PPCHEM Experience with the Application of a Film Forming Amine in the Connah's Quay Power Plant

Experience with the Application of a Film Forming Amine

in the Connah's Quay Triple Stage Combined Cycle Gas
Turbine Power Plant Operating in Cycling Mode
Wolfgang Hater, Bill Smith, Paul McCann, and André de Bache

ABSTRACT
Due to the changing conditions of the energy market, many power plants have various periods of non-operation,
ranging from a few days to months. Unprotected unit shutdown represents a serious corrosion risk and thus a risk for
the integrity of key plant parts, such as the boiler or steam turbine. However, the established conservation methods of
the water-steam cycle are not always applicable under the constraints of the modern power market, with unpredictable
shutdown periods, while at the same time the plants have to remain available and may be required to run at short
notice. Film forming amines (FFAs) offer excellent potential for the required flexible conservation process. The Uniper
combined cycle gas turbine power plant located at Connah's Quay, UK, has assessed the applicability of FFAs for
boiler and steam turbine protection.

Besides a product based on a combination of FFAs with alkalising amines, a newly developed product containing
Author's Copy

solely the FFA was applied. Some key benefits could be demonstrated. The protection of the boiler and steam turbine
could be achieved for a period of at least one month. The technology was able to protect all components of the water-
steam cycle, including the areas of predominantly dry steam. Compared to dehumidification or nitrogen capping,
minimal manpower was required for conservation. By the application of the newly developed product, the drawback of
increased cationic conductivity levels was overcome, which remained close to the normal operation values. Due to the
encouraging results, FFAs are now applied in all 4 units of the Connah's Quay power plant.

INTRODUCTION
Organic cycle chemistries based on film forming amines
(FFAs) are increasingly being used as an alternative to
conventional treatment programs for steam generators.
Successful applications have been reported for both
plants which are continuously operated [1–7] and plants
under wet or dry lay-up [5,8,9]. The FFA molecule, often
also referred to as polyamine or as fatty amine, adsorbs
onto metal/metal oxide surfaces to form a hydrophobic
film or barrier, which prevents corrosion by stopping water
and other corrosive agents from contacting the metal/
metal oxide surface. Furthermore, the thin film fosters the
formation of a smooth and compact iron oxide layer [10],
which also plays an important role in preventing corrosion.
Once formed, the protective film remains intact in both
wet and dry conditions, even after dosing has stopped.
This offers significant potential benefits for the preser -
vation of both drained and (partially) filled plants during
shutdown, especially for plants under a cycling mode of
operation.
The technology of FFAs is now included in internationally
accepted guidelines: The International Association for the
Properties of Water and Steam (IAPWS) has published a
Technical Guidance Document on the three main FFA
molecules that have been the subject of intensive
research and where significant application experience is
available [11], which includes oleylpropylenediamine.
Uniper UK's Connah's Quay combined cycle gas turbine
(CCGT) power station has successfully trialled the use of
film forming technology based on oleylpropylenediamine
(OLDA) from Kurita (Cetamine®) for water-steam cycle
preservation [12]. Over a three-year evaluation period, a
comprehensive monitoring and site assessment pro-
gramme was carried out. This paper reports on the experi-
ences and results obtained.
During inspections at Connah's Quay power plant, the
internal surfaces of the heat recovery steam generator
(HRSG) drums and low-pressure steam turbines were

© 2018 by Waesseri GmbH. All rights reserved.

136 PowerPlant Chemistry 2018, 20(3)

 Experience with the Application of a Film Forming Amine in the Connah's Quay Power Plant
investigated in situ for the presence of OLDA with a newly
developed method [13]. Additionally, boiler tube samples
were taken from the high-pressure evaporator and
reheater stages from two different units of the power plant
for destructive examination and laboratory analysis for the
presence of OLDA.
Connah's Quay Power Plant
Connah's Quay Power Station (Figure 1) consists of four
355 MW single-shaft combined cycle units (Units 1 to 4).
The HRSGs are vertical gas path drum-type boilers with
three pressure stages (0.6, 3.6 and 12 MPa) and reheat.
The final steam temperature is 540 °C. The low-pressure
superheater temperature is ca. 270 °C. Make-up water is
prepared by ion exchange and thermally and mechanically
degassed in two steps in the deaerator. The station has a
wet recirculating hybrid cooling system. Figure 2 shows a
schematic of the water-steam cycle.
The cycle chemistry is based on ammonia dosing to the
feedwater to pH 9.4–9.6 and sodium hydroxide dosing to
the drums to achieve a pH between 9.2 and 9.4 in the
Author's Copy
Figure 1:
The Uniper CCGT power plant in Connah's Quay, United Kingdom.
PowerPlant Chemistry 2018, 20(3)
PPCHEM
high-pressure (HP) drum and between 9.5 and 9.8 in the
intermediate-pressure (IP) and low-pressure (LP) drums.
The station operating regime varies considerably, with
between one and four units running on a daily start-up and
shutdown basis. FFA technology was identified as
a potential flexible preservation option for the plant
due to difficulties establishing conventional preservation
methods.
Starting in December 2013, Cetamine V219 was dosed
into the Unit 4 feedwater with reduced ammonia dosage
and, starting in August 2015, Cetamine G850 was dosed
into the Unit 1 feedwater in addition to ammonia.
Both Cetamine products contain the same FFA molecule
(OLDA). Cetamine G850 contains only OLDA, whereas
Cetamine V219 additionally contains cyclohexylamine.
After dosing was started, the targeted residual FFA con-
centration in the return condensate could be measured in
Unit 4 after 420 hours of operation and in Unit 1 after 380
hours of operation. Residual FFA measurement was done
photometrically with the bengalrose method [14].
137
 PPCHEM Experience with the Application of a Film Forming Amine in the Connah's Quay Power Plant

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
Author's Copy

HP drum HP EV

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
EC economiser
PH preheater
EV evaporator
SH superheater
RH reheater
G generator

RESULTS
General Water Chemistry
The changeover from ammonia/NaOH treatment did not
show a significant influence on pH and direct conductivity.
Steam Purity
Conductivity after cation exchange (CACE) as well as
degassed CACE (DCACE) in Unit 4 treated with OLDA and
cyclohexylamine did not meet the quality requirement of
steam purity to the steam turbines (Figure 3), whereas in
Unit 1 (treated only with OLDA), the steam DCACE was
generally below the required 0.2 µS · cm–1 limit (Figure 4).
However, CACE and DCACE were slightly increased in
comparison to the previous treatment. In Figures 3 and 4,
the cycling operation mode is reflected by intense sharp
spikes in the conductivity readings at unit start-ups.
The formation of acetate and formate was determined by
ion chromatography. In Unit 4 dosed with OLDA and
cyclohexylamine, the cause of the increased CACE was
found to be carbon dioxide and also acetate and formate.
The presence of acetate and formate was also reflected in

138 PowerPlant Chemistry 2018, 20(3)

 Experience with the Application of a Film Forming Amine in the Connah's Quay Power Plant PPCHEM

the DCACE measurement. This result is in accordance
with other studies [15,4]. In contrast, the small elevation in
CACE in the Unit 1 steam was almost all due to carbon
dioxide. Figure 5 shows the average concentrations of
acetate and formate for both units. The increased CACE in
Unit 4 apparently results mainly from decomposition of the
cyclohexylamine. This finding is confirmed by thermolysis
studies under superheater conditions [16]. Figure 6
compares the individual contributions to the CACE in both
units. In contrast to Unit 4, the contribution of low molec-
ular acids is very low in Unit 1. There, the steam purity is
maintained within the quality requirements for turbines.
Plant Inspections
During the trial period, plant inspections were carried out
and various water-steam cycle surfaces tested for the
presence of OLDA. Besides visual inspection and metal-
lurgical studies, three methods of analysis were applied to
determine OLDA on the system surfaces: the droplet test
(test for hydrophobicity), the Kurita wipe test and also
photoelectron spectroscopy (XPS). The droplet test is a
simple and non-specific method to illustrate the wettability
Author's Copy
then transferred from the filter paper into an aqueous solu-
tion, and its presence in this solution is determined by the
bengalrose photometric method. A visible pink colour or a
significant absorbance from the bengalrose method is a
clear proof of OLDA on the surface. The test itself and
examples of its use in power plants are described in [17].
XPS provides the elemental composition of the upper
surface layer as well as information on the bonding state
of the elements. The information depth is ca. 10 nm. In
contrast to the two other methods (droplet and wipe
tests), XPS is generally destructive and cannot be carried
out in situ. These methods are described in detail in [13].
In the following, the findings for selected parts of the
water-steam cycle will be discussed.
Drums All drums were very clean and completely free
from organic deposits, such as gunk-balls. No active
corrosion was observed. Loose iron deposits were signifi-
cantly reduced; this was more pronounced in Unit 4,
which can be attributed to the longer period of treatment
with OLDA (Unit 4: 12 months; Unit 1: 3 months) at the
time of this inspection. Figure 7 shows the appearance of

of a surface. The wipe test removes the FFA from the the HP drum of Unit 4 and the LP drum of Unit 1.
surface by wiping it with a solvent-soaked filter paper. It is

Degassed CACE CACE

2.0

1.8
Start of Cetamine® V219
dosing
Conductivity after Cation Exchange [µS · cm –1]

1.6

1.4

1.2

1.0

0.8

0.6

0.4

0.2

0
10/01/13 01/09/14 04/19/14 07/28/14 11/05/14 02/13/15 05/24/15 09/01/15 12/10/15
Date [m/d/y]

Figure 3:
Conductivity after cation exchange (CACE) and degassed CACE (DCACE) in the reheat steam of Unit 4 treated with Cetamine V219
(OLDA and cyclohexylamine). The spikes mark unit start-ups.

PowerPlant Chemistry 2018, 20(3) 139

 PPCHEM Experience with the Application of a Film Forming Amine in the Connah's Quay Power Plant

2.0

1.8
Start of Cetamine® G850
dosing
1.6
Conductivity after Cation Exchange [µS · cm –1]

1.4

1.2

1.0

0.8

0.6

0.4

0.2
Author's Copy

0
07/15/15 07/25/15 08/04/15 08/14/15 08/24/15 09/03/15 09/13/15
Date [m/d/y]

Figure 4:
CACE in the superheated steam of Unit 1 treated with Cetamine G850 (OLDA). The spikes mark unit start-ups.

25
CO2 Acetate Formate
G850 – Average
Ionisation of pure water
Conductivity after Cation Exchange

20 V219 – Average
Concentration [µg · L –1]

0.6

0.5
15
0.4
[µS · cm –1 ]

10 0.3

0.2
5
0.1
0 0
Acetate Formate Acetate Formate Acetate Formate G850 V219
HP Steam LP Steam IP Steam Unit 1 Unit 4

Figure 5: Figure 6:
Average acetate and formate concentrations measured by ion Average contributions to HP/IP steam CACE for Unit 4
chromatography in steam samples from Unit 4 (Cetamine V219) (Cetamine V219) and Unit 1 (Cetamine G850).
and Unit 1 (Cetamine G850).

140 PowerPlant Chemistry 2018, 20(3)

 Experience with the Application of a Film Forming Amine in the Connah's Quay Power Plant PPCHEM

Figure 7:
Unit 4 HP drum after 12 months of treatment (left) and Unit 1 LP drum after 3 months of treatment (right) with film forming amines (OLDA).

HP Evaporators Tube samples were taken from the (Cetamine G850) in a concentration between 0.4 and 2.3
Unit 4 HP evaporator for metallurgical analysis. The tube atom %, indicating the presence of OLDA on the tube
Author's Copy

sample taken in 2015 after 2 years of treatment with OLDA
showed only minor loose deposits. No active corrosion
was seen. In comparison, the internal surfaces of a Unit 4
HP evaporator tube sample taken in 2012 before
Cetamine dosing was started exhibited an outer layer of
porous magnetite of ca. 100 µm thickness (Figure 8). This
comparison showed that loose iron oxide had been grad-
ually removed by the FFA. However, it did not remove the
underlying dense protective magnetite layer.
The surfaces of the tube samples were further studied by
XPS. Nitrogen bonded to aliphatic organic carbon could
be detected on all surfaces exposed to OLDA-based
treatments, for both Unit 4 (Cetamine V219) and Unit 1
surfaces. The tubes of Unit 4 showed a higher nitrogen
concentration than Unit 1, again reflecting the longer
treatment period with OLDA. Furthermore, a tube from
Unit 4 from 2012 was analysed which had never been
exposed to an OLDA-based treatment and no nitrogen
was detected.
Reheater Tube samples were taken from both units, and
a typical internal appearance was found with no notice-
able change following OLDA treatment (Figure 9). XPS
detected nitrogen bonded to aliphatic carbon between 1.2
and 1.8 atom %, a strong indication of film formation also
under dry steam conditions.

Figure 8:
Removal of loose iron oxide from Unit 4 HP evaporator waterside surfaces – before (left) and after (right) 2 years of treatment with FFAs.

PowerPlant Chemistry 2018, 20(3) 141

 PPCHEM Experience with the Application of a Film Forming Amine in the Connah's Quay Power Plant

Figure 9:
Reheater tubes from Unit 4 (left) and Unit 1 (right) after treatment with OLDA. No noticeable differences following the change of
treatment.
Author's Copy

Figure 10:
Appearance of Stage 5 (final stage) of the LP turbines of Unit 4 (left) and Unit 1 (right) after 12 and 3 months, respectively, of treatment
with FFAs.

LP Turbine Figure 10 shows pictures from the final stage
(Stage 5) of the LP turbine of both units. Surfaces were
very clean and showed clear hydrophobicity. No corrosion
was observed. During a planned shutdown of Unit 1, all
stages of the turbines could be assessed. All surfaces
were clean and free from corrosion. Stages 1–3 had light
magnetite deposits. Hydrophobicity was detected on
Stages 4 and 5 only.
During both inspections, a thorough evaluation of the
accessible turbine stages using the Kurita wipe test was
carried out. OLDA could clearly be measured on the
LP turbine surfaces of both units. It was detected on all
five stages of the Unit 1 LP turbine (only Stage 5 of Unit 4
could be accessed). Table 1 shows selected absorbance
readings corrected for the Blank. For comparison, the
absorbance of the front side of a turbine blade that had
not been exposed to an OLDA treatment is also shown.
Hydrophobicity is apparently not an unambiguous indica-
tion of the presence of OLDA.

142 PowerPlant Chemistry 2018, 20(3)

 Experience with the Application of a Film Forming Amine in the Connah's Quay Power Plant PPCHEM

start/stops of units, with unpredictable shutdown periods,

Sample Absorbance
while at the same time the plants have to remain available
Untreated blade 0.05 and may be required to run at short notice. Two products
Unit 4, Stage 5 were applied: Cetamine V219, a combination of OLDA and
cyclohexylamine, and Cetamine G850, containing only
Front side 0.25 OLDA. The key findings can be summarised as follows:
Trailing edge 0.21
• OLDA could be determined on both water and steam
Disk and roots 0.28 touched surfaces, including HP evaporators, reheaters
Unit 1 and LP steam turbine cylinders.
Stage 5 • There was an evident internal cleaning effect in two
Trailing surface 1.16 units in the HP evaporator: loose iron oxides were
removed, but not the magnetite layer.
Inner front 0.33
• The reliability and maintenance effort of on-line chemi-
Stage 3 cal monitoring sensors were not affected by the film
Front face 0.29 forming amine.
Stage 1 • Alkalising amines led to increased CACE caused by
organic acids and carbon dioxide; treatment with the
Trailing face 0.23
new Cetamine G850 provides steam in accordance
Table 1: with steam quality requirements.
Presence of OLDA as determined by the Kurita wipe test on • Components throughout the water-steam cycle were
turbine surfaces treated with OLDA. For comparison, the value
Author's Copy

protected, including areas that could not be preserved

of an untreated blade is shown.
CHANGING THE TREATMENT CONCEPT TO
OLDA-BASED CHEMISTRY
The results of the trials with OLDA-based treatment
programmes showed an excellent preservation of the
inspected plants for both units. Management and control
of preservation with OLDA-based chemistry is simple. The
treatment concept using Cetamine G850 containing only
OLDA has the benefit of keeping the quality requirements
of steam purity.
by previous nitrogen capping or dehumidified air circu-
lation.
• The preservation with film forming amine requires mini-
mal manpower compared to preservation with nitrogen
capping or dehumidification.
• There was no impact on unit availability or start-up
times.
• The concept of FFA dosage for preservation and
ammonia and sodium hydroxide for pH control has now
been applied successfully for more than two years in all
four units at Connah's Quay.

Due to the overall positive findings, it was decided to

adopt the supplementary treatment with Cetamine G850
REFERENCES
in addition to conventional ammonia and NaOH condi-
tioning for all four units at the Connah's Quay Power [1]
Station as of March 2016. The positive results have been
confirmed by several plant inspections. The cleaning
[2]
effect of OLDA observed in the HP evaporator of Unit 4
has also been seen in a second unit. Since 2017,
Cetamine G850 has also been dosed into the auxiliary [3]
boilers (five Benson-type boilers with an overall 40 t per
hour steam capacity), which are operated mainly during
[4]
start-up and shutdown of the units.
[5]
CONCLUSIONS
The Uniper power station at Connah's Quay evaluated
FFAs as a new treatment concept for meeting the preser- [6]
vation challenges of today's energy market, i.e. frequent
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Hater, W., Digiaro, C., Frayne, C., Proc., International
Water Conference, 2012 (San Antonio, TX, U.S.A.).
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Pittsburgh, PA, U.S.A., Paper IWC-12-20.
Hoock, B., Hater, W., de Bache, A., PowerPlant
Chemistry 2015, 17(5), 283.

PowerPlant Chemistry 2018, 20(3) 143

 PPCHEM Experience with the Application of a Film Forming Amine in the Connah's Quay Power Plant

[7] Sylwestrzak, E., Moszczynski, W., Hater, W.,
Dembowski, T., de Bache, A., VGB PowerTech 2016,
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Author's Copy
Bill Smith, station chemist at Uniper's Connah's Quay
Power Station, commenced working in electricity genera-
tion in the UK at Peterhead Power Station in 1984,
followed by 10 years at a nuclear power plant at Heysham
2 Power Station. He has been a site chemist at Connah's
Quay since 1997.
Paul McCann (M.S., Chemistry, University of Nottingham,
UK) is a specialist in power plant water-steam cycle chem-
istry, corrosion, and water treatment at the Uniper
Technologies Ltd. global consulting unit in the UK. He has
had 18 years of experience in the power industry since
joining in 1999. Paul is vice-chair of the Power Cycle
Chemistry working group of the International Association
for the Properties of Water and Steam (IAPWS). He was
also chair of the British and Irish Association for the
Properties of Water and Steam (BIAPWS) from 2012 to
2016.
André de Bache started his career at the Max Planck
Institute for Bio-Inorganic Chemistry in Mülheim. In 1998
he joined Henkel, where he worked for the department of

129. hygiene and microbiology. In 2004 he started working for

BYK-Chemie in the application technology division of
[14] Stiller, K., Wittig, T., Urschey, M., PowerPlant
additives for plastics. In 2006 he joined Henkel Water
Chemistry 2011, 13(10), 602.
Treatment, and started working in 2008 for ICL Water
[15] Soellner, A., Glueck, W., Hoellger, K., Hater, W., de Solutions in product development for water conditioning,
Bache, A., VGB PowerTech 2013, 93(3), 61. specializing in boiler water treatment. In 2012 he became
the technical manager for boiler water additives, including
[16] Moed, D. H., Verliefde, A. R. D., Rietveld, L. C.,
traditional treatment products as well as products based
Industrial and Engineering Chemistry Research
on film forming amines. In 2014 he became the product
2015, 54(10), 2606.
manager for boiler water additives, filling this position
[17] Hater, W., Jasper, J., Disci-Zayed, D., Paper pre- since February 2015 for Kurita.
sented at the 2nd International Conference on Film
Forming Substances, 2018 (Prague, Czech
Republic). International Association for the
Properties of Water and Steam. CONTACT
Wolfgang Hater
Kurita Europe GmbH
THE AUTHORS Niederheider Strasse 22
40589 Düsseldorf
Wolfgang Hater (Ph.D., Physical Chemistry, Westphalian
Germany
Wilhelms-University, Münster, Germany) started his
professional career in 1989 at Henkel, where he worked E-mail: Wolfgang.Hater@kurita.eu
for the industrial cleaner business. From 1993 until 2015
he worked in different technical positions in the water
treatment divisions of Henkel and BK Giulini. Currently he
is the technical director at Kurita Europe. He is the
co-chairman of the working group Corrosion and Scale
Inhibition of the European Federation of Corrosion and a
member of the Power Cycle Chemistry working group of
the International Association for the Properties of Water
and Steam (IAPWS).

144 PowerPlant Chemistry 2018, 20(3)