Albert Bursik

ABSTRACT
The polyamine/amine treatment is applied in hundreds
and hundreds of fossil plant cycles, particularly in the
industry. Over the last decade, the extent of its appli-
cation in utilities has been increasing. This paper fo-
cuses on the polyamine/amine regime in cycles with
drum boilers, although one case study is presented
which reports on application of this treatment in units
with once-through steam generators. The major hin-
drance with respect to the use of this treatment in util-
ities is the fact that the cation conductivity of steam
increases slightly when this treatment is applied.
Operation experience in industrial power and steam
generation and in utilities demonstrates that a slight
cation conductivity increase in the steam does not
cause any turbine-related problems, assuming that the
pH is correctly set by low-molecular volatile amines
being a part of the polyamine/amine formulation.
Steam cation conductivity-related studies for estab-
lishing the actual interaction of slightly contaminated
steam and turbine materials in the presence of an ad-
equate alkalizing agent (a low-molecular amine with a
favorable distribution behavior), i.e., when the early
condensate is adequately alkaline, are suggested.
AN ALTERNATIVE PLANT CYCLE CHEMISTRY
TREATMENT
The Problem with Organics
In recent years, many publications in the cycle chemistry-
related literature have dealt with a very attractive topic,
namely with organics. A complete listing of all the relevant
references would make use of more space than is at the
author's disposal. One gets the strong impression that this
topic is the only important plant cycle chemistry issue. The
most frequent causes of component failures in plant cy-
cles seem to fall into oblivion or at least become negligi-
ble: flow-accelerated corrosion (a corrosion mechanism
that represents a major potential danger to cycle equip-
ment and staff), corrosion fatigue (not rare with compo-
nents or component parts which come into contact with
both water and steam), underdeposit corrosion (still rela-
tively common in utility boilers and heat recovery steam
generators), and stress corrosion cracking of turbine
blades or discs all seem to be no trouble at all. None of
the problems mentioned count in comparison to the in-
dustry problem with organics [1].
Organic treatment chemicals have been suspect for many
decades. Operators using them have been derided; the
additives themselves have been deprecatingly called
"snake oils." It is not clear who was the first to adopt this
designation, typically used for additives to lubricants or
fuels, for non-traditional and non-conventional additives
to plants and soils, for additives used in the cosmetic in-
dustry (e.g., in skin- and hair-care products), in alternative
medicine, and in many other areas. With the term "snake
oils," the organic cycle additives were put on the same
level with gimcrack [2].
Probably for this reason, the application of organic fossil
plant cycle treatment chemicals organics is considered
very negative and is not covered in any internationally ac-
knowledged cycle chemistry guideline. Dooley's contin-
uum of treatments (Figure 1 [3]) does not include the ap-
plication of organic treatment chemicals either.
Current Situation
The current situation is very interesting. Despite the fact
that the use of organic cycle treatment chemicals is not
advised in any major international cycle chemistry guide-
line, many variations of the amine treatment have been
used for decades in industrial steam and power genera-
tion. The extent of amine treatment use in fossil power
plants is also increasing [2].
Polyamine/Amine Treatment in Industrial und Utility
Power Generation
In an application report, theoretical discussions of pros
and cons of amine use for conditioning a fossil plant cycle
are inappropriate. Nevertheless, some of the most impor-
tant reasons for an operator to decide in favor of feedwa-
ter alkalizing with amines for his or her particular cycle(s)
are:
reduction of corrosion generation and corrosion prod-
uct transport into the boiler,
improvement in the feedwater purity, which results in
decreased blowdown losses,
faster startups (lower corrosion product transport dur-
ing startup).
Polyamine/Amine Treatment A Reasonable Alternative
549 PowerPlant Chemistry 2004, 6(9)
Polyamine/Amine Treatment A Reasonable Alternative for
Conditioning High Pressure Cycles with Drum Boilers
2004 by PowerPlantChemistry GmbH. All rights reserved.
Polyamine/Amine Treatment A Reasonable Alternative
550
PowerPlant Chemistry 2004, 6(9)
All the abovementioned advantages are the result of an
increased pH in the condensing steam (due to a more fa-
vorable distribution behavior of amines in comparison to
ammonia), even in the presence of decomposition prod-
ucts of the amines themselves. The combination of poly-
amines with low-volatile amines dealt with in this paper
reveals further benefits:
as a rule, an additional boiler water treatment is not re-
quired,
the steam generator is self-cleaning (polyamines in
combination with dispersants),
there is an increase in turbine efficiency, and
there is less corrosion during idle periods.
These additional benefits are predominantly the result of
polyamine film forming on all surfaces in the cycle.
Adsorption of surface-active polyamines on metal sur-
faces, e.g., in waterwalls, creates a local high-pH environ-
ment and inhibits corrosion even in the presence of cer-
tain contaminants or when the pH in the bulk is lower than
expected. All operators applying polyamines report on ex-
tremely clean turbine blades. It is easy to understand that
doing without phosphates when conditioning boiler water
results in less mechanical carryover of phosphates and,
for this reason, less turbine blade deposit buildup. In ad-
dition, the presence of surface-active polyamines in the
steam helps in the removal of older turbine blade deposits
and prevents the formation of new deposits even if the
concentration of contaminants in steam is relatively high.
To be honest, amine application also has some disadvan-
tages. In most cases, the cation conductivity of steam (and
condensate and in units without condensate polishers
of feedwater) in units on amine treatment is slightly in-
creased. For this reason, the monitoring of the plant cycle
chemistry may become somewhat complicated. However,
a multiplicity of operators, particularly in industrial steam
and power generation, has decided to capitalize on the
advantages of this treatment and to master the possible
disadvantages.
In the following, the use of a non-traditional polyamine/
amine treatment is demonstrated in some case studies. In
all cases reported, Helamin
1
, a proprietary product con-
taining both polyamines and volatile amines, was used as
the plant cycle treatment chemical. The pressure range
covered in the examples is very wide, as is the range of
main steam temperatures.
APPLICATION EXAMPLES
Case Study 1
A large European refinery operates steam generators (con-
ventional drum boilers, heat recovery steam generators,
and refinery-typical steam-generating systems) with a to-
tal steaming capacity of about 2 050 t h
1
. The two high
pressure boilers (steaming capacity 700 t h
1
each) sup-
ply superheated steam with the following parameters:
pressure 9 MPa (1 305 psi) and temperature 520 C
(968 F). The steam generated in the high pressure and
other boilers is used at different pressure levels in the
range between 0.4 MPa (58 psi) and 8.9 MPa (1 291 psi).
The total length of the steam pipelines is more than
70 000 m (more than 43.5 miles); the condensate lines are
of a corresponding length.
1
Helamin is a registered trademark of Filtro, SA, Geneva,
Switzerland
Figure 1:
Continuum of treatments [3].
The use of the polyamine/amine treatment started in 1993
in the old power plant and later this treatment was used in
all types of boilers (conventional and heat recovery) and in
all other steam-generating refinery systems. There were
several reasons for the conversion from a typical phos-
phate/ammonia/hydrazine treatment to the polyamine/
amine treatment: heavy corrosion and corrosion product
transport in the steam/condensate systems, deposition of
corrosion products in the boilers, and deposits on the tur-
bine blades. It is probably worth mentioning that an equiv-
alent polyamine/polyacrylate proprietary mixture was also
used for preoperational boil-out of the high pressure boil-
ers.
After the application of the new treatment, the corrosion
product transport in the whole system was significantly
reduced, the subsequent boiler and turbine inspections
revealing clean surfaces in both the boilers and the tur-
bines. Figure 2 shows the boiler drum of one of the steam
generators. The photograph was taken during a major
boiler overhaul.
A slight increase in cation conductivity in the cycles is a
typical attendant circumstance of the polyamine/amine
application. The operator reports on cation conductivity in
the range of 0.15 to 0.35 S cm
1
during prolonged oper-
ating periods. Due to problems with raw water organics
passing the makeup system during a few months of the
year, the cation conductivity peaks up to 0.5 S cm
1
.
Even in such situations, the corrosion product generation
and transport is successfully controlled.
The use of the polyamine/amine treatment in a complex
multipressure steam-generating system demonstrates an
important treatment advantage: the same chemical is used
in the same concentration in boilers regardless of the par-
ticular individual system pressure. In comparison to phos-
phate treatment, this fact markedly simplifies both the
boiler water chemistry (pressure-dependent phosphate
concentrations vs. uniform conditions) and its surveillance.
Case Study 2
On a large chemical industry site in Europe (in a nitric acid
production unit), polyamine/amine cycle chemistry treat-
ment was introduced, replacing the classic European
phosphate treatment. Both the boiler (drum pressure
8 MPa (1 160 psi)) and the turbine were supplied by well-
known European original equipment manufacturers. The
major reason for converting the unit from phosphate treat-
ment to polyamine/amine treatment was trouble with tur-
bine fouling. The turbine had to be frequently cleaned
(washed) to recover the turbine performance. After intro-
ducing the new chemical treatment, the turbine washes
were no longer required. Figure 3 depicts the performance
improvement. During the application of the phosphate
551 PowerPlant Chemistry 2004, 6(9)
Figure 2: Boiler drum unit on polyamine/amine
treatment.
Figure 3: Turbine performance phosphate treatment vs. polyamine/amine treatment.
Polyamine/Amine Treatment A Reasonable Alternative
Polyamine/Amine Treatment A Reasonable Alternative
treatment, the mean turbine output was approximately
22.7 MW. After 9 months operation on polyamine/amine
treatment, the plate rating of 25 MW was achieved (with-
out any turbine wash).
Improvement in the boiler and turbine operation and the
efficiency increase realized result in non-negligible sav-
ings. The reader may transfer the improvement achieved
(22.7 MW 25 MW) and thereby the savings realized to
his or her own unit or utility operated on phosphate treat-
ment.
Case Study 3
Inadequate thermal stability of organic cycle treatment
chemicals is often cited as evidence against their use in
fossil plant cycles. It is assumed that these chemicals are
completely decomposed, the final decomposition prod-
ucts being low-molecular organic acids and carbon diox-
ide. In arguing thus, the main residence time of organics
in water-touched and steam-touched boiler parts is com-
pletely disregarded. Considering a particular 14 MPa
(2 030 psi) drum boiler unit as an example, Tavast esti-
mates that the period during which the chemical remains
in the drum system is in the order of one hour (the precise
time depends on the percentage of blowdown), and in the
superheater only in the order of a few tens of seconds [4].
In cycles with once-through boilers, the residence time is
markedly shorter. This case study demonstrates that for
this reason a successful use of polyamine/amine treat-
ment is possible even in cycles with once-through boilers
with high pressures and temperatures.
In one European combined heat and power generating
plant, two cycles with subcritical once-through steam gen-
erators (main steam pressure/temperature 200 bar/
540 C, reheat steam temperature 540 C) have been
treated with the polyamine/amine treatment chemical
since 1996. The units are equipped with condensate pol-
ishers. Another unit was recently commissioned and is
treated with the same chemical. The reason for the plant
cycle treatment selection was long holds during startups
due to a high concentration of iron oxides in the feedwa-
ter when applying the all-volatile treatment (AVT) in units
being subject to frequent shutdowns/startups and load
variations.
During the conversion from the AVT to polyamine/amine
treatment, two parameters have controlled the treatment
chemical dosage: the pH (pH target value > 9) and the
cation conductivity ( 0.2 S cm
1
) in the cycle. The op-
eration practice shows that after the startup, the cation
conductivity reaches values about 0.5 S cm
1
and falls
down to 0.2 S cm
1
in continuous operation.
In 2001/2002, early condensate measurements were car-
ried out, revealing that the early condensate pH is higher
than the bulk steam/condensate pH even in the presence
of low-molecular acids [5]. The early condensate pHs de-
picted in Figure 4 are measured (not calculated) values.
Case Study 4
In a large paper mill, polyamine/amine treatment is applied
in a unit with a drum-type boiler with a steaming capacity
of 125 t h
1
(276 000 lb h
1
). The main steam parameters
are: pressure 9.5 MPa (1 378 psi) and temperature 525 C
(977 F). After commissioning, the treatment used was
ammonia/hydrazine AVT combined with phosphate dos-
ing into the boiler water. As is typical in paper mills, long
steam and condensate lines between the boiler house and
the individual paper machines and frequent air ingress into
the low pressure and high pressure condensates resulted
in heavy corrosion in the boiler peripheral paper mill equip-
552
PowerPlant Chemistry 2004, 6(9)
Figure 4: pH of the early condensate samples a unit
with a once-through steam generator on
polyamine/amine treatment.
Figure 5: Paper mill parts taken from the equipment vs.
a part from the spare part stock.
Polyamine/Amine Treatment A Reasonable Alternative
ment. The unit suffered from heavy corrosion product
transport into the boiler and fast buildup of boiler tube de-
posits. A boiler tube hot side deposit weight of
760 g m
2
was determined. The boiler had to be chemi-
cally cleaned.
After the chemical clean, the unit cycle treatment was con-
verted to polyamine/amine treatment. As a result of the
cycle treatment conversion, the iron content of the con-
densates after a short period with higher iron levels
(cleaning of surfaces in paper mill equipment, outside of
the boiler system) has dramatically decreased to
levels customary in non-industrial power stations
(<< 20 g kg
1
, mostly < 10 g kg
1
). Figure 5 is a com-
parison of the condition of two parts of a drum drier, dis-
mantled from an operating paper machine (two upper
parts), and a part from the spare part stock.
Some Further Examples
Polyamine/amine treatment has a long history in plant cy-
cle treatment, mostly in industrial applications. The opera-
tion conditions in industrial steam-generating systems are
typically more difficult than those in utility units. If a plant
cycle treatment can cope with hard industrial conditions,
why shouldn't this treatment be able to cope with the more
favorable situations in utilities? Concerns with respect to
corrosion caused by breakdown products of organic cycle
treatment chemicals, particularly in areas of beginning
steam condensation (e.g., in a low pressure part of a con-
densing turbine), have resulted in a prejudiced rejection of
this treatment. However, the positive experience in indus-
trial power and steam generation is attracting the atten-
tion of utilities experiencing cycle chemistry problems.
Some examples are mentioned below.
As reported by Galt [7], feedback on the application of
polyamine treatment for on-line boiler cleaning has peaked
the interest of a world-famous South African utility. The
Belgian experience [8] suggests that even in this utility,
some possible application candidates are present. Even
though the trial at a 200 MW unit with drum-type boilers
operating at 12 MPa (1 740 psi) with a main steam tem-
perature of 535 C (995 F) had to be prematurely con-
cluded, a reduction of the average waterwall oxide thick-
ness from around 540 m to 159285 m could be
reached in four months of polyamine/polyacrylate use.
Figure 6 shows the boiler drum internals after polyamine/
polyacrylate application [7].
In many countries all over the world, polyamine/amine
treatment is successfully being applied. For example, in
the Middle East, in tens of power plants generating power
and steam for desalination installations and in refineries,
this treatment is applied. The steaming capacity of the in-
dividual steam generators ranges from 300 t h
1
(661 000 lb h
1
) to 620 t h
1
(1 367 000 lb h
1
), the main
steam pressure from 6.5 MPa (943 psi) to 12.7 MPa
(1 842 psi), and the main steam temperature from 480 C
(896 F) to 540 C (1 004 F). Despite the frequent load
variations induced by alteration between pure power pro-
duction and power production and steam sendout to de-
salination units, the cation conductivity in the cycles is
maintained at a low level ( 0.3 S cm
1
). The major rea-
son for the polyamine/amine treatment application was
corrosion product generation and transport when operat-
ing on traditional plant cycle treatments. Only the applica-
tion of the new treatment has led to iron levels in the order
of < 10 g kg
1
, even in brine heater condensates of the
desalination plants.
In the countries of the former Soviet Union, the use of the
polyamine/amine treatment is also increasing. The pres-
sure of the units treated ranges between 4 MPa (580 psi)
and 14.0 MPa (2 030 psi) and the main steam temperature
between 440 C (824 F) and 560 C (1 040 F). The treat-
ment is applied in the majority of cases in older units with-
out condensate polishers which are experiencing prob-
lems with condenser tightness, heavy corrosion product
generation and transport, boiler tube deposit buildup and
fouling of turbines. The operation results so far confirm
that the polyamine/amine treatment application may help
in establishing reasonable cycle chemistry conditions even
in such complicated cases.
THE EXASPERATING CATION CONDUCTIVITY
The major problem hindering the frequent use of
polyamine/amine treatment in utilities is the cation con-
ductivity problem. The major turbine manufacturers de-
mand cation conductivity of steam < 0.2 S cm
1
; the phi-
losophy of the major industry guidelines is identical. The
fact is neglected that cation conductivity is neither a
chemical nor a physical property of the media. It is actu-
ally a hypothetical matter: it is the conductivity of a sam-
ple in which no other cations except the cation H
+
are
present. This indicates that a value measured does not
have any meaningfulness with respect to the actual prop-
erties of the media. The original media (upstream of the
553 PowerPlant Chemistry 2004, 6(9)
Figure 6: Boiler drum internals after polyamine/ poly-
acrylate application [7].
Polyamine/Amine Treatment A Reasonable Alternative
cation exchanger) may have a high or a low pH; i.e., it may
be non-corrosive or strongly corrosive with respect to iron-
based materials [9]. Industry experience proves that even
at increased cation conductivity, failure- and damage-free
operation of the cycle in the presence of organic alkalizing
agents is possible. This is a result of favorable distribution
coefficients of low-molecular volatile amines. For this rea-
son, in the phase transition zone of a low pressure turbine,
amines are capable not only of coping with their own de-
composition products (e.g., acetates and formates), but
also with certain levels of inorganic contaminants possibly
present in the steam.
The experience in the industrial steam generation proves
that cation conductivities in the range of 0.5 S cm
1
do not cause any turbine-related problems, assuming that
pH is correctly set by low-molecular volatile amines. A se-
rious and deep study of this topic is desirable. The major
turbine manufacturers should carefully investigate whether
the materials and the design of low pressure turbines are
actually so inadequate that the turbines cannot accept
steam with a cation conductivity somewhat higher than
the ominous 0.2 S cm
1
, even though the pH of the early
condensate is markedly higher than 9 and the specific
conductivity of the early condensate is, e.g.,
< 10 S cm
1
. Such evaluations should only focus on
technical issues and not be prejudged by possible war-
ranty aspects. The long-term experience with the poly-
amine/amine treatment demonstrates that a slightly in-
creased cation conductivity does not endanger low pres-
sure parts of condensing turbines.
Bursik et al. have in a somewhat provocative manner
suggested that polyamine/amine treatment should be in-
corporated into Dooley's continuum of treatments [2]. The
more operation experience that is gained with this treat-
ment, the more justifiable this opinion becomes [Figure 7].
REFERENCES
[1] Bursik, A., Staudt, U. W., PowerPlant Chemistry
2001, 3(3), 136.
[2] a) Bursik, A., Bezzoli, P., Graf, A., The Seventh
International Conference on Cycle Chemistry in Fossil
Plants (Houston, TX, U.S.A.), 2003. Electric Power
Research Institute, Palo Alto, CA, U.S.A.
b) Bursik, A., Bezzoli, P., Graf, A., PowerPlant
Chemistry 2003, 5(6), 373.
[3] a) Dooley, B., Shields, K., The Seventh International
Conference on Cycle Chemistry in Fossil Plants
(Houston, TX, U.S.A.), 2003. Electric Power Research
Institute, Palo Alto, CA, U.S.A.
b) Dooley, B., Shields, K., PowerPlant Chemistry
2004, 6(3), 153.
[4] Tavast, J., PowerPlant Chemistry Seminar "Com-
bined Cycles and Heat Recovery Steam Generators
Development, Boiler Tube Failures, Chemistry, and
Monitoring", 2002, Contribution to the discussion.
PowerPlant Chemistry GmbH, Neulussheim,
Germany.
[5] Bursik, L., PowerPlant Chemistry 2002, 4(2), 81.
[6] Grabli, A., Massalha, L., VGB Symposium Industrie-
und Heizkraftwerke, BHKW 2004 (Bochum,
Germany), 2004. VGB PowerTech, Essen, Germany.
554
PowerPlant Chemistry 2004, 6(9)
Figure 7:
Continuum of treatments
including polyamine/amine
treatment [2].
Polyamine/Amine Treatment A Reasonable Alternative
555 PowerPlant Chemistry 2004, 6(9)
[7] Galt, K. J., Proc. (on CD), ESAA Power Station
Chemistry 2004 Conference (Pokolbin, NSW,
Australia), 2004 . Energy Supply Association of
Australia, Melbourne, VIC, Australia.
[8] Roofthooft, R., Eyckmans, M., Verheyden, K., de
Pourcq, D., VGB PowerTech 2001, 81(3), 83.
[9] Bursik, A., PowerPlant Chemistry 2002, 4(10), 597.
THE AUTHOR
Albert Bursik (Ph.D., Chemical Engineering, Institute of
Chemistry and Chemical Technology in Prague, Czech
Republic, Mechanical Engineering, University of Stuttgart,
Germany) has worked for over 35 years as a chemist in
several utilities. Albert Bursik is an Honorary Fellow of the
International Association for the Properties of Water and
Steam and has published more than 200 scientific and
technical publications. He is a professor at the University
of Stuttgart and works as the editor of the PowerPlant
Chemistry journal.
CONTACT
Albert Bursik
PowerPlant Chemistry GmbH
P.O. Box 1269
68806 Neulussheim
Germany
E-mail: editor@ppchem.net