2015 11 06 -- cetamine technology in power plants - swedish conference 2015
TRANSCRIPT
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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
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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
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
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CetamineTechnology
4
BOILER WATER ADDITIVES
AlkalisingAmines
Film Forming Amines
All-in-oneproduct concept
to treat thewhole
water steamcycle
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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)
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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
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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
FILM FORMATION ON METAL SURFACES
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Cetamineuntreated
Protective Film
Metal
Molecules in water phase
8
FILM FORMATION ON METAL SURFACES
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CetamineTreatment
- low micro roughness
- homogeneous surface
Tradit ion al Treatment
- high micro roughness
- inhomogeneous surface
9
MAGNETITE LAYER STABILIZATION
UNIVERSITY OF ROSTOCK, GERMANY
Shell boiler simulation at university of Rostock at steady state
conditions, p = 15 bar
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a) PO4
b) Cetamine V211
(Different Scale)
Cross SectionExamination
of Tube Surfaces
Cetamine Treatment
Traditional Treatment
15 um
5 um
MAGNETITE LAYER STABILIZATION
UNIVERSITY OF ROSTOCK, GERMANY
Shell boiler simulation at university of Rostock at steady stateconditions, p = 15 bar
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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
MAGNETITE LAYER STABILIZATION
PAPER INDUSTRY, ISRAEL
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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
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CetamineTest Kit
CetaminePhotometric Method
CetamineMonitor
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CETAMINE
ANALYSIS
CUSTOMIZED SOLUTIONS
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Closed hot water systemsClosed cooling systems
Industrial and district heating networks
ClosedSystems
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
SteamGenerators
APPROVED APPLICATIONS
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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 turbineMake-up: DI water
Thermal Deaerator: T = 115 to 120 C
Nehlsen Heizkraftwerke GmbH & Co. KG,Stavenhagen, Germany
CETAMINE
- WASTE INCINERATION PLANT
THE PLANT
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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 PLANT
GENERAL FLOW SCHEME
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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
- WASTE INCINERATION PLANT
STEAM PARAMETERS
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CETAMINE
- WASTE INCINERATION PLANT
DEGASSES 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
conductivity[S/cm]
time [hh:mm]
degassed acidic conductivity and CO2-contribution
acidic
conductivity
degassed
acidicconductivity
ca. 16 h
CO2
CETAMINE
- WASTE INCINERATION PLANT
DEGASSES CATIONIC CONDUCTIVITY
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LCOCDLiquid ChromatographyOrganic Carbon DetectionEt
hanolamine
Ammonia
Glycol
LMWA
Cyclohexylamine
concentrations of organiccompounds
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
measured
single components
calculated
cationicconductivity/S/cm
Estimation of contribution of single components to
cationic conductivity
water
amines
LMWA
CO2
0,06
CETAMINE
- WASTE INCINERATION PLANT
THEORETICAL COMPOSITION OF CATIONIC CONDUCTIVITY
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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
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CETAMINE
- WASTE INCINERATION PLANT
MAN TURBO AG TURBINE EXAMINATION REPORT 2011
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CETAMINE
- WASTE INCINERATION PLANT
MAN TURBO AG TURBINE EXAMINATION REPORT 2011
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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
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CETAMINE
- WASTE INCINERATION PLANT
CONCLUSIONS
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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 AMINES
THE PLANT
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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 AMINES
WATER/STEAM CYCLE CHARACTERISTICS
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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
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DRY LAY-UP WITH FILM FORMING AMINES
WATER QUALITY ACCORDING TO VGB-S-010
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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
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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 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
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DRY LAY-UP WITH FILM FORMING AMINES
PROCEDURE
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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)
DRY LAY-UP WITH FILM FORMING AMINES
CONDENDATE 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
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
DRY LAY-UP WITH FILM FORMING AMINES
RESULTS
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Main feed water tank Raw condensate tank
COMPLETE STAND-BY PRESERVATION
DRY LAY-UP WITH FILM FORMING AMINES
PICTURES OF PLANT INSPECTION 2012
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Main feed water tank Degasser dome
DRY LAY-UP WITH FILM FORMING AMINES
PICTURES OF PLANT INSPECTION 2013
COMPLETE STAND-BY PRESERVATION
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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
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DRY LAY-UP WITH FILM FORMING AMINES
CONCLUSIONS
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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
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