Experiences with the application of film forming

amines in the Connahs Quay triple stage CCGT

power plant operating in cycling mode

efficiency for industry

B. Smith (Uniper)
B
(Uniper), P.
P McCann (Uniper)
(Uniper),
W. Hater (Kurita), A. de Bache (Kurita)

Content
Connahs Quay power plant
Water/steam cycle chemistry analysis
Results of plant inspections
Conclusions

U i
Uniper
P
Power
Pl t Connahs
Plant,
C
h Quay,
Q
UK

Gas-Fired CCGT Plant

Commissioned in 1996
4 x 345 MWe
Electrical power to grid
No steam or heat export

U i
Uniper
P
Power
Pl t Connahs
Plant,
C
h Quay,
Q
UK
Type of boilers:

Vertical gas path drum boiler (HRSG)

Steam pressure:

6, 33, 120 bar

Steam temperature:

541C (superheater, reheater), 271 C LP

Condensate return:

> 95 %

Type of steam turbine:

Condensing

Condensate polishing:

None

Make-up water:

DI water plant by ion exchange

Deaerator:

T = 110C (two-stage, thermal, mechanical)

Condenser:
C

S water cooled condenser

Sea

Materials:

Steel, titanium tube nest

C
Connahs
h Quay
Q
W t /St
Water/Steam
C l
Cycle

CO: Condensate
DA: Deaerator
EC: Economiser
PH: Preheater
EV: Evaporator
SH: Superheater
RH: Reheater
LP: Low pressure
IP: Intermediate
pressure
HP: High pressure

O
Operating
ti Challenges
Ch ll
for
f Preservation
P
ti
Recent mode of operation:
Station operating regime varies considerably, between 1 and 4 units running
with daily start-ups and shutdowns
Maximum stand-by period ca. 4 weeks
Units must remain available with short start-up times
Preservation challenges
possible to p
protect all p
plant areas due to p
plant design,
g , e.g.
g Reheater
Not p
cannot be isolated
Established preservation methods are difficult to implement without
compromising start
start-up
up times
Steam turbines not routinely preserved unless more than 2 weeks stand-by
(need to connect dehumidifiers)

W t /St
Water/Steam
C l Treatment
Cycle
T t
t
until
til 2013:
2013

Ammonia
A
i
NaOH

12.2013

Unit 4
Cetamine V219 (FFA + Cyclohexylamine)
Ammonia
NaOH
same as before

08.2015
08 2015

03.2016
03 2016

(feedwater:
(f
d t
pH:
H 9
9.4
4 9.6)
9 6)
(boilers:
pH: HP 9.2 9.4; IP, LP 9.5 9.8)

Unit
U
it 1
Cetamine G850 (FFA)
Ammonia
NaOH
same as before

Feedwater
Feedwater

Feedwater
Feedwater

All four units changed to treatment concept of Unit 1

7

C t i Trials
Cetamine
Ti l
FFA
Adjustment of product dose to achieve 0.1 g/m FFA
Analysis
y byy Bengalrose
g
method
FFA could be detected latest 2 hours after unit start-up

Unit 4
Cetamine V219 (FFA + Cyclohexylamine)
First detected FFA in condensate after 420 hours running; 4 months total time
(ca. 30 start-ups)
Unit 1
Cetamine G850 (FFA only)
First detected FFA in condensate after 380 hours running, total time 3 weeks
((ca. 20 start-ups)
p )
8

Unit
U
it 4 IP R
Reheat
h t St
Steam:
(Degassed) Conductivity After Cation Exchange

Start of Cetamine V219

dosing

U it 1 HP Steam:
Unit
St
C d ti it After
Conductivity
Aft C
Cation
ti E
Exchange
h

Start of Cetamine G850

dosage

10

Comparison
C
i
off Monitoring
M it i Data
D t from
f
U it 4 (V219) and
Unit
d
Unit 1 (G850)
Acetate and formate concentrations in HP, IP and LP Steams

11

Comparison
C
i
off Monitoring
M it i Data
D t from
f
U it 4 (V219) and
Unit
d
Unit 1 (G850)
Contributions to HP/IP Steam Conductivity After Cation Exchange

12

Treatment
T
t
t Results:
R
lt HRSG D
Drums
(Unit 4: 12.2014 12 months V219)

High Pressure Drum

I t
Intermediate
di t Pressure
P
D
Drum

Reduced amount of iron oxide in HP Drum

No organic deposits
13

Treatment
T
t
t Results:
R
lt HRSG D
Drums
(Unit 1: 10.2015 3 months G850)

High Pressure Drum

Low Pressure Drum

More iron oxide deposits in HP Drum compared to Unit 4

No organic deposits
14

T t
Treatment
t Results:
R
lt HP E
Evaporator
t B
Boiler
il Tubes
T b
Unit 4: (10.2015)

Unit 1 (8.2015)

15

T t
Treatment
t Results:
R
lt Unit
U it 4 HP E
Evaporator
t Tubing
T bi

2012

2015

100 m

50 m

Removal of loose deposits after two years treatment with FFA

16

T t
Treatment
t Results:
R
lt Reheater
R h t Tubes
T b
U it 4
Unit

Unit 1

Typical appearance, no noticable change following FFA treatment

17

XPS St
Studies
di off Boiler
B il Tube
T b Samples
S
l
Samples studied:
Unit 4
From
F
2012 ((no FFA)
HP Evaporator
From 2015 (2 years V219)
HP Evaporator
Reheater

Photoelectronspectroscopy (XPS)
Elemental composition of surface (nm)
Depth profiles
Information on chemical structure via
binding energy
Typical XPS spectrum

Unit 1
From 2015 (3 months G 850)
HP Evaporator
p
Reheater

18

R
Results
lt off XPS St
Studies
di
Main components
Carbon (mainly aliphatic)
Oxygen
Steel material (Fe, Cr, Ni)
Traces of F (cutting)
Nitrogen (mainly organic amine)
N as organic amine detected on all
s rfaces exposed
surfaces
e posed to FFA
No N detected on untreated surfaces

Tube sample

N-content
[At %]

Unit 4
HP E
Evaporator
t
2012 (no FFA)
2015

0
0.9 2.3

Reheater 2015

1.2

Unit 1 ((2015))
HP Evaporator

0.4 0.7

Reheater

1.8

19

T t
Treatment
t Results:
R
lt LP Steam
St
T bi
Turbines,
St
Stage
5 (fi
(finall stage)
t
)
Unit 4

Unit 1

Clean hydrophobic surfaces

20

T t
Treatment
t Results:
R
lt LP Steam
St
T bi
Turbine,
Unit
U it 1,
1 Stages
St
1-5
15
Top:
front face
Bottom: rear/trailing face

Stage 1

Stage 2

Stage 3

Stage 4

Stage 5

Clean surfaces (light iron oxide deposits)

Hydrophobicity observed on Stages 4 and 5
21

K it Surface
Kurita
S f
T t Results:
Test
R
lt LP Steam
St
T bi
Turbine,
Units
U it 1 & 4

Kurita Test:
Qualitative test of FFA presence
- Removal of FFA from surface
- Determination of FFA byy
Bengalrose method
- Pink colour => positive proof
- Absorbance
Positive readings on LP turbines
- Unit 4, Stage 5
- Unit 1
1, Stages 1
1-5
5

Sample

Absorbance

Blank
Untreated blade
Unit 4, Stage 5
- front side
- trailing edge
- disk and roots
Unit 1,
- Stage 5
- trailing surface
- inner front
- Stage 3
- front face
- Stage 1
- trailing face

0.16
0.21
0.30
0 26
0.26
0.33

1.21
0.38
0 34
0.34
0.28

22

C
Conclusions
l i
New treatment concept with film forming amines evaluated
FFA could be determined on both water and steam touched surfaces, including
HP Evaporator, Reheater, LP Steam Turbine cylinders
Cleaning effect evident in Unit 4 HP Evaporator - removal of loose iron oxides,
but not magnetite layer
Alkalising amines led to increased CACE caused by organic acids and carbon
dioxide; new Cetamine G850 in accordance with steam quality requirements
Protection of components throughout the water/steam cycle,
cycle including areas
that could not be preserved by nitrogen capping or dehumidified air circulation
Minimal manpower for preservation compared to nitrogen
g capping
g or
dehumification
No impact on unit availability or start-up times

Acknowledgement

to John C. Greene for analytical support

24

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