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

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

Cetamine¥
PO4,¥
PO4,¥ Cetamine¥
300

Technically relevant domain

250
Relative Enhancement of k [%]

200

150

100

50
Figure 1:
Relative improvement in the heat transfer
0 coefficient k when the film-forming amine is
10 4 10 5 10 6
used compared with treatment with trisodium
Heat Flux Density [W · m–2 ]
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 directly after switching to film-forming amines is com-
increase in active bubble nucleation on the surface when pletely covered with bubbles because of the surface-active
compared with the inorganic method could be observed. effect. The nucleate boiling of the water and an increased
turbulence result from bubble formation and detachment,
The following freeze-frame images from video recordings intensifying the cooling of the heating surface.
(see Figure 2) are used to visualize the boiling process at a
comparatively low heat flux density for practical boiler In addition, when the amine program is used, a lowering
·
operation of about q = 1 · 104 W · m–2. This low heat flux of the necessary heat flux density for activating bubble
density was deliberately chosen in order to visualize the formation on the heating surface is observed. According
influence of film-forming amines on the boiling process as to this, if the organic feedwater additive is used, then
at higher heat flux densities differences in the number of nucleate boiling already occurs at a lower heating surface
active nucleation sites are rather difficult to observe with loading than when inorganic conditioning is applied. The
the naked eye. working range of nucleate boiling with its high heat
transfer coefficient is increased accordingly when film-
The left-hand image in Figure 2 shows the forming amines are used [2].
operating condition at the end of the
trisodium phosphate treatment (PO4,∞ after
an operating time of about 300 h); the 1 400 Tube A244
right-hand image shows the boiling
PO4 Tube A244 SE3
process on the identical test tube directly 1 200
Tube A244 SE5
after switching to the film-forming amine
Fe (pure)
method, PO4, ∞ 씮 Cetamine0 .2 1 000
Fe3O4 (synthetic)
Lin [Cps]

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

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 PPCHEM

·
It can be seen that treatment with the film-forming amines of the experimentally determined value of q for both the
results in the formation of thinner and also more uniform organic and the inorganic reference treatment with Na3PO4.
oxide layers than those obtained by treatment with
trisodium phosphate, substantiating Figures 5 and 6. The In the experiment burn-out I was brought about by
oxide layer formed under phosphate conditions increases increasing the strength of the electric current through the
only slightly after switching to film-forming amines. test tube step-by-step. After the required current strength
However, the switch results in the oxide layer becoming was reached a waiting period was observed until the
more homogeneous, as is indicated by the reduced stand- recorded physical parameters achieved a stable condi-
ard deviation. Surface roughness is also reduced [6]. 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.
INFLUENCE OF THE FILM-FORMING AMINE ON
POSSIBLE CRITICAL OPERATING CONDITIONS Figure 7 uses freeze-frame images to show the burn-out I
of a test heating surface after exceeding the critical heat
Despite these positive effects of the film-formers on heat flux density using a phosphate-treated test tube as an
transfer during boiler operation and the heating surface example.
properties, certain misgivings exist concerning the nega-
tive effects of organic treatment on critical operating con- Figure 8 contains the determined measured values in a
ditions in steam boilers. In the past various organic feed- · ·
k – q plot. The individual pairs of values of k and q form a
water additives have already been studied experimentally straight line in a double-logarithmic plot, the so-called
with respect to their effect on critical operating conditions boiling curve, characteristic for the respective boiling
(the so-called boiling crises) [7]. A negative influence of regime (convective/nucleate), treatment type and period.
the conditioning agent used on the studied operating con- For orientation purposes, the characteristic boiling curve
ditions could not be observed. for the trisodium phosphate treatment has been included
in the plot. The range of values given in the literature for
The theoretically possible boiling crises in steam boilers ·
the critical heat flux density qkrit when boiling chemically
are briefly explained below. In thermal experiments the pure water at ps = 2 bar is marked gray in the plot. The val-
influence of film-forming amines on the critical operating ues stated in the literature lie between 1.4 · 106 W · m–2 and
conditions for shell boilers was investigated systematically. 1.8 · 106 W · m–2 [8].

First Type of Boiling Crisis, Burn-Out I The tests show that the constituents of the product
· Cetamine V211 do not affect the position of the critical
If a critical value for the heat flux density q is achieved dur- heat flux density. The formation of an oxide layer also has
ing nucleate boiling, then all the nucleation sites that can ·
no measurable influence on qkrit. The experimental mean
be activated on the heating surface are occupied by ·
of the critical heat flux densities of qkrit = 1.77 · 106 W · m–2
steam bubbles. Heat transfer can no longer be increased lies far outside the domain of technically relevant heat flux
by raising the heat flux density, as the bubbles that already densities and, within the limits of the measuring accuracy,
exist become increasingly bigger and therefore more is the same for both types of treatment studied.
unstable. They hinder each other during detachment and
coalesce. This results in the formation of a local closed The fear that conditioning the heating surface with the
steam film between the heating surface and the boiling film-forming amine studied could result in an increased
water. Heat transfer within the steam film is extremely low sensitivity to burn-out I is unfounded.
(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-
Second Type of Boiling Crisis, Burn-Out II
rial is reached in fractions of a second. The heating sur-
face burns through, the so-called burn-out I. The second type of boiling crisis is a phenomenon of flow
boiling. This process plays no role in saturated pool boil-
The value of the critical heat flux density for water ing and is only mentioned for the sake of completeness.
increases during saturated pool boiling as the saturation
pressure increases (up to about 64 bar). The lower the sat- Normally, during flow boiling, a two-phase mixture flows
uration pressure, the larger is the risk of a burn-out I. This is through a tube wetted with boiling water. When a critical
why a lower saturation pressure of ps = 2 bar (Ts = heat flux density from the inner tube wall to this two-phase
120.21 °C) was selected for the experimental determina- mixture is exceeded, the cooling liquid film dries out. The
tion of the critical heat flux density. If an influence of the change to pure steam flow without the evaporative cool-
film-forming amines on the value of the critical heat flux ing in the wall film at the given heat flux density causes the
density does exist, then it can be detected by comparison heating surface to dry out and overheat (dry-out).

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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 PPCHEM

Third Type of Boiling Crisis, Burn-Out III were kept stationary for at least 6 h in order to enable
deposition of the film-former constituents – if any should
Film-forming amines have the intrinsic property of forming
occur. In accordance with the aim of the study, the partic-
organic films on all boiler surfaces coming into contact
ular test heating surface used was suddenly subjected to
with water and steam [5]. The possibility of the deposition
two different deliberately excessive heat flux densities of
of a thick layer of the organic conditioning agent, for · ·
q = 4 · 105 W · m–2 and q = 8 · 105 W · m–2.4 The system was
example after an overdose, and an associated negative
provided a minimum pause of 6 h between the tests.
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 heat flux density was generated by sudden applica-
tion of strong electric currents to the model heating sur-
The assumption is that thick-film adsorption of the film- face; the current strengths used were based on experi-
former on the heating surface during standstill or at a ence. (A precise presetting of a required heat flux density
lower pressure range without heating leads to the surface was not possible because of the temperature dependency
cavities being covered up [7]. Application of the sudden of the electric heating in the system used. The set heating
stress of a high heat flux density (flame on) means that surface stresses were in an acceptable proximity to the
these cavities could not be activated because of the values mentioned above and are meaningful with respect
organic film. The result would be, similar to burn-out I, that to the assumed effect.)
the material temperature would suddenly rise dramatically
in a fraction of a second. If the material softening (-melt- The resulting increase in the heating surface temperature
ing) temperature were to be reached, then this would caused by the flow of electric current through the (tem-
destroy the heating surface (burn-out III). perature-dependent) ohmic resistance of the test tube
was then compared with the measured data of an inorgan-
According to these scenarios conditions similar to those ically conditioned reference heating surface (by definition
encountered in practice were created by the use of an a burn-out III is not possible) over a similar time. Any vari-
arrangement specially designed for studying boiling ations in the time-dependent behavior of the mean test
processes in pool boilers [6], in order to study in detail the tube temperature can be used to draw conclusions about
influence of the film-forming amine contained in Cetamine the risk or occurrence of a burn-out III. In order to evaluate
V 211 on the activation of the nucleation points. This was the effect of the concentration of film-forming amines in
done by producing cold-start conditions (system tempera- the boiler water on the risk of a burn-out III, in addition to
ture corresponding to ambient temperature3); a sudden the standard concentration (0.5–1.0 mg · L–1 film-forming
heating surface stress was also simulated starting from amine in condensate) two further intentionally chosen
stand-by conditions (ps = 2 bar, Ts = 120.21 °C), without excessive concentrations (10 mg · L–1 and 100 mg · L–1)
the test heating surface being active. Both conditions were investigated.

3 4
The corresponding saturation pressure is far below the ambi- Maximum heating surface loads/heat flux densities in fire tube
ent pressure and permits penetration of atmospheric air into boilers (shell boilers) are normally below 3 · 105 kW · m–2.
the pressure vessel. A slight (nitrogen) overpressure is applied
in order to ensure the leak tightness of the apparatus.

10x10 5 1 500

9x10 5 Normal 1 350

5
Critical
8x10 1 200
Mean Wall Temperature [°C]

Burn-out III
Heat Flux Density [W · m–2 ]

7x10 5 1 050
5
6x10 900

5x10 5 750
5
4x10 600
5
3x10 450
Figure 9:
5
2x10 300
Schematic diagram showing
1x10 5 150 various curves for the heating
surface temperature and heat flux
0 0
0 2 4 6 8 10 12 14 16 18 20 density under normal and critical
Time [s] conditions, and for burn-out III in
an electrically heated system.

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PPCHEM Film-Forming Amines in Shell Boilers

Figure 9 is a diagram illustrating the expected effects and Figure 10 shows an example of the start-up process for a
showing three possible time-dependent curves of heat test heating surface conditioned with 100 mg · L–1 film-
flux density and mean tube wall temperature from a cold forming amine (standard concentration: 0.5–1 mg · L–1)
start and direct application of 4 · 105 W · m–2. compared with an inorganically treated reference surface.
(NB: After overloading the heat flux density a manual cor-
Normal Behavior After an electric current is impressed rection was dispensed with for the reference heating sur-
on the test tube, its mean wall temperature increases lead- face.)
ing to a rising heat flux density. Both physical quantities
develop asymptotically for a normal start-up (solid line in As an example for the loading of a heating surface with
Figure 9). 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
Critical Behavior An already critical impact of an amine in the condensate starting from stand-by (ps =
organic layer on the mean wall temperature by suppress- 2 bar) is shown in Figure 11 in comparison with the inor-
ing nucleation on the surface is demonstrated by the ganic reference method. Both tests show normal curves
dashed line in Figure 9. Desorption processes result in an for the tube temperature and heat flux density. The tem-
over-swing of mean wall temperature and heat flux den- perature curves of organically and inorganically condi-
sity, respectively. Desorption sets in after the boundary tioned heating surfaces are virtually identical. Covering up
layer reaches a certain superheat. When desorption of the of the nucleation points on the surface either does not
organic film "allows" nucleation to set in (if the boundary take place, or it does not manifest itself in any way in the
layer temperature approaches the saturation temperature heating-up behavior.
at the actual system pressure), bubble formation on the
surface leads to an enhanced heat transfer to the boiling The studied scenarios with their parameters and the
or even subcooled water (subcooled boiling results in observed result of the particular test are shown in Table 2.
remarkably high heat transfer coefficients). This eventually
decreases the wall temperature and the heat flux density It can be seen that even the use of a 100-fold concentra-
to the desired operation. tion of the film-forming amine in the product Cetamine has
no measurable influence on the activation of nucleation
Burn-out III If the desorption processes took longer points.
than the electrical heating to cause material temperatures
higher than its melting point, a burn-out III would occur In none of the studied scenarios could a variation in the
(dotted line in Figure 9). Nucleation would be prevented by temperature curve be observed in comparison with the
a thick organic layer covering potentially available nuclei. reference treatment with phosphate within the limits of
The thermal load would increase rapidly due to the high measuring error.
tube temperature. As the tube burned out, the power sup-
ply would be interrupted and the heat flux density would
drop to zero.

100 mg · L –1 film-forming amine

Inorganically treated reference
10x10 5 200

9x10 5 180
5
8x10 160
Mean Wall Temperature [°C]
Heat Flux Density [W · m–2 ]

7x10 5 140

6x10 5 120
5
5x10 100
5
4x10 80
5
3x10 60
System temperature (water)
2x10 5 40
Figure 10:
1x10 5 20
Cold-start test with 100 mg · L–1
0 0 film-forming amine in compari-
0 20 40 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 operational range of heat flux densities in shell boilers.
answers to important questions concerning the use of At the same time the use of film-forming amines
film-forming amines (Cetamine) in steam generators, extends the usable range of nucleate boiling in steam
where they are increasingly being used with success. generators by reducing the necessary heat flux density
Tests were carried out in test steam generators under con- for nucleation.
trolled conditions to study the three following application
areas: • Influence of film-forming amines on oxidic protective
film formation
• Influence of film-forming amines on boiling behavior
and heat transfer In both the studied treatment programs the desired pro-
tective layers are formed of magnetite/hematite.
The results presented here clearly prove that the heat
However, the covering layers after film-forming amine
transfer coefficient from the heated tube surface to the
treatment are clearly more homogeneous, thinner and
boiler water is considerably increased by the use of
have a considerably lower degree of roughness in com-
film-forming amines in comparison to treatment with
parison with phosphate-treated tubes, when bare tubes
phosphate.
are used as the starting point. After switching from
With film-forming amines, additional nucleation sites for phosphate to film-forming amine treatment the already-
bubble formation are activated which, as shown by formed covering layer only grows to a slight extent;
video recordings, manifest themselves in a consider- however, it becomes more uniform, which is reflected
ably more intensive bubble formation throughout the 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-
Veränderungen der Wärmeübergangskoeffizienten ment.
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,
1968 40(18), 897.
[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-
Germany
heit bei der Wärmeübertragung beim Sieden von
Wasser in Großwasserraumkesseln, 2002. VGB
E-mail: [email protected]
PowerTech Service GmbH, Essen, Germany, VGB
TW 192.
[8] VDI-Wärmeatlas (Ed.: VDI-Gesellschaft Verfahrens-
technik und Chemieingenieurwesen), 2006.
Springer-Verlag, Berlin/Heidelberg, Germany.

48 PowerPlant Chemistry 2012, 14(1)