Filmforming Amines

General aspects and application

in power plants today
Matarvattenkonferensen
Stockholm, Sweden
10. 11. November 2015

Andre de Bache
Dr. Wolfgang Hater

CONTENT
INTRODUCTION
THE CETAMINE TECHNOLOGY
FILM FORMATION ON METAL SURFACES
MAGNETITE LAYER STABILIZATION
CETAMINE ANALYTICAL METHOD

CASE STUDY I
IMPACT ON CATIONIC CONDUCTIVITY

CASE STUDY II
DRY LAY-UP WITH CETAMINE

REFERENCES AND CONCLUSIONS

30/11/2015

BOILER WATER ADDITIVES

All-Volatile-Treatment (AVT) concepts

pH adjustment realized by volatile alkalizing agents
Treatment Concept

Agent 1

Agent 2

AVT-R

Volatile Treatment for pH adjustment

+ Reducing agent

Ammonia
Alkalizing Amines

Hydrazin
Carbohydrazid
DEHA

AVT-O

Volatile Treatment for pH adjustment

Ammonia
Alkalizing Amines

OT

Volatile Treatment for pH adjustment

+ FFA (Filmforming Amines)

Ammonia

Oxygen

AVT-F

Volatile Treatment for pH adjustment

+ FFA (Filmforming Amines)

Alkalizing Amines
Ammonia

FFA

BOILER WATER ADDITIVES

Cetamine Technology

Alkalising
Amines

Film Forming Amines

All-in-one
product concept
to treat the
whole
water steam
cycle

CETAMINE FILMING AMINE (CFA)

1
2
R -NH-R -

-NH
n
2

R1 is an unbranched alkyl chain with 12 to 18 carbon atoms

R2 is a short-chain alkyl group with usually 1 to 4 carbon atoms

n is between 0 and 7

BENEFITS OF CETAMINE TECHNOLOGY

Film formation on metal surfaces

Magnetite layer stabilization

Improved heat transfer
Compatibility with online sensors
Cetamine Photometric Method
Wet and dry lay-up of industrial systems
Savings in energy and water

FILM FORMATION ON METAL SURFACES

Adsorption and Formation of a Protective

Film on Metal Surfaces

Hydrophobic Barrier between Water and

Metal
3

1. Adsorption
2. Ion - ion
2
1

2
1

3. Hydrophobic bond
1

FILM FORMATION ON METAL SURFACES

Metal
Protective Film
Molecules in water phase

untreated

Cetamine

MAGNETITE LAYER STABILIZATION

UNIVERSITY OF ROSTOCK, GERMANY

Traditional Treatment

Cetamine Treatment

- high micro roughness

- inhomogeneous surface

- low micro roughness

- homogeneous surface

Shell boiler simulation at university of Rostock at steady state

conditions, p = 15 bar

MAGNETITE LAYER STABILIZATION

UNIVERSITY OF ROSTOCK, GERMANY

a) PO154um

Cross Section
Examination
of Tube Surfaces

Traditional Treatment

(Different Scale)

b)
Cetamine
V211
Cetamine
Treatment
5 um

Shell boiler simulation at university of Rostock at steady state

conditions, p = 15 bar

MAGNETITE LAYER STABILIZATION

PAPER INDUSTRY, ISRAEL
Iron Oxide Layer Development in 90 bars Water-Tube Boiler, Paper Industry
Acid pickling

Acid pickling

Acid pickling

Internal limit at 500 g/m

Online cleaning

Ammonia
Phosphate
1

FFA Treatment

Cetamine V211
Cetamine V2100

According to ASTM 3483-05 Standard Test Methods for Accumulated Deposition in Steam Generator Tubes

COMPATIBILITY WITH ONLINE SENSORS

Compatibility of Cetamine with SWAN Online-Sensors
Cetamine

FFA product 2

FFA product 3

Conductivity

YES

pH

YES

YES

Sodium

YES

YES

YES

Oxygen

YES

YES

YES

Cetamine products are compatible with relevant online-sensors used

under these test conditions
Full study was published by SWAN Analytical Instruments in
PowerPlant Chemistry 2012, 14(9) Impact of Film-Forming Amines on
the Reliability of Online Analytical Instruments
12

CETAMINE ANALYSIS
CUSTOMIZED SOLUTIONS

Cetamine Photometric Method

Cetamine Test Kit

Cetamine Monitor
13

APPROVED APPLICATIONS

Closed hot water systems

Closed cooling systems
Industrial and district heating networks

Closed
Systems

APPROVED APPLICATIONS

Low to High Pressure Systems

Power Plants (Turbines)
Food Industry (Direct Food Contact)
Alkaline Boiling-Out (VGB-S-513-00)
Wet and Dry Lay-Up

Steam
Generators

CASE STUDY I
CETAMINE - WASTE INCINERATION PLANT
IMPACT ON CATIONIC CONDUCTIVITY

30/11/2015

16

CETAMINE - WASTE INCINERATION PLANT

THE PLANT

Nehlsen Heizkraftwerke GmbH & Co. KG,

Stavenhagen, Germany

Plant:
Type of system:
Fuel:

Waste Inceneration
Water-tube (CHP)
Refuse Derived Fuel (RDF)

Rated Thermal Input:

48 MW

Pressure:
Steam temperature:
Steam production:

42 bar
400 C (after superheater)
55 t/h

Return of condensate:

ca. 95 %

Turbine manufacturer:

MAN Turbo AG

Type of turbine:
Make-up:
Thermal Deaerator:

Extraction condensing turbine

DI water
T = 115 to 120 C

CETAMINE - WASTE INCINERATION PLANT

GENERAL FLOW SCHEME
Return of condensate ca. 95 %
4 different condensates

EC1

Feedwater

EC2

EC3

DI-watertank
Steam drum
LP

HP
Boiler

SH3 SH2 SH1

EDI
Reversed osmosis

Consumer

Ion exchanger
Town water

Dosage of Cetamine V211

CETAMINE - WASTE INCINERATION PLANT

STEAM PARAMETERS

Steam on turbine

VGB-S-010-T00
AL 1

plant

direct conductivity

S/cm

---

5.8

cationic conductivity

S/cm

0.5 *

0.6

degassed cat. cond.

S/cm

0.2

0.4

---

9.4

pH-value
Na

ppb

<5

---

Fe

ppb

< 20

< 20

Cu

ppb

<3

---

SiO2

ppb

< 20

< 10

CFA

ppm

---

0.3

* Higher action values may be defined if the increase of cationic conductivity can be attributed to
carbon dioxide and organic decomposition products can be excluded.

CETAMINE - WASTE INCINERATION PLANT

DEGASSES CATIONIC CONDUCTIVITY

CETAMINE - WASTE INCINERATION PLANT

DEGASSES CATIONIC CONDUCTIVITY
degassed acidic conductivity and CO2-contribution
0,80
0,70

conductivity [S/cm]

0,60

acidic
conductivity

0,50
degassed
acidic
conductivity

0,40
0,30

CO2

0,20
0,10

ca. 16 h
0,00
16:33

18:57

21:21

23:45

2:09

time [hh:mm]

4:33

6:57

9:21

Cyclohexylamine

Ammonia

Ethanolamine

Glycol

LMWA

LC OCD
Liquid Chromatography
Organic Carbon Detection

concentrations of organic
compounds
ppb C (carbon)
concentrations of ammonia
ppb N (nitrogen)

CETAMINE - WASTE INCINERATION PLANT

THEORETICAL COMPOSITION OF CATIONIC CONDUCTIVITY

1,0

Estimation of contribution of single components to

cationic conductivity

cationic conductivity / S/cm

0,9
0,8
0,7
0,6
0,5

0,06
0,12

0,4

0,12

0,3

0,58

0,2

0,16

water
amines

LMWA

0,1

0,18

0,0
cationic conductivity
measured

single components
calculated

CO2

CETAMINE - WASTE INCINERATION PLANT

VGB TUBE EXAMINATION REPORT 2011
Combustion chamber
facing half-shell

Combustion chamber
averting half-shell

Compact topotactical oxide layer which is tightly bonded with

the material.
The magnetite coating is predominantly even with a thickness
of <10m and shows no defects or growth disturbances.

CETAMINE - WASTE INCINERATION PLANT

MAN TURBO AG TURBINE EXAMINATION REPORT 2011

CETAMINE - WASTE INCINERATION PLANT

MAN TURBO AG TURBINE EXAMINATION REPORT 2011

CETAMINE - WASTE INCINERATION PLANT

CONCLUSIONS

Cationic conductivity not in line with

VGB-S-010-T-00
Reasons have been investigated
All other parameters in line with
VGB-S-010-T-00
Plant treated right from the start with
Cetamine
Inspected evaporator tubes in excellent
condition according to VBG
Inspected turbine in excellent condition
according to MAN
27

CASE STUDY II
CETAMINE - BROWN COAL FIRED CHP PLANT
DRY LAY-UP

30/11/2015

28

DRY LAY-UP WITH FILM FORMING AMINES

THE PLANT

Brown coal fired power plant (construction: 1999)

Combined heat & power
Supply of nearby city with
District heat 90 MW
Electricity
62 MW
1 Gas turbine
(ABB)
1 HP steam turbine
(ABB)
1 IP/LP steam turbine (ABB)

29

DRY LAY-UP WITH FILM FORMING AMINES

WATER/STEAM CYCLE CHARACTERISTICS

Make-up water:

DI-water

Boiler pressure:

144 bar

Steam temperature:

540 C (Superheater)

Steam capcity:

205 t/h

Cycle chemistry:

AVT(O) (Ammonia)
condensate pH: 8.8

Condenser material:

steel, brass

Condensate polishing unit:

Ion exchanger

30

DRY LAY-UP WITH FILM FORMING AMINES

WATER QUALITY ACCORDING TO VGB-S-010

Acid conductivity:
Fe (AAS graphite tube):
SiO2:

approx. 0.1 S/cm

< 2 g/L
< 5 g/L

As of 2009 decrease of heat consumption

Therefore, economic operation not possible during summer
=> Dry lay-up for 4 to 5 months necessary

31

DRY LAY-UP WITH FILM FORMING AMINES

Conventional dry lay-up not satisfying

Complete emptying of units impossible
(sagging tubes & parts)
Plant not equipped for Nitrogen blanketing
Start-up condensate contains high Fe levels
(e.g. in 2011 ca. 50 to 90 g/L)

Re-engineering of plant too expensive

Dry lay-up with filmforming amines

32

DRY LAY-UP WITH FILM FORMING AMINES

PROCEDURE

1 month before shut down changeover from ammonia dosage to film

formig amine based product
Dosage of undiluted product proportional to make-up water using same
equipment
By-passing of Condensate Polishing Unit
Control parameter in main steam and condensate:
FFA concentration > 0.2 and < 1 mg/L
pH > 8.8
Acid conductivity < 1 S/cm

(additional measurement of degassed acid conductivity)

Feeding of turbine with warm dried air during shut-down

Restart of water/steam cycle with ammonia
33

DRY LAY-UP WITH FILM FORMING AMINES

CONDENDATE PARAMETERS WITH CETAMINE IN 2012

Parameter

Unit

Specification

Measurement

FFA
Conductivity
Direct
Acid
Degassed

mg/L

> 0.2 and < 1.0

0.1 - 0.6

< 1.0

5.5 7.5
0.9 1.2
0.2 0.4

Dose rate:

S/cm
S/cm
S/cm

20 mg/L make-up water

100 mg/L make-up water (last days)

34

DRY LAY-UP WITH FILM FORMING AMINES

RESULTS
System free of corrosion and deposits (visual inspection)
Start-up condensate fully in spec within 5 to 12 hours
approx. 24 h gain in time

Start-up
condensate

Conductivity
[S/cm]

Acid
conductivity
[S/cm]

O2
[g/L]

SiO2
[g/L]

Na
[g/L]

Fe
[g/L]

Cu
[g/L]

Specification

< 5.0

< 0.3

< 20

< 30

< 20

< 20

< 10

Measurement
2012
2013
2014 #

3.89
6.25
3.04

0.29
0.18
0.28

14
n.d.
n.d.

<5
<5
17

<2
n.d.
n.d.

<2
<2
8

<1
n.d.
n.d.

after 4 h; start-up of turbine delayed by non WSC related issues

35

DRY LAY-UP WITH FILM FORMING AMINES

PICTURES OF PLANT INSPECTION 2012

Main feed water tank

Raw condensate tank

COMPLETE STAND-BY PRESERVATION

36

DRY LAY-UP WITH FILM FORMING AMINES

PICTURES OF PLANT INSPECTION 2013

Main feed water tank

Degasser dome

COMPLETE STAND-BY PRESERVATION

37

DRY LAY-UP WITH FILM FORMING AMINES

CONCLUSIONS

Successful dry lay-up of water/steam cycle with film forming

amines
Complete plant protection due to hydrophobic protective film
Significantly lower iron levels in start-up condensate
Faster restarts after shut-down periods
Long lasting film stability under wet and dry conditions
Highly felxible treatment concept tolerating flexible system
operation
No need of dry air or nitrogen

38

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40

CONTACT SLIDE

Andre DE BACHE
Technical Product Manager Boiler Water
Niederheider Strae 22
D-40589 Dsseldorf
Phone + 49 (0)2 11 797 84 10
Email
andre.debache@kurita.eu
Web
www.kurita.eu

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