2015 11 06 -- Cetamine Technology in Power Plants - Swedish Conference 2015

7/24/2019 2015 11 06 -- Cetamine Technology in Power Plants - Swedish Conference 2015

1/42


2/42

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 2

CONTENT


3/42

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

CarbohydrazidDEHA

AVT-O Volatile Treatment for pH adjustmentAmmonia

Alkalizing Amines

OT Volatile Treatment for pH adjustment+ FFA (Filmforming Amines) Ammonia Oxygen

AVT-FVolatile Treatment for pH adjustment

+ FFA (Filmforming Amines)

Alkalizing Amines

AmmoniaFFA


4/42

CetamineTechnology

4

BOILER WATER ADDITIVES

AlkalisingAmines

Film Forming Amines

All-in-oneproduct concept

to treat thewhole

water steamcycle


5/42

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)


6/42

Film formation on metal surfaces

Magnetite layer stabilization

Improved heat transfer

Compatibility with online sensors

CetaminePhotometric Method

Wet and dry lay-up of industrial systems

Savings in energy and water

6

BENEFITS OF CETAMINE

TECHNOLOGY


7/42

Adsorption and Formation of a Protective

Film on Metal Surfaces

Hydrophobic Barrier between Water andMetal

1 1 1

2 2

3 3

1. Adsorption

2. Ion - ion

3. Hydrophobic bond



8/42

Cetamineuntreated

Protective Film

Metal

Molecules in water phase

8



9/42

CetamineTreatment

- low micro roughness

- homogeneous surface

Tradit ion al Treatment

- high micro roughness

- inhomogeneous surface

9


UNIVERSITY OF ROSTOCK, GERMANY

Shell boiler simulation at university of Rostock at steady state

conditions, p = 15 bar


10/42

a) PO4

b) Cetamine V211

(Different Scale)

Cross SectionExamination

of Tube Surfaces

Cetamine Treatment

Traditional Treatment

15 um

5 um


UNIVERSITY OF ROSTOCK, GERMANY

Shell boiler simulation at university of Rostock at steady stateconditions, p = 15 bar


11/42

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

Acid pickling

AmmoniaPhosphate

FFA TreatmentCetamineV211

CetamineV2100

Internal limit at 500 g/m

Online cleaning

Acid picklingAcid pickling

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

1


PAPER INDUSTRY, ISRAEL


12/42

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 usedunder these test conditions

12

COMPATIBILITY WITH ONLINE SENSORS


13/42

CetamineTest Kit

CetaminePhotometric Method

CetamineMonitor

13

CETAMINE

ANALYSIS

CUSTOMIZED SOLUTIONS


14/42

Closed hot water systemsClosed cooling systems

Industrial and district heating networks

ClosedSystems

APPROVED APPLICATIONS


15/42

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

SteamGenerators

APPROVED APPLICATIONS


16/42

CETAMINE

- WASTE INCINERATION PLANT

IMPACT ON CATIONIC CONDUCTIVITY

30/11/2015 16

CASE STUDY I


17/42

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 turbineMake-up: DI water

Thermal Deaerator: T = 115 to 120 C

Nehlsen Heizkraftwerke GmbH & Co. KG,Stavenhagen, Germany

CETAMINE


THE PLANT


18/42

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


GENERAL FLOW SCHEME


19/42

Steam on turbine VGB-S-010-T00AL 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

pH-value --- 9.4Na ppb < 5 ---

Fe ppb < 20 < 20

Cu ppb < 3 ---

SiO2 ppb < 20 < 10CFA ppm --- 0.3

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

CETAMINE


STEAM PARAMETERS


20/42

CETAMINE


DEGASSES CATIONIC CONDUCTIVITY


21/42

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

conductivity[S/cm]

time [hh:mm]

degassed acidic conductivity and CO2-contribution

acidic

conductivity

degassed

acidicconductivity

ca. 16 h

CO2

CETAMINE


DEGASSES CATIONIC CONDUCTIVITY


22/42

LCOCDLiquid ChromatographyOrganic Carbon DetectionEt

hanolamine

Ammonia

Glycol

LMWA

Cyclohexylamine

concentrations of organiccompounds

ppb C (carbon)

concentrations of ammonia

ppb N (nitrogen)


23/42

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

measured

single components

calculated

cationicconductivity/S/cm

Estimation of contribution of single components to

cationic conductivity

water

amines

LMWA

CO2

0,06

CETAMINE


THEORETICAL COMPOSITION OF CATIONIC CONDUCTIVITY


24/42

Combustion chamberfacing half-shell

Combustion chamberaverting half-shell

Compact topotactical oxide layer which is tightly bonded with

the material.

The magnetite coating is predominantly even with a thickness

of


25/42

CETAMINE


MAN TURBO AG TURBINE EXAMINATION REPORT 2011


26/42

CETAMINE


MAN TURBO AG TURBINE EXAMINATION REPORT 2011


27/42

Cationic conductivity not in line withVGB-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

CETAMINE


CONCLUSIONS


28/42

CETAMINE

- BROWN COAL FIRED CHP PLANT

DRY LAY-UP

30/11/2015 28

CASE STUDY II


29/42

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

THE PLANT


30/42

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


WATER/STEAM CYCLE CHARACTERISTICS


31/42

Acid conductivity: approx. 0.1 S/cm

Fe (AAS graphite tube): < 2 g/L

SiO2: < 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


WATER QUALITY ACCORDING TO VGB-S-010


32/42

Conventional dry lay-up not satisfyingComplete 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



33/42

1 month before shut down changeover from ammonia dosage to filmformig 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


PROCEDURE


34/42

Parameter Unit Specification Measurement

FFA

Conductivity

Direct

AcidDegassed

mg/L

S/cm

S/cmS/cm

> 0.2 and < 1.0

< 1.0

0.1 - 0.6

5.5 7.5

0.9 1.20.2 0.4

34

Dose rate: 20 mg/L make-up water

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


CONDENDATE PARAMETERS WITH CETAMINE

IN 2012


35/42

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

35

Start-upcondensate 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


RESULTS


36/42

36

Main feed water tank Raw condensate tank

COMPLETE STAND-BY PRESERVATION


PICTURES OF PLANT INSPECTION 2012


37/42

37

Main feed water tank Degasser dome


PICTURES OF PLANT INSPECTION 2013

COMPLETE STAND-BY PRESERVATION


38/42

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

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


CONCLUSIONS


39/42

39


40/42

40


41/42

CONTACT SLIDE

Andre DE BACHE

Technical Product Manager Boiler WaterNiederheider Strae 22

D-40589 Dsseldorf

Phone + 49 (0)2 11 797 84 10

Email [email protected]

Web www.kurita.eu
mailto:[email protected]://www.kurita.eu/http://www.kurita.eu/http://www.kurita.eu/mailto:[email protected]


42/42

THANK YOU FOR YOUR ATTENTION

Learn more by visiting

www.kurita.eu

This document is confidential. Any kind of reproduction, change, transfer to a third party or disclosure of this document,

even extracts, requires the prior written consent of Kurita Europe GmbH.
http://www.kurita.eu/http://www.kurita.eu/

Documents

2015 11 06 -- Cetamine Technology in Power Plants - Swedish Conference 2015