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Filmforming Amines

General aspects and application

in power plants today

Matarvattenkonferensen

Stockholm, Sweden

10. – 11. November 2015

Andre de Bache

Dr. Wolfgang Hater

• 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

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CONTENT

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BOILER WATER ADDITIVES

All-Volatile-Treatment (AVT) conceptspH adjustment realized by volatile alkalizing agents

Treatment Concept Agent 1 Agent 2

AVT-RVolatile Treatment for pH adjustment

+ Reducing agent

Ammonia

Alkalizing Amines

Hydrazin

Carbohydrazid

DEHA

AVT-O Volatile Treatment for pH adjustmentAmmonia

Alkalizing Amines

OTVolatile Treatment for pH adjustment

+ FFA (Filmforming Amines)Ammonia Oxygen

AVT-FFAVolatile Treatment for pH adjustment

+ FFA (Filmforming Amines)

Alkalizing Amines

AmmoniaFFA

Cetamine® Technology

4

BOILER WATER ADDITIVES

Alkalising

Amines

Film Forming Amines

All-in-one

product concept

to treat the

whole

water steam

cycle

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R1-NH-R2-n-NH2

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

CETAMINE® FILMING AMINE (CFA)

• 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

6

BENEFITS OF CETAMINE® TECHNOLOGY

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• Adsorption and Formation of a Protective

Film on Metal Surfaces

• Hydrophobic Barrier between Water and

Metal

1 1 1

2 2

3 3

1. Adsorption

2. Ion - ion

3. Hydrophobic bond

FILM FORMATION ON METAL SURFACES

Cetamine®untreated

Protective Film

Metal

Molecules in water phase

8

FILM FORMATION ON METAL SURFACES

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Cetamine® Treatment

- low micro roughness

- homogeneous surface

Traditional Treatment

- high micro roughness

- inhomogeneous surface

9

MAGNETITE LAYER STABILIZATIONUNIVERSITY OF ROSTOCK, GERMANY

Shell boiler simulation at university of Rostock at „steady state“

conditions, p = 15 bar

a) PO4

b) Cetamine V211

(Different Scale)

Cross Section

Examination

of Tube Surfaces

Cetamine Treatment

Traditional Treatment

15 um

5 um

MAGNETITE LAYER STABILIZATIONUNIVERSITY OF ROSTOCK, GERMANY

Shell boiler simulation at university of Rostock at „steady state“

conditions, p = 15 bar

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Iron Oxide Layer Development in 90 bars Water-Tube Boiler, Paper Industry

Acid pickling

Ammonia

PhosphateFFA Treatment

Cetamine® V211

Cetamine® V2100

Internal limit at 500 g/m²

Online cleaning

Acid pickling Acid pickling

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

1

MAGNETITE LAYER STABILIZATIONPAPER INDUSTRY, ISRAEL

Compatibility of Cetamine with SWAN Online-Sensors

Cetamine® FFA product 2 FFA product 3

Conductivity YES X X

pH YES YES X

Sodium YES YES YES

Oxygen YES YES YES

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”

Cetamine® products are compatible with relevant online-sensors used

under these test conditions

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COMPATIBILITY WITH ONLINE SENSORS

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Cetamine® Test Kit

Cetamine® Photometric Method

Cetamine® Monitor

13

CETAMINE® ANALYSISCUSTOMIZED SOLUTIONS

Closed hot water systems

Closed cooling systems

Industrial and district heating networks

Closed

Systems

APPROVED APPLICATIONS

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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

APPROVED APPLICATIONS

CETAMINE® - WASTE INCINERATION PLANT

• IMPACT ON CATIONIC CONDUCTIVITY

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CASE STUDY I

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Plant: Waste Inceneration

Type of system: Water-tube (CHP)

Fuel: Refuse Derived Fuel (RDF)

Rated Thermal Input: 48 MW

Pressure: 42 bar

Steam temperature: 400 °C (after superheater)

Steam production: 55 t/h

Return of condensate: ca. 95 %

Turbine manufacturer: MAN Turbo AG

Type of turbine: Extraction condensing turbine

Make-up: DI water

Thermal Deaerator: T = 115 to 120 °C

Nehlsen Heizkraftwerke GmbH & Co. KG,

Stavenhagen, Germany

CETAMINE® - WASTE INCINERATION PLANTTHE PLANT

DI-water-

tank

SH3

Feedwater

Steam drum

EC3EC2EC1

Dosage of Cetamine V211

Boiler SH2 SH1

HPLP

Consumer

Town water

Ion exchanger

Reversed osmosis

EDI

Return of condensate ca. 95 %

4 different condensates

CETAMINE® - WASTE INCINERATION PLANTGENERAL FLOW SCHEME

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Steam on turbineVGB-S-010-T00

AL 1Ø plant

direct conductivity μS/cm --- 5.8

cationic conductivity μS/cm 0.5 * 0.6

degassed cat. cond. μS/cm 0.2 0.4

pH-value --- 9.4

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 PLANTSTEAM PARAMETERS

CETAMINE® - WASTE INCINERATION PLANTDEGASSES CATIONIC CONDUCTIVITY

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0,00

0,10

0,20

0,30

0,40

0,50

0,60

0,70

0,80

16:33 18:57 21:21 23:45 2:09 4:33 6:57 9:21

co

nd

uctivity [

μS

/cm

]

time [hh:mm]

degassed acidic conductivity and CO 2-contribution

acidic

conductivity

degassed

acidic conductivity

Δ

ca. 16 h

CO2

CETAMINE® - WASTE INCINERATION PLANTDEGASSES CATIONIC CONDUCTIVITY

LC – OCD

Liquid Chromatography –

Organic Carbon DetectionEth

an

ola

min

e

Am

mo

nia

Gly

co

l

LM

WA

Cyc

loh

ex

yla

min

e

concentrations of organic

compounds

ppb C (carbon)

concentrations of ammonia

ppb N (nitrogen)

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0,58

0,18

0,16

0,12

0,12

0,0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1,0

cationic conductivity

measuredsingle components

calculated

cati

on

ic c

on

du

ctiv

ity

/ μ

S/c

m

Estimation of contribution of single components to cationic conductivity

water

amines

LMWA

CO2

0,06

CETAMINE® - WASTE INCINERATION PLANTTHEORETICAL COMPOSITION OF CATIONIC CONDUCTIVITY

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 <10μm and shows no defects or growth disturbances. “

CETAMINE® - WASTE INCINERATION PLANTVGB TUBE EXAMINATION REPORT 2011

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CETAMINE® - WASTE INCINERATION PLANTMAN TURBO AG TURBINE EXAMINATION REPORT 2011

CETAMINE® - WASTE INCINERATION PLANTMAN TURBO AG TURBINE EXAMINATION REPORT 2011

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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

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CETAMINE® - WASTE INCINERATION PLANTCONCLUSIONS

CETAMINE® - BROWN COAL FIRED CHP PLANT

• DRY LAY-UP

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CASE STUDY II

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•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)

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DRY LAY-UP WITH FILM FORMING AMINESTHE PLANT

• 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

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DRY LAY-UP WITH FILM FORMING AMINESWATER/STEAM CYCLE CHARACTERISTICS

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• Acid conductivity: approx. 0.1 µS/cm

• Fe (AAS graphite tube): < 2 µg/L

• SiO2: < 5 µg/L

As of 2009 decrease of heat consumption

Therefore, economic operation not possible during summer

=> Dry lay-up for 4 to 5 months necessary

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DRY LAY-UP WITH FILM FORMING AMINESWATER QUALITY ACCORDING TO VGB-S-010

•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 µg/L)

•Re-engineering of plant too expensive

•Dry lay-up with filmforming amines

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DRY LAY-UP WITH FILM FORMING AMINES

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• 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 µS/cm

(additional measurement of degassed acid conductivity)

• Feeding of turbine with warm dried air during shut-down

• Restart of water/steam cycle with ammonia

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DRY LAY-UP WITH FILM FORMING AMINESPROCEDURE

Parameter Unit Specification Measurement

FFA

Conductivity

Direct

Acid

Degassed

mg/L

µS/cm

µS/cm

µS/cm

> 0.2 and < 1.0

< 1.0

0.1 - 0.6

5.5 – 7.5

0.9 – 1.2

0.2 – 0.4

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Dose rate: 20 mg/L make-up water

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

DRY LAY-UP WITH FILM FORMING AMINESCONDENDATE PARAMETERS WITH CETAMINE® IN 2012

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• 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

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Start-up

condensate

Conductivity

[µS/cm]

Acid

conductivity

[µS/cm]

O2

[µg/L]

SiO2

[µg/L]

Na

[µg/L]

Fe

[µg/L]

Cu

[µg/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

DRY LAY-UP WITH FILM FORMING AMINESRESULTS

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Main feed water tank Raw condensate tank

COMPLETE STAND-BY PRESERVATION

DRY LAY-UP WITH FILM FORMING AMINESPICTURES OF PLANT INSPECTION 2012

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37

Main feed water tank Degasser dome

DRY LAY-UP WITH FILM FORMING AMINESPICTURES OF PLANT INSPECTION 2013

COMPLETE STAND-BY PRESERVATION

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

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DRY LAY-UP WITH FILM FORMING AMINESCONCLUSIONS

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39

40

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CONTACT SLIDE

Andre DE BACHE

Technical Product Manager Boiler Water

Niederheider Straße 22

D-40589 Düsseldorf

Phone + 49 (0)2 11 797 84 10

Email andre.debache@kurita.eu

Web www.kurita.eu

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