure 5.
While with specific conductivity measurement (Figure 4)
the trace contamination with NaCl (10 g L1) could not be
detected, cation conductivity measurement (Figure 5)
makes the detection of this relatively low contamination
possible.
For this reason, the cation conductivity measurement is
the most important and most commonly used monitoring
technique for an accurate surveillance of plant cycle
chemistry. This is not only true in the case of the feedwater
treatment discussed in this lesson, but also for all other
quality-related considerations regarding other plant cycle
streams (e.g., boiler water and steam).
Figure 5:
Cation conductivity of ammoniated feedwater (0.5 mg L1
ammonia) with and without the presence of contaminants as a
function of temperature.
black line without contaminants
blue line with 10 g L1 NaCl
Feedwater Treatment and the Purity of the Feedwater
In terms of reliability, availability, and efficiency of any plant
cycle, the highest possible purity of the feedwater (and
naturally of all other cycle streams) is advisable. Expressed
in terms of cation conductivity values, the lowest possible
cation conductivity should be aspired to. This means that
operation of cycles with chemically pure water (specific
and cation conductivities of 0.055 S cm1 at 25 C) is (at
least theoretically) the optimum.
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Let us come back to the real world. Plant cycles are not
operated with chemically pure water (with water sub-
stance, H2O) without any contamination. In practice, we
deal with technically pure water, i.e., with water containing
some contaminants although they are only present at a
very low level. The achievable cycle purity depends on
many factors, such as the nature of the raw water used for
makeup preparation, the makeup water treatment, the
tightness of the condenser with respect to cooling water or
air ingress, the presence (or absence) of a condensate pol-
isher, the purity of cycle treatment chemicals, etc.
There is also a marked difference between high-pressure
utility cycles and typical cogeneration and industrial cycles
with respect to the purity of the plant cycle. In particular in
cogeneration and industrial cycles with condensate return
from the industrial production, the cycle purity may be to
some extent deteriorated (contaminants from the industrial
production are transported via condensate return into the
plant cycle, e.g., in refineries, sugar and paper mills, and in
the chemical industry). Table 1 shows the typical cation
conductivity of the feedwater in different cycles. The val-
ues stated refer to the steady-state operation. During
startup and cycling and peaking operation, the purity of
the cycle is very often impaired.
The following is a ranking of the individual feedwater treat-
ments with respect to the tolerable feedwater quality (the
treatment requiring the lowest cation conductivity is listed
as the first, and the treatment tolerating a moderately
increased cation conductivity as the last):
oxygenated treatment (OT);
all-volatile treatment without an oxygen scavenger
(AVT-O) and all-volatile treatment with additional dosing
of an oxygen scavenger (AVT-R);
all-volatile treatment based on the use of volatile
amines;
all-volatile treatment based on the use of volatile
amines and polyamines.
FEEDWATER TREATMENT AND THE OPERATING
MODE
As discussed in Lesson 3, the operating mode markedly
affects chemistry in the plant cycle. While during continu-
ous steady-state operation the purity of the feedwater is
more easily maintained in the optimum range, during
startup and in cycling or peaking operation the quality of
the operating fluid very often deteriorates (i.e., a cation
conductivity increase in plant cycle streams occurs). The
major goal of the staff responsible for chemistry in such
units is to optimize the operation procedures with the
objective of reducing the length of operation periods with
increased cation conductivity as much as possible.
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Typical cation conductivity Cation conductivity

of the feedwater of the feedwater in best units
Cycle
1
[S cm at 25 C]

Utility cycles with once-through boilers 0.2 0.1 0.15

Utility cycles with high-pressure drum boilers P 0.2 0.2

Industrial cycles without condensate return 0.4 P 0.2

Industrial cycles with condensate return 1.0 P 0.3

Table 1:
Feedwater cation conductivity in different plant cycles.

Most of the possible measures are not chemistry-related.
For this reason, a close cooperation with engineers and
operating staff is absolutely essential. If for some reason a
fast improvement of the cycle purity cannot be attained
(the operation periods with increased cation conductivity
still remain too long), it is probable that unit reliability, avail-
ability, and efficiency will be affected.
From the chemistry standpoint, it may be necessary to
convert cycle chemistry (the feedwater treatment) from a
treatment with more stringent requirements on the feedwa-
ter quality to a "more tolerant" treatment. However, this has
to be considered as a last resort. All cycle chemistry-
improving measures are of a higher priority.
We appreciate any questions and comments on the past
lessons and on this lesson, as well as all in-advance ques-
tions on the next three lessons. With your help, we will be
able to optimize the content of the course lessons.
CLOSING REMARK
This lesson, like all others in this series, is intended to help
all non-chemists responsible for chemistry-related tasks,
all power industry newcomers, and all engineers, whether
chemists or non-chemists, to learn the fossil cycle chem-
istry basics. It is a great challenge for us to support you in
your efforts to improve the plant cycle chemistry in your
plants.

FEEDWATER TREATMENTS
In this lesson, the focus has been on primary, yet general
aspects in connection with feedwater treatments. The indi-
vidual feedwater treatments will be dealt with in the follow-
ing lessons:

Lesson 5
All-Volatile Treatment
Lesson 6
Oxygenated Treatment
Lesson 7
Amine-Based Feedwater Treatments

316 PowerPlant Chemistry 2008, 10(5)