Determination of Oleyl Propylenediamine, a Commonly Used Film Forming Amine PPCHEM

Determination of Oleyl Propylenediamine, a Commonly Used

Film Forming Amine, on the Surfaces of Water-Steam Cycles
Bill Smith, Paul McCann, Kazuyoshi Uchida, Shintarou Mori, Julia Jasper, and Wolfgang Hater

ABSTRACT
Organic cycle chemistry based on oleyl propylenediamine (OLDA), a commonly used film forming amine (FFA), pro-
vides an excellent treatment option for water-steam cycles, especially for plants operating in cycling mode where
preservation is required during shutdowns but unit availability must be maintained. Uniper has successfully trialled this
treatment in the triple-pressure combined cycle gas turbine (CCGT) power plant at Connah's Quay, United Kingdom.

During a trial phase over almost three years at Connah's Quay, a comprehensive monitoring and control program was
carried out. This paper reports the results of studies to determine the presence of OLDA on the surfaces of the water-
steam cycles in two units. These included inspections of the heat recovery steam generator (HRSG) drums and low-
pressure steam turbines during plant outages and, additionally, the sampling and off-site analysis of boiler tubes taken
from the high-pressure evaporator and reheater circuits. A study on superheater tubes from a pilot boiler at the Kurita
Global Technology Center in Japan complemented the field results.

Three different methods of analysis were applied: the non-specific hydrophobicity or droplet test using a spray of
Author's Copy

demineralised water, Kurita's own newly developed surface wipe test specific for OLDA, and x-ray photoelectron
spectroscopy to check for amine nitrogen on material surfaces. The first two tests were carried out on-site, the third
one off-site.

OLDA could be detected on the surfaces of all investigated components of the water-steam cycles from both units at
Connah's Quay. This included components operated not only under wet conditions, but also under dry conditions. The
film forming amine was also detected on the superheater tubes from the pilot boiler treated with FFA-based cycle
chemistry. The film forming amine could not be measured on surfaces which had not been exposed to a cycle
chemistry with FFAs.

The OLDA film was present on all surfaces of the water-steam cycle in components that were examined in the
Connah's Quay units. A key operational control was to ensure that a small residual FFA concentration was analytically
detected in the condensate before unit shutdown. This finding supports the practical approach for the control of
FFA-based cycle chemistry, where the analytical proof of FFA in the condensate indicates complete film formation in
the water-steam cycle. The Kurita wipe test is an easy tool to apply which enables operators to verify complete film
formation by the specific measurement of OLDA on water-steam cycle surfaces during plant inspections.

The results strongly indicated that OLDA is present on surfaces throughout the complete water-steam cycle in both
water circuits and in dry steam stages. Therefore, the technology has the capability to protect all components in water-
steam cycles if the FFA is applied correctly.

INTRODUCTION
Organic cycle chemistry based on film forming amines amine, adsorbs onto metal/metal oxide surfaces to form a
(FFAs) is increasingly being used as an alternative to con- hydrophobic film or barrier, which prevents corrosion by
ventional treatment programs for steam generators. stopping water and other corrosive agents from contact-
Successful applications have been reported for both ing the metal/metal oxide surface. Furthermore, the thin
plants which are continuously operated [1–7] and plants film fosters the formation of a smooth and compact iron
under wet or dry lay-up [5,8,9]. The film forming amine oxide layer [10], which is also an important step towards
molecule, often also referred to as polyamine or as fatty preventing corrosion.

© 2017 by Waesseri GmbH. All rights reserved.

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 PPCHEM Determination of Oleyl Propylenediamine, a Commonly Used Film Forming Amine

Once formed, the protective film remains intact in both conditions of a superheater or a reheater, i.e. whether gas
wet and dry conditions, even after dosing has stopped. phase absorption takes place, or whether it adsorbs only
This offers significant potential benefits for the preserva- when moisture is present (wet steam).
tion of both drained and (partially) filled plants during shut-
down, especially for plants under the cycling mode of Three methods of surface analysis of different informative
operation. value and complexity were applied during the inspections:
the simple droplet test for surface hydrophobicity, a newly
The technology of film forming amines is now included in developed in-situ semi-quantitative test for FFA on sur-
internationally accepted guidelines: The International faces, and x-ray photoelectron spectroscopy (XPS) for the
Association for the Properties of Water and Steam determination of amine nitrogen.
(IAPWS) has published a technical guidance document on
the three main film forming amine molecules that have
been the subject of intensive research and for which
WATER-STEAM CYCLES
significant application experience is available [11], which
includes oleyl propylenediamine (OLDA) (Chemical The main part of the studies was done at the Connah's
Abstracts Service (CAS) Number: 7173-62-8). Quay CCGT power station by plant inspections during
outages. Tube samples were taken during planned shut-
Uniper UK's Connah's Quay combined cycle gas turbine downs. For completeness, tube samples from the super-
(CCGT) power station has successfully trialled the use of heater of the pilot steam generator were analysed as well.
film forming technology based on OLDA from Kurita
(Cetamine®) for water-steam cycle preservation [12].
Connah's Quay Power Plant
During a three-year evaluation period, a comprehensive
monitoring and site assessment programme was carried Connah’s Quay power station (Figure 1) consists of four
Author's Copy

out. This paper addresses two key questions: 345 MW single-shaft combined cycle units (Units 1 to 4).
The heat recovery steam generators (HRSGs) are vertical
• How can the film be measured on the surfaces of mate-
gas path drum-type boilers with three pressure stages
rials?
(0.6, 3.6 and 12 MPa) and reheat. The final steam tem-
• Does the film form throughout the entire water-steam perature is 540 °C. The station has a wet recirculating
cycle? hybrid cooling system. Figure 2 shows the water-steam
cycle.
In practice, film formation is judged to be complete when
the FFA molecule can be detected by analysis in the
condensate before the injection point. The analytical proof
of the FFA in the return condensate verifies the complete
distribution of FFA throughout the water-steam cycle. As a
consequence, it is an important indication, but not a
straightforward proof, of complete film formation. Also, it
is not fully clear whether the film formation takes place in
areas of dry steam, e.g. in the superheater and reheater
stages.

Therefore, during inspections at Connah's Quay power

plant, the internal surfaces of heat recovery steam genera-
tor (HRSG) drums and low-pressure steam turbines were
investigated in situ for the presence of OLDA. Additionally,
Figure 1:
boiler tube samples were taken from high-pressure evapo-
The Uniper CCGT power plant in Connah's Quay, United
rator and reheater stages from two different units of the Kingdom.
power plant for destructive examination and laboratory
analysis for the presence of OLDA.
The cycle chemistry is based on ammonia dosing to the
Furthermore, in a pilot plant study carried out in the Kurita feedwater to pH 9.4 to 9.6 and sodium hydroxide dosing
Global Technology Center in Japan, tube samples from to the drums to achieve a pH between 9.2 and 9.4 in the
the superheater of a steam generator operated under con- high-pressure (HP) drum and between 9.5 and 9.8 in the
trolled conditions both with and without FFA-based water- intermediate-pressure (IP) and low-pressure (LP) drums.
steam cycle chemistry were analysed in detail. The main
purpose of the study was to clarify whether the OLDA The station operating regime varies considerably between
molecule adsorbs onto metal surfaces under dry steam one and four units running on a daily start-up and shut-

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 Determination of Oleyl Propylenediamine, a Commonly Used Film Forming Amine PPCHEM

Exhaust

CO PH

Degasser
DA EV

Feedwater tank
HP EC 1 IP/LP EC 1

LP drum
LP EV
Ammonia
NaOH Cetamine®
V219/G850
HP EC 2 IP EC 2

IP drum
IP EV

NaOH

SH
G
HP IP LP
HP EC 3 SH Steam turbines

HP drum HP EV
Author's Copy

NaOH
SH RH Condenser

Gas turbine
G

Figure 2:
Flow scheme of the water-steam cycle of the Connah's Quay power plant. The areas of different pressure are marked by colour.
DA deaerator SH superheater
EC economiser RH reheater
PH preheater G generator
EV evaporator CO condensate

down basis. Film forming amine technology was identified operation. Residual FFA measurement was done photo-
as a potential flexible preservation option for the plant metrically with the Bengal rose method [13].
due to difficulties establishing conventional preservation
methods.
Pilot Boiler
®
Since December 2013, Cetamine V219 has been dosed The pilot boiler (Figure 3) consists mainly of a deaerator,
into the Unit 4 feedwater with reduced ammonia dosage, feedwater tank, boiler, electrically heated superheater and
and, since August 2015, Cetamine® G850 has been dosed condenser (heat exchanger). The circuit material is stain-
into the Unit 1 feedwater additionally to ammonia. less steel. The maximum operating pressure of the boiler
is 10.5 MPa (310 °C) and the maximum superheater
Both products contain the same FFA molecule (OLDA). temperature is 600 °C. Figure 4 shows a schematic of the
Cetamine G850 contains only OLDA, whereas Cetamine pilot boiler [14]. Since the tubes from the superheater
V219 additionally contains cyclohexylamine (CAS-No.: could not be removed without reasonable effort, an
108-91-8). After initial dosing, the targeted residual FFA in exchangeable test tube leading from the outlet of the
the return condensate could be measured in Unit 4 after superheater to the heat exchanger was installed. The test
420 hours of operation and in Unit 1 after 380 hours of tube was made from a typical superheater material and

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 PPCHEM Determination of Oleyl Propylenediamine, a Commonly Used Film Forming Amine

Figure 3: Figure 5:
The pilot boiler at the Kurita Global Technical Center in Japan. View of the pilot plant superheater and the tube installation.

carefully cleaned before installation.

The first part of the tube was insulated Before
and equipped with a thermometer Superheater
(< 10.5 MPa, < 600 °C)
Author's Copy

(Figure 5), which enabled the monitor-

ing of the outer temperature of the Make-up Cation
Pressure
water conductivity
tube during the experiments. H/E control valve

Deaerator H/E
For the internal surface investigations, Feedwater DCC
(140 °C)
the tubes were removed and cut into <10 µg·kg –1 tank H/E Condensate
pieces. Samples from the insulated Condensate
part before the heat exchanger (dry Circulating
steam (superheater) conditions) and a pump Test boiler
H/E

< 10.5 MPa H/E

piece from the part after the heat
Feedwater < 310 °C
exchanger (condensate condition) pump Blowdown
were examined. Chemical 2
After
Chemical 1
The test conditions are listed in
Table 1. The pilot boiler was first oper-
Figure 4:
ated with a higher FFA product
Schematic of the pilot boiler and illustration of the position of test tubes (before: before
dosage without condensate return to
heat exchanger; after: after heat exchanger).
prefilm the surfaces. Then the boiler
DCC degassed cation conductivity measurement
was flushed completely, refilled with H/E heat exchanger
demineralised water, the tube from the

Test Run Identification Cycle Chemistry Boiler Pressure Test Duration Superheater Temperature
[°C] [MPa] [days] [°C]
Blank AA 100 3 450
450 OLDA + AA 100 3 450
500 OLDA + AA 100 3 500
550 OLDA + AA 100 7 550
Table 1:
Survey of test conditions in pilot boiler superheater tests.
OLDA film forming amine
AA alkalizing amine

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superheater to the heat exchanger was replaced by a new the solution is the proof of OLDA on the surface. By meas-
untreated tube, and the test was started. The product uring the absorption readings from plant samples and
dose during this phase was 20 mg · L–1 of commercial comparing to a sample blank, the wipe test can be evalu-
product (0.4 mg · L–1 OLDA, additionally alkalizing amines ated semi-quantitatively. The analysis step can be done
(AA)) to the make-up water. As a blank, an analogue trial separately later, e.g. in a laboratory.
was carried out with the same formulation, but without
OLDA, i.e. with alkalizing amines only. The alkalizing Tests with prefilmed coupons have shown that the OLDA
amines used to adjust the pH in the water-steam cycle is not completely removed by the wiping.
were 2-diethylaminoethanol (CAS-No.: 180-37-8) and
monoethanolamine (CAS-No.: 141-43-5).
XPS (X-Ray Photoelectron Spectroscopy)
During the start and stop of the trial, which was necessary During the interaction of X-ray radiation with the sample
to exchange the test tube, the test tube was in wet condi- electrons, it is possible that inner energy levels are
tions for a period of about 1.0 to 1.5 hour, which was only ionised. For instance, if the K-energy level (1s-state) is
approximately 1.0 to 1.5 % of the total test period. ionised, then at least the binding energy of this state must
be transferred to the electron to allow the photoelectron to
leave the sample surface. In an XPS spectrometer, the
photoelectrons pass through a hemisphere-condenser
METHODS OF ANALYSIS
(analyser) and are recorded with a channeltron detector.
For the determination of OLDA on the internal surfaces of The intensity of the photoelectron is graphed against its
components in the water-steam cycles, three different test binding energy, where the intensity is proportional to the
methods were applied. The hydrophobicity test (droplet concentration and the position of the line (binding energy)
test) and the wipe test can be used on-site during plant describes the chemical nature of the element. A high
Author's Copy

inspections. X-ray photoelectron spectroscopy is carried vacuum (< 10–7 Pa) is necessary to avoid a deceleration of
out on small samples under high vacuum and thus is not the generated photoelectrons by residual gas in the pres-
suitable for on-site studies. sure container.

Due to the fact that each element has a characteristic

Hydrophobicity (Droplet Test)
binding energy, the element composition of the surface
The test for hydrophobicity, or the droplet test, is very can be determined. The intensity correlates with the con-
simple and easy to apply. Therefore, it is very frequently centration of the specific element on the surface. The
used in practice in order to qualitatively evaluate the pres- energy of the photoelectron is influenced by its "next
ence of FFA on a surface. In case of hydrophobicity, the neighbours", i.e. their binding states. This causes a shift of
droplets have a typical round shape. The hydrophobicity the lines in the spectrum from which further information
can be quantified by contact angle measurement [15], but can be derived, e.g. the level of oxidation can be deter-
this is not suitable for plant inspections. mined. Furthermore, functional groups as well as their
proportions can be determined from a detailed analysis of
It should be noted that the hydrophobicity test is not spe- the characteristic lines. In case of FFA on the surface of a
cific for FFA. Furthermore, the test results can be deterio- material, the carbon peak should show carbon mainly
rated by porous materials on the surfaces. bonded to carbon or hydrogen and also carbon bonded to
nitrogen. Carboxylate or ketone functional groups are not
expected.
Wipe Test
Due to the limitations of the hydrophobicity test, there is a With XPS, elements from helium to uranium can be identi-
need for a simple test for the presence of OLDA on sur- fied with a detection limit in the upper ppm range. The
faces that can be done during plant inspections and which information depth is approximately 1 to 5 nm (approxi-
is specific for the FFA. mately 10 to 50 atom layers).

Consequently, Kurita has developed the so-called wipe For the determination of the FFA on material surfaces, the
test, which was applied during the plant inspections of survey spectrum providing the general surface composi-
both units at Connah's Quay. The OLDA on the surface is tion was measured. Furthermore, the N-1s and the C-1s
transferred into solution. This first step can be carried out peaks in higher resolution were recorded.
during plant inspections, e.g. boiler drum internal exami-
nations. XPS has already been applied for studying FFA on sur-
faces [1,16].
The presence of OLDA can then be determined using the
Bengal rose method for solution analysis. A pink colour of

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 PPCHEM Determination of Oleyl Propylenediamine, a Commonly Used Film Forming Amine

RESULTS
All three test methods were applied to study the presence
of OLDA on the surfaces of the water-steam cycle of Units
1 and 4 at Connah's Quay. The hydrophobicity test and
the wipe test were used during plant inspections. XPS
studies were used to analyse tube samples taken from the
HRSGs. Selected tube sample surfaces were evaluated a c
with the wipe test as well.

The superheater tubes taken from the pilot boiler were

submitted only to XPS study since the small tube diameter
prevented evaluation with the two other methods; for the
wipe test, the available surface size was too small. Any
droplet formation could not be evaluated adequately.
b d
Connah's Quay Power Plant
Figure 6:
Table 2 summarises the applied test methods and tube Hydrophobicity test on Connah's Quay low-pressure steam
samples taken at Connah's Quay. Additionally, the start turbine blades.
date and duration of the OLDA-based treatments are a) Unit 1, Stage 5: good hydrophobicity
given. b) Unit 4, Stage 5: good hydrophobicity
c) Unit 4, Stage 5: not exposed to film forming amine: poor
Hydrophobicity test During the inspection of the Unit 4 hydrophobicity
Author's Copy

HRSG IP and HP drums, the hydrophobicity test did not d) Unit 1, Stage 4: mixed hydrophobicity
provide clear results. Therefore, this test was omitted
during the inspection of the Unit 1 drums.

From the LP steam turbine inspections, Figure 6 clearly removed from Unit 4 before the OLDA treatment was
shows good hydrophobicity of surfaces in Stage 5 (final started was also evaluated. In this case, the water
row) in the LP turbines from both Unit 1 (Figure 6a) and droplets spread immediately, showing no evidence of a
Unit 4 (Figure 6b). For comparison, a Stage 5 turbine blade hydrophobic film (Figure 6c).

Sampling Date Duration of OLDA Methods Applied

Treatment
Drums Unit 1 LP, IP, HP 10.2015 2 months V
Unit 4 IP, HP 12.2014 12 months H, W, V
1)
HP evaporator Unit 1 Top of bank 10.2015 2 months W, X
Bottom of bank2) 10.2015 2 months X
Unit 4 08.2015 20 months X
2012 Not treated X
Reheater Unit 1 12.2015 4 months X
Unit 4 10.2015 22 months X
LP turbine Unit 1 Stage 5 09.2015 2 months H, W, V
Stage 1 to 5 10.2015 2 months H, W, V
Unit 4 Stage 5 12.2014 12 months H, W, V

Table 2:
Summary of investigations and test methods applied at Connah's Quay power plant.
H hydrophobicity test X XPS
W wipe test V visual inspection
1) 2)
evaporator outlet evaporator inlet

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The removal of the Unit 1 LP steam turbine rotor allowed

access to all five blade stages. After water spraying, the
blades showed changes of hydrophobicity between the
wet and dry stages. Stage 5 (wet) showed good
hydrophobicity on both front and trailing faces. Stage 4,
which is the moisture transition zone, showed mixed
hydrophobicity (Figure 6d). Stages 1 to 3 (dry) showed no
droplet beading and no hydrophobicity. Most of the
droplet spreading occurred on surfaces where light iron
oxide deposits were present.

Wipe test During the inspection of the Unit 4 IP and HP

drums, a prototype version of the wipe test was applied.
The photometric absorption readings showed significantly
increased values compared to the blank, which were
partially caused by fine iron oxide. Filtration of the solution
removed the OLDA, so that the respective contributions
from iron oxide and from OLDA could not be distin-
guished.

Also during the evaluation of the HP evaporator tube from

Unit 1 (top of bank), very fine iron oxide particles were
removed from the surface with the wipe test. By a new,
Author's Copy

special procedure, these particles could be removed with-

out significant loss of OLDA in the solution. Figure 7 Figure 7:
shows the colour for the wipe test for the top and bottom Samples from wipe test on high-pressure evaporator tube (top
halves (6 and 12 o'clock orientation) of the boiler tubes of bank) from Connah's Quay Unit 1: Blank (left), 12 o'clock
after they were sectioned horizontally. These are then (middle), 6 o'clock (right). The number gives the absorbance
reading of the sample.
compared to the blank. The pink colours as well as the
absorption readings clearly prove the presence of OLDA
on the surface of the evaporator tube. Stage 5 in Unit 1, the keyway blade root of Stage 4
showed a significant positive signal. Table 3 shows
During the inspections of the LP turbines from Unit 1 and selected absorbance data from the wipe tests of the LP
Unit 4, the surfaces in Stage 5 were submitted to exten- turbines.
sive evaluation with the wipe test due to ready in-situ
access. In total, 10 different locations from Stage 5 of Unit Overall, it seems that the distribution of OLDA on the
1 and 16 locations from Stage 5 of Unit 4 were tested, as turbine from Unit 4 is more even than in Unit 1, which
well as structural steelwork in the turbine exhaust. In addi- could reflect the much longer time of the treatment with
tion, a blade from Unit 4 was tested which had been film forming amines. However, the data has to be com-
removed before any FFA treatment. Each wipe test sample pared with care, since the surface areas from the different
showed a clear pink colour and a significantly higher locations that were wiped will have differed considerably.
absorbance value compared to the blank. The only excep-
tions were the keyway blade root in Stage 5 in Unit 1 and,
as expected, the blade not exposed to OLDA treatment. XPS (x-ray photoelectron spectroscopy) A total of 4
For the keyway blade root test, the accessible surface HP evaporator tubes and 2 reheater tubes were analysed
area was very small, which is possibly the reason why the by x-ray photoelectron spectroscopy. The tubes were
qualitative test did not provide a positive reading. sectioned horizontally (i.e. cut at 3 and 9 o'clock positions)
to give two half shells. The bottom half shell is called
Furthermore, wipe tests from all stages of the Unit 1 LP 6 o'clock and the upper one 12 o'clock. Furthermore, the
turbine were taken from both the trailing face and from the tubes were cut into pieces of smaller lengths for analysis.
front face of the turbine blades. Stage 4 (moisture transi-
tion zone) was sampled in more detail at 6 locations. With For the waterside surface of each sample, the survey
the exception of one location on the front face of Stage 4 spectrum was taken and the elemental composition deter-
and one location on the front face of Stage 1, the mined at three different positions. Figure 8 shows a typical
absorbance values were all above the blank, though a few survey spectrum. The composition of the surface consists
of the locations with only slightly elevated readings of carbon, oxygen, the elements from the tube steel,
(ca. 15 % higher than the blank). Contrary to the result for impurities from the water-steam cycle (e.g. sodium, sili-

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 PPCHEM Determination of Oleyl Propylenediamine, a Commonly Used Film Forming Amine

Unit and Turbine Stage Location Wipe Test Absorbance Value

Blank 0.19

Untreated blade, Stage 5 0.21

Unit 1
– Stage 5 Trailing face 1.21
Inner front 0.38
Keyway blade root 0.20
– Stage 4 Front face 0.19–0.32
Trailing face 0.21–0.25
Keyway blade root 0.26
– Stage 3 Front face 0.34
– Stage 1 Trailing face 0.28
Front face 0.16
Unit 4
– Stage 5 Disk and blade roots 0.33
Front face 0.25–0.33
Trailing surface 0.30–0.33
Blade edge 0.26–0.30
Author's Copy

Table 3:
Detection of film forming amine (OLDA) on the surface of the LP turbines from Unit 1 and Unit 4 of the Connah's Quay power plant by
the wipe test. A range of absorbance values indicates that several locations were analysed.

1.50E+05
Survey

1.00E+05
Fe2p3 01s
Counts per s

5.00E+04 Mn2p3 Cr2p3

Ti2p N1s C1s P2p
0.00E+00
Figure 8:
–5.00E+04 Typical XPS survey spectrum of a tube
1 000 900 800 700 600 500 400 300 200 100 0 sample from a water-steam cycle exposed
Binding Energy [eV] to a treatment with film forming amines.
The C-1s and N-1s peaks are marked.

con) and, in some cases, contaminants from the cutting the XPS spectrum of the pure film forming amine (OLDA)
process (potassium and fluoride). Nitrogen could not be was evaluated in the same manner. Figure 10 shows
detected on the HP evaporator tube from 2012 before the examples of the C-1s and N-1s spectra and the deconvo-
FFA treatment. However, nitrogen was found in all of the lution. The relative portion of the individual functional
samples that had been exposed to FFA treated water or groups should be taken with care, since the spectra are
steam (Figure 9) and also on the reheater tube surfaces not well structured and thus the fit is not unambiguous.
that had been exposed to dry steam. The positive results
of the wipe test on the Unit 1 HP evaporator tube taken Carbon predominantly (90 ± 6 %) is present on the sur-
from the top of the bank also qualitatively confirmed the faces as aliphatic carbon (C-C or C-H bonds) (binding
findings of the XPS study. energy: 284.3 eV) or bonded to a more electronegative
element like nitrogen or oxygen (binding energy: 286.1 eV).
Furthermore, detailed spectra of the C-1s and N-1s peaks This is in good accordance with the presence of FFA on
were measured for the majority of samples and deconvo- the surface. Nitrogen is found on the surface as organic
luted with a standard set of binding energies representing amine to more than 90 %, which confirms the finding of
frequently occurring functional groups. For comparison, the C-1s spectra and also discounts ammonia as the

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Unit 1 Unit 4
3.0
Nitrogen Concentration [Atom-%]

HP evaporator
2.5
Reheater
2.0 Figure 9:
Nitrogen content [atom %] of tube
1.5
surfaces from Connah’s Quay power
plant measured by XPS. The HP
1.0
evaporator tube from 2012 had not been
0.5 exposed to film forming amine cycle
chemistry. For the HP evaporator boiler
0 0
0 tube data, the left column indicates the
Top Bottom 2012 2015 value for the 6 o'clock position and the
of Bank
right column the result for the 12 o'clock
position.

1.20E+04
284.6 eV
C-1s
1.00E+04
Counts per s

8.00E+03

6.00E+03 286.2 eV
4.00E+03 287.8 eV
288.9 eV
Author's Copy

2.00E+03

0.00E+00
295 294 293 292 291 290 289 288 287 286 285 284 283 282 281 280 279
Binding Energy [eV]

1.45E+03
399.4 eV
N-1s
1.40E+03
401.3 eV
Figure 10:
Counts per s

398.4 eV
1.35E+03
X-ray photoelectron spectra and
1.30E+03
deconvolution of waterside surfaces from
396.5 eV tube samples of the water-steam cycle of
1.25E+03 Connah's Quay power plant: (top) C-1s
peak of reheater tube from unit 4;
1.20E+03 (bottom) N-1s peak of the HP evaporator
406 405 404 403 402 401 400 399 398 397 396 395 394 393 (bottom of bank, 6 o'clock) from Unit 1.
Binding Energy [eV] The tubes had been exposed to film
forming amine based cycle chemistry.

source. It can be noted that the average binding energy of Pilot Boiler
the nitrogen is shifted about 0.7 eV to higher values com-
In this study, tubes from the pilot boiler were exposed to
pared to the pure OLDA molecule, which reflects the par-
OLDA under very controlled conditions, partially under dry
tial binding of the nitrogen to the metal or metal oxide.
steam conditions (before condenser) and also under wet
This effect has also been reported in the literature [17].
conditions (after condenser).
The XPS spectra were measured between some weeks
Due to the small diameter of the tubes, hydrophobicity
and three years after tube sampling. A loss of OLDA from
could not be observed. Furthermore, the surface area of
a surface under normal storage is very unlikely due to the
the tube under dry steam conditions was too small to
stability of the molecule. In order to exclude effects during
carry out the wipe test. Therefore, the tubes were investi-
storage, a second sample from the Unit 1 HP evaporator
gated by XPS only.
was measured after three months of storage. The results
were in good agreement with the earlier sample, confirm-
Analogously to the tube samples from the Uniper
ing the stability of the film.
Connah's Quay power plant, the survey spectra were
measured to get the surface composition. Carbon,

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 PPCHEM Determination of Oleyl Propylenediamine, a Commonly Used Film Forming Amine

oxygen, elements from the steel material and impurities Furthermore, the C-1s and N-1s spectra were measured in
from the water-steam cycle (e.g. sodium, silicon) were higher resolution and deconvoluted in the same manner
found, as for the power plant tubes. Additionally, lead as for the Connah's Quay tubes. Figure 12 shows the
could be detected, which was a contaminant from solder- spectra of two tubes under superheater conditions (before
ing. Nitrogen was not found at a significant concentration condenser) treated for three (450 °C) and seven days
in the blank tube (only treated with alkalising amines), but (550 °C) with a combination of OLDA as FFA and alkalising
could be clearly detected in all tubes exposed to OLDA amines, together with the spectrum of pure OLDA.
under both dry and wet operating conditions, i.e. before
and after the condenser (Figure 11).

1.0
Nitrogen Concentration [Atom-%]

Before condenser
0.8 After condenser

0.6
Figure 11:
0.4 Nitrogen content [atom %] of tube
surfaces from superheater tube samples
0.2 of a pilot boiler measured by XPS.
Organic cycle chemistry based on film
0
forming amine and alkalising amines had
Blank 450 °C 500 °C 550 °C been applied. Only alkalising amines were
used as cycle chemistry for the blank.
Author's Copy

4.50E+03 398.8 eV
OLDA
4.00E+03 400.4 eV
Counts per s

3.50E+03

401.8 eV
3.00E+03
396.4 eV
2.50E+03

2.00E+03
406 405 404 403 402 401 400 399 398 397 396 395 394 393
Binding Energy [eV]

2.40E+03
399.7 eV
450 °C
2.35E+03
398.4 eV
Counts per s

2.30E+03 401.5 eV 396.5 eV

2.25E+03

2.20E+03
406 405 404 403 402 401 400 399 398 397 396 395 394 393
Binding Energy [eV]

2.30E+03 399.6 eV
398.6 eV 550 °C
2.28E+03
Counts per s

2.26E+03

2.24E+03
401.7 eV Figure 12:
2.22E+03 396.5 eV
N-1s x-ray photoelectron spectra of
2.20E+03 OLDA (top) and surfaces of superheater
tube samples from the pilot boiler
2.18E+03
406 405 404 403 402 401 400 399 398 397 396 395 394 393 exposed to OLDA-based cycle chemistry
Binding Energy [eV] (middle, bottom). The superheater
temperature is indicated on the spectrum.

138 PowerPlant Chemistry 2017, 19(3)

 Determination of Oleyl Propylenediamine, a Commonly Used Film Forming Amine PPCHEM

Carbon predominantly (91 ± 4 %) is present on the sur- FFA was found on the surfaces of reheater tube samples
faces as aliphatic carbon (C-C or C-H bonds) (binding from both units and also on the superheater tubes from
energy: 284.3 eV) or bonded to a more electronegative the pilot generator. The superheater tubes had been
element like nitrogen or oxygen (binding energy: 286.1 eV). treated with a combination of OLDA and alkalizing amines
This is in good agreement with the presence of FFA on the under controlled and stable conditions at three different
surface. Nitrogen is found on the surfaces as organic dry steam temperatures. A blank tube treated with alkaliz-
amine, also to more than 90 %, which confirms the finding ing amines did not show any nitrogen on the surface.
of the C-1s spectra. The average binding energy of the
nitrogen on the surfaces is shifted about 0.5 eV to higher OLDA could be detected on Stage 5 of the LP steam
values compared to the pure OLDA molecule (399.9 eV). A turbine in both Connah's Quay units and also on all other
significant influence of the dry steam temperature could stages of the Unit 1 LP turbine that were accessible during
not be observed. a plant outage. It could not be detected on a turbine blade
that had not been exposed to a FFA-based cycle chemistry.
The data obtained in the pilot plant study fully agree with
the XPS results from the power plant tubes. The presence The results strongly indicate that OLDA adsorbs to
of organic amines on the surfaces of the superheater surfaces throughout the complete water-steam cycle in
tubes is proof that OLDA adsorbs on metal surfaces under both water and dry steam stages. This demonstrates that
dry steam conditions. FFA technology can be used to protect all components in
water-steam cycles.

The OLDA film could be detected on all surfaces analysed

CONCLUSIONS
at Connah's Quay after treatment for only two months and
The presence of OLDA, a commonly used film forming once the FFA had been analytically detected in the con-
Author's Copy

amine, on the surfaces of the water-steam cycle was stud- densate (before the FFA injection point) for a short time.
ied in two different units at Uniper's Connah's Quay power This finding supports the practical approach for the con-
plant. During plant inspections, the HRSG drums and LP trol of FFA-based cycle chemistry, where the analytical
steam turbines were examined in situ for the presence of proof of FFA in the condensate indicates a complete film
OLDA. HRSG HP evaporator and reheater boiler tube formation in the water-steam cycle. The wipe test is an
samples were also taken for surface analysis off-site. The easy to apply tool which enables operators to verify film
units had been operated with a cycle chemistry based on formation by the specific measurement of OLDA on the
OLDA for some months in one unit and for around 3 years water-steam cycle surfaces during inspections.
in the other unit. A study on superheater tubes from a pilot
boiler at the Kurita Global Technology Center comple-
mented the field results.
ACKNOWLEDGEMENT
For the determination of the FFA on the water-steam cycle The authors would like to thank Kirstin Zimmer and André
surfaces, three different test methods were applied. The de Bache for their support and scientific input and Karina
test on hydrophobicity (droplet test) is very simple and easy Bittigau and Alfred Zibula from the Henkel group for carry-
to apply; however, it is not specific for FFA and can some- ing out the XPS studies.
times be ambiguous. The newly developed wipe test is
selective for OLDA and can be used during site inspections.
X-ray photoelectron spectroscopy (XPS) provides the ele-
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PowerPlant Chemistry 2017, 19(3) 139

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AUTHORS
Bill Smith, station chemist at Uniper's Connah's Quay
CONTACT
power station, commenced working in electricity genera-
tion in the UK at Peterhead Power Station in 1984, Wolfgang Hater
followed by 10 years at a nuclear power plant at Heysham Kurita Europe GmbH
2 Power Station. He has been site chemist at Connah's Niederheider Strasse 22
Quay since 1997. 40589 Duesseldorf
Germany
Paul McCann (M.S., Chemistry, University of Nottingham,
UK) is a specialist in power plant water-steam cycle chem- E-mail: [email protected]
istry, corrosion, and water treatment at the Uniper
Technologies Ltd. global consulting unit in the UK. He has
had 17 years of experience in the power industry since join-
ing in 1999. Paul is vice-chair of the Power Cycle Chemistry

140 PowerPlant Chemistry 2017, 19(3)