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LESSON 7
Feedwater Treatment with Organic Chemicals
INTRODUCTION
In Lesson 4, the four possible feedwater treatments were
listed.
(1) Oxygenated treatment (dosing of oxygen and ammo-
nia), OT;
(2) All-volatile treatment (dosing of ammonia) without an
oxygen scavenger, typically called oxidizing all-volatile
treatment, AVT(O);
(3) All-volatile treatment (dosing of ammonia) with addi-
tional dosing of an oxygen scavenger (typically
hydrazine), usually denoted as reducing all-volatile
treatment, AVT(R);
(4) All-volatile treatment based on the use of different
amines and in some cases with the parallel application
of an oxygen scavenger (hydrazine substitutes).
The first three of these have already been dealt with in the
earlier lessons. Lesson 5 outlined both the oxidizing and
reducing all-volatile treatments and Lesson 6 the oxy-
genated treatment. The writer of these two lessons had a
fairly easy job. In the internationally acknowledged plant
cycle chemistry guidelines, e.g., in those issued by the
Electric Power Research Institute, Palo Alto, CA, U.S.A. or
PowerTech, Essen, Germany, these treatments are exten-
sively elucidated. Guide values for these treatments are
available although some minor differences between the
two sources mentioned exist.
The situation is markedly different with respect to the
application of organic plant cycle treatment chemicals.
None of the internationally acknowledged plant cycle
chemistry guidelines deals with this subject. Nevertheless,
organic plant cycle treatment chemicals are in use by
many, predominantly industrial, steam and power produc-
ers. The users mostly rely on information supplied by the
respective chemical vendor or on their own operation
experience.
2008 by PowerPlantChemistry GmbH. All rights reserved.
496
PPChem 101 Fossil Cycle Chemistry
FOSSIL CYCLE CHEMISTRY
The benefit of exclusive dependence on vendors is always
debatable. While the major tasks of all steam and power
producers are optimizing efficiency and ensuring long-
term availability and reliability of the plant, the vendor (or
its salesperson) is interested in sales. Naturally, there are
many serious chemical vendors and/or salespersons.
Unfortunately, not all vendors and salespersons are quite
as trustworthy. (This is true for the entire marketplace, not
only for plant cycle treatment chemicals.)
The potential user has the following problems:
As a rule, the chemicals to be applied are proprietary
mixtures of various chemicals. The actual chemical
composition is not revealed. The obligatory Material
Safety Data Sheets typically do not contain sufficient
and enlightening information about the individual mix-
ture components and their concentrations.
Data about the thermal stability of these products are
hardly known and are not available to the final user.
Due to a partial or complete decomposition of these
proprietary mixtures at elevated temperatures/pres-
sures, the produced steam contains the final decompo-
sition products of all organics, carbon dioxide (CO2) and
noteworthy concentrations of low-molecular weight
organic acids such as formic and acetic acid. Because
of this, the cation conductivity of the condensed steam
is often markedly increased. In this way, the most
important cycle chemistry monitoring parameter, the
cation conductivity, loses its meaningfulness: the
operator does not know whether the increase indicates
the ingress of dangerous contaminants into the cycle or
is a consequence of the abovementioned decomposi-
tion of the chemical additive.
The increased cation conductivity of the steam may be
a problem with respect to the turbine manufacturer war-
ranty. Nearly all turbine manufacturers demand steam
cation conductivity values as stated when discussing
the all-volatile treatment.
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Despite all of this, the organic plant cycle treatment chemi-
cals are successfully used in a great many steam and
power generating cycles in industrial and cogenerating
plants and also in utilities operating cycles with circulation
boilers at pressures lower than 12 MPa (1 740 psi).
Application in cycles operating at pressures higher than
12 MPa is also reported. In the last decade, promising
results have been achieved with the application of organic
additives in combined cycle units with drum-type heat
recovery steam generators.
WHAT ARE THE TYPICAL COMPONENTS OF
ORGANIC ADDITIVES FOR THE FEEDWATER
TREATMENT?
The most typical components of organic plant cycle addi-
tives may be subdivided into four groups:
Volatile alkalizing amines such as, e.g., morpholine,
ethanolamine, cyclohexylamine, and dimethylamine
Polycarboxylates
Oxygen scavengers (hydrazine substitutes), e.g., carbo-
hydrazide, diethylhydroxylamine, and methyl ethyl
ketoxime
Film-forming diamines/polyamines
These components are generally used in combined pro-
prietary mixtures/blends.
Successful longtime experience with the use of amines in
secondary cycles of nuclear power plants with pressur-
ized-water reactors (PWRs) is available. However, this
experience is not completely applicable to fossil cycles. In
contrast to the majority of utility fossil units operating at
high pressures, the pressure in a secondary cycle typically
ranges only between 68 MPa (8701 160 psi). The sec-
ond very important difference is the steam temperature. In
utilities, the temperature of the main (superheated) and
reheated steam is generally considerably higher
(450650 C or 8421 202 F) than that of the saturated
steam produced in secondary cycles of PWRs
(275295 C or 527563 F).
For this reason, the decomposition rates of amines in fos-
sil cycles is distinctly higher than in secondary cycles of
PWRs. Figure 1 shows as an example the effect of mor-
pholine addition in a typical refinery cycle. In a study by
Carvalho et al. (2001), cation conductivities in the range of
0.20.9 S cm1 in utility cycles (boiler pressures
12.519.8 MPa and superheat temperatures 440482 C /
1 8002 800 psi and 824900 F), 0.31.0 S cm1 in
hydrocarbon and chemical processing industries (boiler
pressures 10.412.5 MPa and superheat temperatures
375480 C / 1 5001 800 psi and 707896 F), and 0.5
1.9 S cm1 in independent power producer cycles (boiler
pressures 6.311.7 MPa and superheat temperatures
480513 C / 9001 680 psi and 896955 F) were
reported. The study indicates that these plants have oper-
ated for extensive periods with no steam turbine damage
or deposition using proprietary amine blends.

Volatile Alkalizing Amines

The volatile amines increase the
feedwater pH as ammonia does.
However, the major reason for the
application of volatile alkalizing
amines is their favorable distribution
behavior in comparison to that of
ammonia. This is in particular impor-
tant for inhibiting corrosion in cycle
components in which the first con-
densation of the steam occurs. This
happens, for example, on the sur-
faces of low-pressure turbine
blades, in feedwater heaters, in con-
densers, and in the case of steam
sendout in various components of
an industrial plant. The application
of these additives results in a
marked reduction in the corrosion
product level in the returned con-
densate and in feedwater and con-
tributes in this way to the avoidance
of deposit buildup in boiler tubes:
fewer deposits in the boiler tubes, Figure 1:
fewer under-deposit corrosion- Cation conductivity and pH of steam in an industrial unit with and without addition of
caused boiler tube failures. morpholine in the feedwater (Savelkoul, Janssen and Verhoef, 2001).

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It seems that suitable amine blends are capable of neutral- cycling or peaking mode during startup, the corrosion
izing their own decomposition products and in this way of product concentration is very low.
inhibiting corrosion in the early condensation areas.

Polycarboxylates MONITORING CYCLE CHEMISTRY IN UNITS ON

Polycarboxylates (applied in the form of sodium salts) rep-
resent a typical example of sludge dispersants and scale
control polymers used for avoiding deposition on or on-
load cleaning of water-touched boiler surfaces and for
controlling the boiler water pH. Although polycarboxylates
are relatively temperature-stable, their application in boil-
ers with operation pressures higher than 8 or 10 MPa is
questionable (because of their excessive decomposition).
Oxygen Scavengers
In cycles with mixed metallurgy, reducing conditions in the
whole cycle are vital (see Lesson 5 in this series). If for
some reason hydrazine cannot be used as a reducing
agent, the application of hydrazine substitutes such as
carbohydrazide, diethylhydroxylamine, and methyl ethyl
ketoxime is possible. As is the case with all organic plant
cycle additives, these oxygen scavengers are also decom-
posed at higher temperatures.
Oxygen scavengers, sometimes reported as passivators,
are very often a part of proprietary blends offered by ven-
dors of organic plant cycle treatment chemicals.
ORGANIC FEEDWATER TREATMENT
Cation Conductivity
As mentioned above, the use of organic plant cycle treat-
ment chemicals is typically accompanied by an increase in
cation conductivity throughout the plant cycle. The opera-
tor has problems in indentifying whether this increase is
exclusively caused by decomposition products of the
additives used or whether there is ingress of contaminants
into the cycle. While an increase caused by additive
decomposition products may be relatively harmless
(assuming that these decomposition products are neutral-
ized by the additives themselves), an ingress of contami-
nants such as chlorides or sulfates has as a rule a detri-
mental effect.
Figure 2 demonstrates the cation conductivity dilemma: a
1
cation conductivity of 0.5 S cm can be caused by
1
about 770 g kg (ppb) carbon dioxide, which may be
relatively harmless, or can be caused by non-harmless
anions like chloride, sulfate, formate, or acetate in concen-
1
trations between 40 and 80 g kg (ppb). It is clear that
the operator needs some additional guidance to make
adequate operation decisions.

Film-Forming
Diamines/Polyamines
In the last two decades, proprietary
mixtures of alkalizing volatile
amines and diamines or poly-
amines have been available and in
use. The application of these
blends even in high-pressure cy-
cles with superheated steam tem-
peratures above 500 C results, in
contrast to mixtures of solely
volatile amines, in a low cation
conductivity of the steam. A cor-
rect application assumed, values
1
of 0.3 S cm can be reached.
This indicates a high thermal sta-
bility of the diamines/polyamines.
The advantage of the application of
blends containing diamines/poly-
amines is comprehensive corro-
sion protection and the formation
of a long-lasting, relatively stable
Figure 2:
polyamine film on the surfaces of 1
the units. This is advantageous Single contaminant concentrations resulting in a cation conductivity of 0.5 S cm . An
innumerable number of contaminant combinations may cause the same cation
particularly for units operated in
conductivity.

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By monitoring degassed cation conductivity, the contribu- THE STATUS OF THE FEEDWATER TREATMENT
tion of carbon dioxide is eliminated. However, all other WITH ORGANIC CHEMICALS AMONG THE
anions, such as chlorides, sulfates, acetates, and formats, OTHER FEEDWATER TREATMENTS
cannot be eliminated by this technique. The only reason-
Although the internationally acknowledged plant cycle
able alternative to reliably determine the type of contami-
chemistry guidelines nearly completely neglect this feed-
nants is ion chromatography. Although on-line ion chro-
water treatment, its application is in many cases justifiable.
matographs are available on the market, not all operators
Dooley introduced the modified continuum of treatments
would be ready to spend money on this (additional) instru-
in 2003 (Figure 3). The width of the wedge or funnel in
mentation or would have adequately qualified personnel at
which the continuum of treatments is located is propor-
their disposal to make use of it.
tional to the level of possible contaminant in the cycle. So
the point of the funnel represents a plant with a conden-
sate polisher or a very tight condenser. The open end
Concentration of Organic Additives represents plants without polishing, using seawater or
Since the operator does not know the precise composition high-salinity cooling, or having a cooling tower. The better
of the proprietary blend of chemicals used, the operator's the air in-leakage control, the nearer to the point of the
chemist is hardly capable of determining the actual con- wedge. Those treatments located in the continuum nearer
centration of the individual components. Determination of to the open end are those which can better counteract
the actual concentration is very often replaced by meas- contamination. In this part of the continuum of treatments,
urement of the dose used, which
is set according to vendor re-
commendations. Other operators
rely on pH measurement as an
indirect monitoring parameter,
since the pH depends on the
concentration of the product
used.

In the case of diamines/poly-

amines, determination of the
concentration is even more diffi-
cult because these amines are
adsorbed not only on the sur-
faces of the plant cycle compo-
nents but also on the surfaces of
all measuring devices. Most of
the operators use simplified
methods and are satisfied when
the diamine/ polyamine compo-
nent is detectable in the final
condensate.

Remark
In the presence of film-forming
amines, the sensitivity of conduc-
tivity, cation conductivity, and
oxygen sensors could possibly
be affected. For this reason, Figure 3:
more frequent cleaning of elec- Summary of possible boiler water and feedwater treatments for fossil plants as a function
trodes and more frequent oxygen of equipment and equipment capability (Dooley, 2003).
sensor membrane replacement
OT oxygenated treatment
should be considered. Cation
AVT(O) oxidizing all-volatile treatment
exchanger columns of the cation
conductivity measuring instru- AVT (R) reducing all-volatile treatment
mentation may also be affected. PC phosphate continuum
Unfortunately, detailed investiga- PC(L) phosphate treatment with lower level of phosphate
tions of this matter are not avail- PC(H) phosphate treatment with higher level of phosphate
able in the literature.
CT caustic treatment

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the feedwater treatment with organic chemicals has its CLOSING REMARK
important position and justification, as depicted in
This lesson, like all others in this series, is intended to help
Figure 4.
all non-chemists responsible for chemistry-related tasks,
all power industry newcomers, and all engineers, whether
There are many utility and industrial units operating under
chemists or non-chemists, to learn the fossil cycle chem-
complicated conditions: simple makeup water treatment,
istry basics. It is a great challenge for us to support you in
no condensate polishers, possible ingress of contaminants
your efforts to improve the plant cycle chemistry in your
via condenser or return condensate from the industrial
plants.
processes, frequent startups, etc. In addition, a lack of per-
sonnel qualified in chemistry and an insufficient extent of
chemistry-related instrumentation may further complicate
the operations. In such cases, the application of a feedwa-
ter treatment with organic chemicals may be appropriate.
However, the operator should acquire and implement infor-
mation about abovementioned problems and complica-
tions.

Figure 4:
Continuum of treatments including amine treatment (Bursik, 2003).
OT oxygenated treatment
AVT(O) oxidizing all-volatile treatment
AVT (R) reducing all-volatile treatment
PC phosphate continuum
PC(L) phosphate treatment with lower level of phosphate
PC(H) phosphate treatment with higher level of phosphate
CT caustic treatment

500 PowerPlant Chemistry 2008, 10(8)