Filmforming Amines General aspects and application in power plants today

Filmforming Amines General aspects and application in power plants today Matarvattenkonferensen Stockholm, Sweden 10. 11. November 2015 Andre de Bache Dr. Wolfgang Hater

30/11/2015 2 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

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 4

CETAMINE FILMING AMINE (CFA) R 1 - NH-R 2 - n -NH 2 R 1 is an unbranched alkyl chain with 12 to 18 carbon atoms R 2 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 6

FILM FORMATION ON METAL SURFACES Adsorption and Formation of a Protective Film on Metal Surfaces Hydrophobic Barrier between Water and Metal 3 3 2 2 1 1 1 1. Adsorption 2. Ion - ion 3. Hydrophobic bond

FILM FORMATION ON METAL SURFACES Metal Protective Film Molecules in water phase untreated Cetamine 8

MAGNETITE LAYER STABILIZATION UNIVERSITY OF ROSTOCK, GERMANY Traditional Treatment - high micro roughness - inhomogeneous surface Cetamine Treatment - low micro roughness - homogeneous surface Shell boiler simulation at university of Rostock at steady state conditions, p = 15 bar 9

MAGNETITE LAYER STABILIZATION UNIVERSITY OF ROSTOCK, GERMANY a) PO 4 15 um 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

1 MAGNETITE LAYER STABILIZATION PAPER INDUSTRY, ISRAEL Iron Oxide Layer Development in 90 bars Water-Tube Boiler, Paper Industry Acid pickling Acid pickling Internal limit at 500 g/m² Acid pickling Online cleaning Ammonia Phosphate FFA Treatment Cetamine V211 Cetamine V2100 1 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 X X ph YES YES X 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 Plant: Type of system: Fuel: Waste Inceneration Water-tube (CHP) 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 PLANT GENERAL FLOW SCHEME Return of condensate ca. 95 % 4 different condensates Feedwater EC1 EC2 EC3 DI-watertank Steam drum LP HP EDI Reversed osmosis Ion exchanger Town water Consumer Boiler SH3 SH2 SH1 Dosage of Cetamine V211

CETAMINE - WASTE INCINERATION PLANT STEAM PARAMETERS Steam on turbine VGB-S-010-T00 AL 1 Ø 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 --- SiO 2 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

conductivity [μs/cm] CETAMINE - WASTE INCINERATION PLANT DEGASSES CATIONIC CONDUCTIVITY 0,80 degassed acidic conductivity and CO 2 -contribution 0,70 0,60 0,50 0,40 0,30 0,20 acidic conductivity degassed acidic conductivity ΔCO 2 0,10 ca. 16 h 0,00 16:33 18:57 21:21 23:45 2:09 4:33 6:57 9:21 time [hh:mm]

LMWA Glycol Ethanolamine Ammonia Cyclohexylamine LC OCD Liquid Chromatography Organic Carbon Detection concentrations of organic compounds ppb C (carbon) concentrations of ammonia ppb N (nitrogen)

cationic conductivity / μs/cm CETAMINE - WASTE INCINERATION PLANT THEORETICAL COMPOSITION OF CATIONIC CONDUCTIVITY 1,0 0,9 0,8 0,7 0,6 0,5 0,4 0,3 0,2 0,1 0,0 Estimation of contribution of single components to cationic conductivity 0,58 cationic conductivity measured 0,06 0,12 0,12 0,16 0,18 single components calculated water amines LMWA 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 <10μm 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: Boiler pressure: Steam temperature: Steam capcity: Cycle chemistry: Condenser material: Condensate polishing unit: DI-water 144 bar 540 C (Superheater) 205 t/h AVT(O) (Ammonia) condensate ph: 8.8 steel, brass Ion exchanger 30

DRY LAY-UP WITH FILM FORMING AMINES WATER QUALITY ACCORDING TO VGB-S-010 Acid conductivity: Fe (AAS graphite tube): SiO 2 : approx. 0.1 µs/cm < 2 µg/l < 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 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 µg/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 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 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 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 Dose rate: 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 [µs/cm] Acid conductivity [µs/cm] O 2 [µg/l] SiO 2 [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 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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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 Web andre.debache@kurita.eu www.kurita.eu

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