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PPCHEM Film-Forming Amines in Shell Boilers

Film-Forming Amines in Shell Boilers

Holger Topp, Wolfgang Hater, Andre de Bache, and Christian zum Kolk

ABSTRACT
Studies were conducted with the aim of providing answers to important questions concerning the use of film-forming
amines in steam generators. Tests were carried out in test steam generators under controlled conditions to study the
three following application areas: the influence of film-forming amines on boiling behavior and heat transfer, the influ-
ence of film-forming amines on oxidic protective layer formation, and the influence of film-forming amines on critical
operating conditions. In the experiments water treatment with trisodium phosphate (which is normally used with shell
boilers) was compared with treatment with film-forming amines. In all three areas the treatment with film-forming
amines achieved comparable or better results than the treatment with trisodium phosphate.

INTRODUCTION
The safe operation of steam generators depends on vari-
ous factors. The resistance of the heating surface to
chemical and thermomechanical effects plays a major
role. The heat transfer from the heating surface to the boil-
ing liquid has a serious effect on the surface temperature.
The working life of the heat exchanger accordingly suffers
under dynamic influences (start-up and shutdown, perfor-
mance gradients resulting from firing and steam tapping)
and the physicochemical interactions between the heating
surface and the boiler water. The heating surface material
and, in particular, oxide layers have a considerable effect
on heat transfer [1,2].
When the superheated surface comes into contact with
boiler water at a saturation temperature of above approxi-
mately 180 °C, an oxide layer of magnetite (Fe3O4) and/or
hematite (Fe2O3) is formed without the necessity of having
free oxygen present; because of its passivating effect
such a layer is desirable [3,4]. The formation and conser-
vation of such an oxide layer can be supported by the
addition of an alkalizing medium and the resulting excess
of hydroxide ions. In this respect trisodium phosphate is
the classic conditioning agent for shell boilers.
Because of a comparatively small thermal coefficient of
expansion, this protective layer does not withstand with-
out damage thermal stress in the base material (steel) dur-
ing alternating loads or start-up and shutdown processes.
The result is often smaller cracks in the protective layer
down to the now unprotected base material, where further
oxidation processes occur. As the oxide layer thickness
increases, the material undergoes a constant weakening,
leading to a possible failure. In addition, the heat transfer
coefficient is reduced because of the lower thermal con-
ductivity of the oxide layer; this means that the material
temperature of the heat transfer surface increases [1,2].
Alongside the classic feedwater treatment with inorganic
additives, the use of organic corrosion inhibitors based on
film-forming amines has proven itself in practice [5]. These
film-formers have the ability to form a molecular film at
interfaces; this film has a physical/chemical inhibiting
character. For one thing, the film-formers influence the
local electrochemical potential of the (metallic) heating
surface material because of their amino group. In addition,
the organic film prevents to a great extent direct contact
between the boiler water and the metallic or already oxi-
dized surface. Because of the steam volatility of the film-
forming amines, a small detectable excess in the conden-
sate allows the conclusion that the whole medium-con-
tacting boiler surface is covered by the organic protective
film.
The addition of these organic corrosion inhibitors has
been shown to reduce the surface tension of the water
compared to steam [2], which theoretically can have a
positive effect on heat transfer and therefore on the heat-
ing surface temperature. The lowering of the surface
tension has the consequence that the necessary super-
heating for bubble formation is reduced and the onset of
nucleate boiling (ONB) occurs at a comparatively low
heating surface loading.
In order to study the influence of the various feedwater
additives mentioned on the heating surface properties, an
experiment was carried out in which water treatment with

© 2012 by Waesseri GmbH. All rights reserved.

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Film-Forming Amines in Shell Boilers
trisodium phosphate (which is normally used with shell
boilers) was compared with treatment with film-forming
amines.
Systematic studies have shown that a thermal experiment
is suitable for describing the effect of feedwater additives
on the boiling process [6]. In this way observation of the
development of the heat transfer coefficient due to sur-
face changes caused by layer formation as a function of
time can be used to formulate precise statements about
the morphology of the heating surface. By using this
method it can be shown that the types of water treatment
used have different effects with respect to the heating sur-
face, which again has an important influence on saturated
pool boiling heat transfer.
INFLUENCE OF FILM-FORMING AMINES ON
SATURATED POOL BOILING HEAT TRANSFER
The experimentally1 determined reduction of the heat
transfer coefficient as a function of time occurs in both the
investigated types of treatment (organic/inorganic), start-
ing from bare metallic heating surfaces through to thermal
stationarity, with good agreement with first order kinetics.
In the experiment under normal operating conditions in
shell boilers (saturation pressure ps = 15 bar, heat flux
· face-active effects of the film-former; this nucleation
density q = 4 · 104 – 3 · 105 W · m–2) using the product
Cetamine® V 211 (hereafter mentioned as Cetamine) as
1
The cold-drawn precision steel tubes made from the material
1.0308 used as the test heating surface are in accordance
with DIN EN 10305-1 and are directly resistance-heated with
alternating current. The feedwater complies with the guide-
lines of VGB R 450. Further information about the test condi-
tions can be found in the literature [2].
Cetamine¥
PO4,¥
PO4,¥
300
Technically relevant domain
250
Relative Enhancement of k [%]
200
150
100
50
0 coefficient k when the film-forming amine is
10 4 10 5
Heat Flux Density [W · m–2 ]
PowerPlant Chemistry 2012, 14(1)
PPCHEM
an example of an organic corrosion inhibitor based on
film-forming and alkalizing amines, a significant increase
in the heat transfer coefficient in comparison to the inor-
ganic treatment could be demonstrated at all times [6].
Figure 1 shows the relative improvement of the heat trans-
fer coefficient k at the point of thermal equilibrium
(index ∞) for the particular organic treatment of the feed-
·
water as a function of the heat flux density q compared
with the classic standard conditioning with trisodium
phosphate.
In Figure 1, Cetamine refers to treatment with film-forming
amines and PO4 to inorganic feedwater conditioning with
trisodium phosphate starting with metallic (i.e., non-oxi-
dized) heating surfaces. PO4, ∞ 씮 Cetamine indicates the
change from treatment with trisodium phosphate to condi-
tioning with film-forming amines after establishing a
steady-state thermal heating surface condition, i.e., after
the formation of a complete oxide layer. For small heat flux
densities the improvement in heat transfer compared with
classic conditioning is up to 150 % after use of the film-
forming amine starting with a metallic heating surface and
up to 80 % after changing the treatment method. This
effect decreases as the heat flux density increases, as the
increasing boundary layer superheating leads to further
bubble nucleation on the surface even without the sur-
causes an improved heat removal.
A significant increase in the heat transfer coefficient in the
investigated range of heat flux densities is to be noted,
both when starting from tubes whose metallic surfaces
were treated with film-forming amines and also for tubes
that were converted from trisodium phosphate treatment
to treatment with film-forming amine.
Cetamine¥
Figure 1:
Relative improvement in the heat transfer
10 6
used compared with treatment with trisodium
phosphate at ps = 15 bar.
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PPCHEM Film-Forming Amines in Shell Boilers

Figure 2:
·
Freeze-frame images of the boiling process at ps = 15 bar and q = 1 · 104 W · m–2.
Left: Trisodium phosphate method at the end of treatment.
Right: The very same test heating surface directly after switching to film-forming amine treatment.

An improved heating surface cooling resulting from the
increase in active bubble nucleation on the surface when
compared with the inorganic method could be observed.
The following freeze-frame images from video recordings
(see Figure 2) are used to visualize the boiling process at a
comparatively low heat flux density for practical boiler
·
operation of about q = 1 · 104 W · m–2. This low heat flux
density was deliberately chosen in order to visualize the
influence of film-forming amines on the boiling process as
at higher heat flux densities differences in the number of
active nucleation sites are rather difficult to observe with
the naked eye.
The left-hand image in Figure 2 shows the
operating condition at the end of the
trisodium phosphate treatment (PO4,∞ after
an operating time of about 300 h); the
right-hand image shows the boiling
process on the identical test tube directly
after switching to the film-forming amine
method, PO4, ∞ 씮 Cetamine0 .2
Lin [Cps]
directly after switching to film-forming amines is com-
pletely covered with bubbles because of the surface-active
effect. The nucleate boiling of the water and an increased
turbulence result from bubble formation and detachment,
intensifying the cooling of the heating surface.
In addition, when the amine program is used, a lowering
of the necessary heat flux density for activating bubble
formation on the heating surface is observed. According
to this, if the organic feedwater additive is used, then
nucleate boiling already occurs at a lower heating surface
loading than when inorganic conditioning is applied. The
working range of nucleate boiling with its high heat
transfer coefficient is increased accordingly when film-
forming amines are used [2].
1 400 Tube A244
PO4 Tube A244 SE3
1 200
Tube A244 SE5
Fe (pure)
1 000
Fe3O4 (synthetic)

Whereas at the end of the inorganic treat- 800

ment only a few nucleation sites are active,

600
and therefore convective heat transfer
dominates with a considerably lower heat 400
transfer coefficient, the same test tube
200
2
To avoid a cross-influence under the types
0
of conditioning used, the different proce- 8 10 20 30 40 50 60 70 80
dures were carried out in two structurally 2-Theta [°]
identical and technically calibrated test
apparatuses. This meant that a change in
treatment required the immediate transfer of Figure 3:
the particular test tube from one test boiler X-ray diffraction diagram for a test heating surface after treatment with trisodium
to the other (in a hot condition). phosphate.

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Film-Forming Amines in Shell Boilers PPCHEM

Analytical investigations after a long

Tube A160 period of operation with the two feed-
1 400
Tube A160 SE3
water additives mentioned above show
Cetamine significant differences in the morphology
Tube A160 SE5
1 200 of the oxide layer formed. While the
Fe (pure)
trisodium phosphate treatment leaves
Fe3O4 (synthetic)
1 000 clear inhomogeneities on the tube sam-
ples, the surface of the steel tubes condi-
Lin [Cps]

800 tioned with film-formers are seen to be

homogeneous to a large extent and
600
"close-grained." Figure 5 shows these
morphological variations using confocal
400
micrographs (confocal laser scanning
microscopy, CLSM).
200

8 10 20 30 40
2-Theta [°]
Figure 4:
X-ray diffraction diagram for a test heating surface after treatment with film-
forming amine.
EFFECT OF FILM-FORMING AMINES ON THE
SURFACE STRUCTURE OF THE TEST HEATING
SURFACE
As an oxide layer is formed after treatment with both inor-
ganic and with film-forming amines at a corresponding
saturation temperature of Ts = 198.3 °C, the two following
X-ray diffraction diagrams (Figures 3 and 4) have been
obtained for two test heating surfaces.
Evidently the organic film does not suppress oxide layer
formation.
However, the tested heating surface samples show con-
siderable differences in the condition of their surfaces.
50 60 70 80
It could additionally be shown that the
thickness of the oxide layer also depends
on the type of treatment. Because of its
porosity and considerably lower thermal
conductivity in comparison with the
metallic surface, the oxidic layer on the
surface impedes heat transfer. Under the
assumption of the same oxide layer
properties and the same heat flux den-
sity, the surface temperature of the heat
transferring unit decreases as the layer
thickness increases.
The oxide layer thicknesses obtained after achievement
of thermal stationarity were quantified by using cross-
sectional analyses of the tube heating surfaces.
Figure 6 shows representative micrographs of the oxide
layer under a confocal microscope.
The results of the evaluation of all cross-sections analyzed
and the necessary treatment duration until steady-state
heat transfer conditions are summarized in Table 1.

500 500
30 30
z[µm]

z[µm]

20 400 20 400
10 10
300 300
0 0
]

100 200 100 200

m

m
[µ

[µ

200 200
y

x [µm 300 100 x [µm 300 100

] 400 ] 400
0 0
500 500

Figure 5:
CLSM micrographs of the heating surfaces after treating the formerly bare metal steel tubes with trisodium phosphate, PO4,∞ (left), in
comparison to conditioning with film-forming amines, Cetamine∞ (right).

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PPCHEM Film-Forming Amines in Shell Boilers

Figure 6:
CLSM micrographs of heating surface cross-sections treated with
a) PO4
b) Cetamine after achieving thermal stationarity.
The measuring points for determining the thickness are marked with 1–4.
Note: The images have a different scale.

Necessary Treatment Average Oxide Layer Standard Deviation

Type of Treatment
Duration [h] Thickness [µm] [µm]
PO4, ∞ 96 15.2 ± 6.1
Cetamine∞ 80 5.9 ± 1.6
PO4,∞ 씮 Cetamine∞ 430* 15.8 ± 3.2
Table 1:
Comparison of measured oxide layer thicknesses on heating surfaces after achievement of thermal stationarity for different treatment
programs.
* The value for the time given for switching from trisodium phosphate to film-forming amines applies solely to the necessary
treatment duration with the film-forming amines. It does not contain the previous treatment time up to stationarity of the heat
transfer under the inorganic program.

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Film-Forming Amines in Shell Boilers
It can be seen that treatment with the film-forming amines
results in the formation of thinner and also more uniform
oxide layers than those obtained by treatment with
trisodium phosphate, substantiating Figures 5 and 6. The
oxide layer formed under phosphate conditions increases
only slightly after switching to film-forming amines.
However, the switch results in the oxide layer becoming
more homogeneous, as is indicated by the reduced stand-
ard deviation. Surface roughness is also reduced [6].
INFLUENCE OF THE FILM-FORMING AMINE ON
POSSIBLE CRITICAL OPERATING CONDITIONS
Despite these positive effects of the film-formers on heat
transfer during boiler operation and the heating surface
properties, certain misgivings exist concerning the nega-
tive effects of organic treatment on critical operating con-
ditions in steam boilers. In the past various organic feed-
water additives have already been studied experimentally
with respect to their effect on critical operating conditions
(the so-called boiling crises) [7]. A negative influence of
the conditioning agent used on the studied operating con-
ditions could not be observed.
The theoretically possible boiling crises in steam boilers
are briefly explained below. In thermal experiments the
influence of film-forming amines on the critical operating
conditions for shell boilers was investigated systematically.
First Type of Boiling Crisis, Burn-Out I
· Cetamine V211 do not affect the position of the critical
If a critical value for the heat flux density q is achieved dur-
ing nucleate boiling, then all the nucleation sites that can
be activated on the heating surface are occupied by
steam bubbles. Heat transfer can no longer be increased
by raising the heat flux density, as the bubbles that already
exist become increasingly bigger and therefore more
unstable. They hinder each other during detachment and
coalesce. This results in the formation of a local closed
steam film between the heating surface and the boiling
water. Heat transfer within the steam film is extremely low
(Leidenfrost effect), which results in a drastic reduction of
the heat transfer coefficient and therefore the cooling of
the heating surface. The melting temperature of the mate-
rial is reached in fractions of a second. The heating sur-
face burns through, the so-called burn-out I.
The value of the critical heat flux density for water
increases during saturated pool boiling as the saturation
pressure increases (up to about 64 bar). The lower the sat-
uration pressure, the larger is the risk of a burn-out I. This is
why a lower saturation pressure of ps = 2 bar (Ts =
120.21 °C) was selected for the experimental determina-
tion of the critical heat flux density. If an influence of the
film-forming amines on the value of the critical heat flux
density does exist, then it can be detected by comparison
PowerPlant Chemistry 2012, 14(1)
PPCHEM
·
of the experimentally determined value of q for both the
organic and the inorganic reference treatment with Na3PO4.
In the experiment burn-out I was brought about by
increasing the strength of the electric current through the
test tube step-by-step. After the required current strength
was reached a waiting period was observed until the
recorded physical parameters achieved a stable condi-
tion. This condition was maintained for about several sec-
onds. If no burn-out I occurred during this period, the next
higher electric current strength was set.
Figure 7 uses freeze-frame images to show the burn-out I
of a test heating surface after exceeding the critical heat
flux density using a phosphate-treated test tube as an
example.
Figure 8 contains the determined measured values in a
· ·
k – q plot. The individual pairs of values of k and q form a
straight line in a double-logarithmic plot, the so-called
boiling curve, characteristic for the respective boiling
regime (convective/nucleate), treatment type and period.
For orientation purposes, the characteristic boiling curve
for the trisodium phosphate treatment has been included
in the plot. The range of values given in the literature for
·
the critical heat flux density qkrit when boiling chemically
pure water at ps = 2 bar is marked gray in the plot. The val-
ues stated in the literature lie between 1.4 · 106 W · m–2 and
1.8 · 106 W · m–2 [8].
The tests show that the constituents of the product
heat flux density. The formation of an oxide layer also has
·
no measurable influence on qkrit. The experimental mean
·
of the critical heat flux densities of qkrit = 1.77 · 106 W · m–2
lies far outside the domain of technically relevant heat flux
densities and, within the limits of the measuring accuracy,
is the same for both types of treatment studied.
The fear that conditioning the heating surface with the
film-forming amine studied could result in an increased
sensitivity to burn-out I is unfounded.
Second Type of Boiling Crisis, Burn-Out II
The second type of boiling crisis is a phenomenon of flow
boiling. This process plays no role in saturated pool boil-
ing and is only mentioned for the sake of completeness.
Normally, during flow boiling, a two-phase mixture flows
through a tube wetted with boiling water. When a critical
heat flux density from the inner tube wall to this two-phase
mixture is exceeded, the cooling liquid film dries out. The
change to pure steam flow without the evaporative cool-
ing in the wall film at the given heat flux density causes the
heating surface to dry out and overheat (dry-out).
43
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PPCHEM Film-Forming Amines in Shell Boilers

Figure 7:
Freeze-frame images of the burn-out I of a test tube after trisodium phosphate treatment. The location of burn-out I on the heating
surface was observed to be random.
Heat Transfer Coefficient [W · m –2 · K –1 ]

5
10

PO4,0
O 4,0
eP PO4,0
urv qcrit = 1.77·10 6 W · m–2
Technically relevant in gc
B oil PO4,¥
domain
Cetamine0

Cetamine0
VDI Heat Atlas [8]
Cetamine¥

Cetamine¥

PO4 Cetamine¥
10 4
6
10 5 10 7
10
Heat Flux Density [W · m –2 ]

Figure 8:
Experimentally determined values for the critical heat flux density at ps = 2 bar for the different types of conditioning.
Index 0 means that the determination was carried out on a bare tube.
Index ∞ = at thermal stationarity.
·
qkrit critical heat flux density

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Film-Forming Amines in Shell Boilers
Third Type of Boiling Crisis, Burn-Out III
Film-forming amines have the intrinsic property of forming
organic films on all boiler surfaces coming into contact
with water and steam [5]. The possibility of the deposition
of a thick layer of the organic conditioning agent, for
example after an overdose, and an associated negative
influence on the behavior of steam boilers under changing
stresses is discussed. A possible result would be the third
type of boiling crisis, burn-out III.
The assumption is that thick-film adsorption of the film-
former on the heating surface during standstill or at a
lower pressure range without heating leads to the surface
cavities being covered up [7]. Application of the sudden
stress of a high heat flux density (flame on) means that
these cavities could not be activated because of the
organic film. The result would be, similar to burn-out I, that
the material temperature would suddenly rise dramatically
in a fraction of a second. If the material softening (-melt-
ing) temperature were to be reached, then this would
destroy the heating surface (burn-out III).
According to these scenarios conditions similar to those
encountered in practice were created by the use of an
arrangement specially designed for studying boiling
processes in pool boilers [6], in order to study in detail the
influence of the film-forming amine contained in Cetamine
V 211 on the activation of the nucleation points. This was
done by producing cold-start conditions (system tempera-
ture corresponding to ambient temperature3); a sudden
heating surface stress was also simulated starting from
stand-by conditions (ps = 2 bar, Ts = 120.21 °C), without
the test heating surface being active. Both conditions
3 4
The corresponding saturation pressure is far below the ambi-
ent pressure and permits penetration of atmospheric air into
the pressure vessel. A slight (nitrogen) overpressure is applied
in order to ensure the leak tightness of the apparatus.
10x10 5
9x10 5
5
8x10
Heat Flux Density [W · m–2 ]
7x10 5
5
6x10
5x10 5
5
4x10
5
3x10
5
2x10
1x10 5
0 0
0 2 4 6 8 10
Time [s]
PowerPlant Chemistry 2012, 14(1)
PPCHEM
were kept stationary for at least 6 h in order to enable
deposition of the film-former constituents – if any should
occur. In accordance with the aim of the study, the partic-
ular test heating surface used was suddenly subjected to
two different deliberately excessive heat flux densities of
· ·
q = 4 · 105 W · m–2 and q = 8 · 105 W · m–2.4 The system was
provided a minimum pause of 6 h between the tests.
The heat flux density was generated by sudden applica-
tion of strong electric currents to the model heating sur-
face; the current strengths used were based on experi-
ence. (A precise presetting of a required heat flux density
was not possible because of the temperature dependency
of the electric heating in the system used. The set heating
surface stresses were in an acceptable proximity to the
values mentioned above and are meaningful with respect
to the assumed effect.)
The resulting increase in the heating surface temperature
caused by the flow of electric current through the (tem-
perature-dependent) ohmic resistance of the test tube
was then compared with the measured data of an inorgan-
ically conditioned reference heating surface (by definition
a burn-out III is not possible) over a similar time. Any vari-
ations in the time-dependent behavior of the mean test
tube temperature can be used to draw conclusions about
the risk or occurrence of a burn-out III. In order to evaluate
the effect of the concentration of film-forming amines in
the boiler water on the risk of a burn-out III, in addition to
the standard concentration (0.5–1.0 mg · L–1 film-forming
amine in condensate) two further intentionally chosen
excessive concentrations (10 mg · L–1 and 100 mg · L–1)
were investigated.
Maximum heating surface loads/heat flux densities in fire tube
boilers (shell boilers) are normally below 3 · 105 kW · m–2.
1 500
Normal 1 350
Critical
1 200
Mean Wall Temperature [°C]
Burn-out III
1 050
900
750
600
450
Figure 9:
300
Schematic diagram showing
150 various curves for the heating
surface temperature and heat flux
12 14 16 18 20 density under normal and critical
conditions, and for burn-out III in
an electrically heated system.
45
Heft2012-01:Innenseiten 09.01.12 11:11 Seite 46
PPCHEM
Figure 9 is a diagram illustrating the expected effects and
showing three possible time-dependent curves of heat
flux density and mean tube wall temperature from a cold
start and direct application of 4 · 105 W · m–2.
Normal Behavior After an electric current is impressed
on the test tube, its mean wall temperature increases lead-
ing to a rising heat flux density. Both physical quantities
develop asymptotically for a normal start-up (solid line in
Figure 9).
Critical Behavior An already critical impact of an
organic layer on the mean wall temperature by suppress-
ing nucleation on the surface is demonstrated by the
dashed line in Figure 9. Desorption processes result in an
over-swing of mean wall temperature and heat flux den-
sity, respectively. Desorption sets in after the boundary
layer reaches a certain superheat. When desorption of the
organic film "allows" nucleation to set in (if the boundary
layer temperature approaches the saturation temperature
at the actual system pressure), bubble formation on the
surface leads to an enhanced heat transfer to the boiling
or even subcooled water (subcooled boiling results in
remarkably high heat transfer coefficients). This eventually
decreases the wall temperature and the heat flux density
to the desired operation.
Burn-out III If the desorption processes took longer
than the electrical heating to cause material temperatures
higher than its melting point, a burn-out III would occur
(dotted line in Figure 9). Nucleation would be prevented by
a thick organic layer covering potentially available nuclei.
The thermal load would increase rapidly due to the high
tube temperature. As the tube burned out, the power sup-
ply would be interrupted and the heat flux density would
drop to zero.
10x10 5
9x10 5
5
8x10
Heat Flux Density [W · m–2 ]
7x10 5
6x10 5
5
5x10
5
4x10
5
3x10
2x10 5
1x10 5
0 0
0 20 40
46
Film-Forming Amines in Shell Boilers
Figure 10 shows an example of the start-up process for a
test heating surface conditioned with 100 mg · L–1 film-
forming amine (standard concentration: 0.5–1 mg · L–1)
compared with an inorganically treated reference surface.
(NB: After overloading the heat flux density a manual cor-
rection was dispensed with for the reference heating sur-
face.)
As an example for the loading of a heating surface with
4 · 105 W · m–2, the behavior of a test heating surface with a
standard concentration of 0.5–1.0 mg · L–1 film-forming
amine in the condensate starting from stand-by (ps =
2 bar) is shown in Figure 11 in comparison with the inor-
ganic reference method. Both tests show normal curves
for the tube temperature and heat flux density. The tem-
perature curves of organically and inorganically condi-
tioned heating surfaces are virtually identical. Covering up
of the nucleation points on the surface either does not
take place, or it does not manifest itself in any way in the
heating-up behavior.
The studied scenarios with their parameters and the
observed result of the particular test are shown in Table 2.
It can be seen that even the use of a 100-fold concentra-
tion of the film-forming amine in the product Cetamine has
no measurable influence on the activation of nucleation
points.
In none of the studied scenarios could a variation in the
temperature curve be observed in comparison with the
reference treatment with phosphate within the limits of
measuring error.
100 mg · L –1 film-forming amine
Inorganically treated reference
200
180
160
Mean Wall Temperature [°C]
140
120
100
80
60
System temperature (water)
40
Figure 10:
20
Cold-start test with 100 mg · L–1
film-forming amine in compari-
60 80 100 120 140 160 180 200 son with inorganically treated
Time [s] reference at a heat flux density
·
of q = 8 · 105 W · m–2.
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Film-Forming Amines in Shell Boilers PPCHEM

0.5–1.0 mg · L–1 film-forming amine

Inorganically treated reference
10x10 5 150

9x10 5 Mean tube wall temperature 135

8x10 5 120
Saturation temperature
Heat Flux Density [W · m–2 ]

7x10 5 105

Temperature [°C]
Manual adjustment
6x10 5 90

5x10 5 75
Heat flux density
4x10 5 60

3x10 5 45

2x10 5 30 Figure 11:

1x10 5 15 Warm-start test with 10 mg · L–1
film-forming amine in
0 0
0 20 40 60 80 100 120 140 160 180 200 comparison with inorganically
Time [s] treated reference after a sudden
·
load of q = 4 · 105 W · m–2.

Cetamine Concentration Heat Flux Density Condition Behavior

[mg · L–1] [103 W · m–2] (start-up/standby) (normal/critical/burn-out III)
~ 400 start-up + standby normal
0.5–1.0
~ 800 start-up + standby normal
~ 400 start-up + standby normal
10
~ 800 start-up + standby normal
~ 400 start-up + standby normal
100
~ 800 start-up + standby normal
Table 2:
Summary of the results of burn-out III tests.

SUMMARY
The studies presented here had the aim of providing
answers to important questions concerning the use of
film-forming amines (Cetamine) in steam generators,
where they are increasingly being used with success.
Tests were carried out in test steam generators under con-
trolled conditions to study the three following application
areas:
• Influence of film-forming amines on boiling behavior
and heat transfer
The results presented here clearly prove that the heat
transfer coefficient from the heated tube surface to the
boiler water is considerably increased by the use of
film-forming amines in comparison to treatment with
phosphate.
With film-forming amines, additional nucleation sites for
bubble formation are activated which, as shown by
video recordings, manifest themselves in a consider-
ably more intensive bubble formation throughout the
operational range of heat flux densities in shell boilers.
At the same time the use of film-forming amines
extends the usable range of nucleate boiling in steam
generators by reducing the necessary heat flux density
for nucleation.
• Influence of film-forming amines on oxidic protective
film formation
In both the studied treatment programs the desired pro-
tective layers are formed of magnetite/hematite.
However, the covering layers after film-forming amine
treatment are clearly more homogeneous, thinner and
have a considerably lower degree of roughness in com-
parison with phosphate-treated tubes, when bare tubes
are used as the starting point. After switching from
phosphate to film-forming amine treatment the already-
formed covering layer only grows to a slight extent;
however, it becomes more uniform, which is reflected
by a reduction in surface roughness.

PowerPlant Chemistry 2012, 14(1) 47

Heft2012-01:Innenseiten 09.01.12 11:11 Seite 48

PPCHEM Film-Forming Amines in Shell Boilers

• Influence of film-forming amines on critical operating THE AUTHORS

conditions
Holger Topp (Ph.D., Mechanical Engineering, University
The critical heat flux density of the treated test heating of Rostock, Germany) worked as a research associate at
surfaces was determined, using bare tubes as a start- the University of Rostock from 2006 until 2010. In 2010 he
ing point and after achieving thermal stationarity at received a Ph.D. on the topic of heat transfer in shell boil-
2 bar. The measured values for the tubes treated with ers. Since 2011, he has been working in the area of cabin
film-forming amines and phosphate agree within the development and heating applications in the aerospace
limits of measuring accuracy and lie in the range of val- industry for Astrium RST Rostock GmbH.
ues given in the literature for pure water.
Wolfgang Hater (Ph.D., Physical Chemistry, Westphalian
In addition, tests were made of the behavior of condi-
Wilhelms-University, Münster, Germany) joined Henkel in
tioned heating surfaces, both from a cold start and from
1989. He worked for the industrial cleaner business until
stand-by, using two excessively high heat flux densi-
1993. He later became the manager of the Technology
ties. The curves for the tube temperature and heat flow
Department of the Henkel Water Treatment Group. Since
density as a function of time show the same form, even
2008, Wolfgang Hater has been working at BK Giulini in
at an extreme overdose of film-forming amines, as
Ludwigshafen and is the technical manager of BKG Water
obtained during similar tests using phosphate as the
Solutions.
conditioning agent.
Andre de Bache (Laboratory Engineer) started his career
The results presented here provide no indication at all
at the Max-Planck-Institute for Bio-Inorganic Chemistry. In
that there is any difference between the two treatment
1998 he joined Henkel and worked for the Department of
methods with respect to the investigated boiling crises.
Hygiene and Microbiology. In 2004 he started working for
BYK-Chemie in the application technology division of
Additives for Plastics. In 2006 he joined Henkel Water
Treatment. Since 2008 he has been working for BK Giulini
REFERENCES
Water Solutions in product development for water condi-
[1] Steinbrecht, D., Zu den Ursachen zeitlicher tioning. He has specialized in the field of boiler water treat-
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beim Sieden von Wasser an Stahlheizflächen, 1983.
Technische Hochschule Otto von Guericke Christian zum Kolk (M.S., Chemistry, Cologne University
Magdeburg, Germany, Habilitation Treatise. of Applied Sciences, Germany) started his career in the
Water Treatment Department of Henkel KGaA in 2004,
[2] Topp, H., On the Interaction of Chemically Con-
after studying chemical engineering and plant design. He
ditioned Water with Steel Heating Surfaces during
worked in different fields of expertise including cooling
Saturated Pool Boiling, 2011. Ph.D. Thesis, Uni-
and boiler water treatment before he specialized in the
versity of Rostock, Germany.
field of membrane treatment for desalination processes.
[3] Hömig, H., Physikochemische Grundlagen der Since 2008 he has been working for BKG Water Solutions
Speisewasserchemie, 1963. Vulkan-Verlag, Essen, in product development as a technical manager for water
Germany, 3rd Edition. conditioning.
[4] Kirsch, H., Pollmann, S., Chemie Ingenieur Technik,
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[5] Hater, W., Olivet, D., VGB PowerTech, 2009 89(3), CONTACT
375.
Wolfgang Hater
[6] Topp, H., Steinbrecht, D., Hater, W., de Bache, A., BK Giulini GmbH
PowerPlant Chemistry, 2010 7(12), 388. Niederheider Straße 22
40589 Düsseldorf
[7] Backhaus, E., Steinbrecht, D., Erhöhung der Sicher-
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E-mail: wolfgang.hater@BK-giulini.com
PowerTech Service GmbH, Essen, Germany, VGB
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48 PowerPlant Chemistry 2012, 14(1)