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Measurements of Feed Water FF
Measurements of Feed Water FF
Ref: Chemical guidelines for water/steam cycle of fossil fired units, Union of the Electricity Industry - EURELECTRIC, 2000
EN 12952 - Water tube boilers and auxiliary
installation
EN 12952-12: Requirements for boiler feed water and boiler water quality
Demineralised
Feed water
Parameter Unit and Injection
with concentration of salts Water
Pressure MPa 0.05 – 2.0 0.05 – 4.0 4.0 - 10 Full range
H+ conductivity μS cm-1 - - - < 0.2
pH at 25 °C★ > 9.2 > 9.2 > 9.2 > 9.2
Concentration of Ca + Mg mmol L-1 <0.02 <0.01 <0.005
Concentration of of Na + K mg L-1 - - - < 0.010
Concentration of Fe mg L-1 < 0.05 < 0.03 < 0.02 < 0.020
Concentration of Cu mg L-1 < 0.02 < 0.01 < 0.003 < 0.003
Concentration of SiO2 mg L-1 - - - < 0.020
Concentration of O2 mg L-1 < 0.02 < 0.02 < 0.02 < 0.1
Conc. of oil and grease mg L-1 < 1.0 < 0.5 < 0.5 < 0.5
Organic comp. TOC mg L-1 < 0.5 < 0.2
★) Note: for Cu alloys pH should be limited to 8.7 – 9.2
EN 12952-12: Requirements for boiler feed
water and boiler water quality
CSN 07 7401: Water and steam for heating and power plants – pressure < 8 MPa
Pressure [MPa]
Parameter Unit
0.15 – 2.5 2.5 – 6.5 6.5 – 8.0
Conductivity (25 °C) μS/cm 7000 (6000a) 2700 (2000a) 500
Salinity mmol/L 60 18 3
Alkalinity (evident) mmol/L 2 - 10 1-5 0.1 – 1.0
Soluble P2O5 mg/L 10 - 30 5 - 12 2 - 10
SiO2 mg/L 70 40 (20b)
pH
• pH = -log a (H3O+) or activity a (H3O+) = 10-pH e.g. pH 9 activity (conc.) of H+ = 10-9 mol/kg
• SI unit: non-dimensional parameter
• Measuring instrument: pH-Meter – voltage between measuring electrode (e.g. glass) and reference electrode
• Parameter of quality: acidity rate of water influencing reactions between ions in water, stability or aggression of water (corrosion, incrusts
deposits etc.)
Iron
• Symbol: ρ – mass concentration, c – molar concentration
• Fe concentration : total concentration FeII + FeIII in water, total concentration of soluble FeII + FeIII in water, conc. of soluble FeII in water
• Measuring instrument: VIS spectrometer + color of sample with chemical agent – measurement at 510 nm wavelength
• Parameter of quality: immunity, corrosion or passivation of material (e.g.Fe3O4)
Quantities of water quality
Alkalinity
• Alkalinity– capability of water media to react wit H+ ions- depends upon final pH value
(ACN4.5) - total alkalinity = c(OH-) + c(HCO3-) + 2(CO32-) – c(H+) + c(A-)
(ACN8.3) - composite alkalinity= c(OH-) + c(H2 CO3) + (CO32-) – c(H+) + c(A-)
(ACN10.6) – caustic alkalinity= c(OH-) - c(HCO3-) - 2c(H2 CO3) – c(H+) + + c(A-)
• Symbol: ANC, BNC ρ – mass concentration, c – molar concentration
• SI unit: mg / L-1, mmol / L-1
• Measuring instrument: burette for titration method
• Parameter of quality: pH value in alkaline region, passivation of the boiler, tubes and pipelines material
Copper, Cobalt, Nickel, Zinc, Cadmium and Lead
• Cu, Co, Ni, Zn, Cd, Pb – concentration in 3 different ranges A: mg/L, B: μg/L, C: μg/L
• Measuring instrument: flame AAS spectrometry Co (240.7 nm), Ni (232.0 nm), Cu (324.7 nm) , Zn (213.8 nm),
• Cd (228.8), Pb (283.3 nm, 217.0 nm)
• Parameter of quality: measure of copper and copper alloys corrosion or passivation - with phosphate = solids e.g.
Cu3(PO4)2, Cu2(PO4) OH, Cu3(PO4) (OH)3 – anticorrosive layers in Cu tubes – solubility depends upon pH value
Dissolved oxygen
• Symbol: ρ – mass concentration, c – molar concentration
• Measuring instrument: potentiometer with O2 electrode
• Parameter of quality: concentration of oxygen in combination with pH, protective magnetite layer formation,
reduction of Fe content in water
Chemical systems for conditioning feed-water
systems
Chemical systems for conditioning feed-water fall into two groups:
Reducing (ammonia or an amine with hydrazine)
• (AVT) - All Volatile Treatment, in which:
• protection steel is based on low solubility of iron oxides at elevated pH
Oxidizing (oxygen with a low concentration of ammonia)
• (OT) treatment, in which:
• very low anion concentrations (low acid conductivity),
• protection of steel - based on low solubility of iron oxides at elevated oxidation-reduction potential.
Limited concentration range vs. experience indicates:
• two protection mechanisms act simultaneously
• no distinguished border lines between these types of conditioning.
• continuum of suitable operation conditions in a broad range with high pH and low oxygen concentration at one
end, and low pH and high oxygen concentration at the other.
• achievable purity of feed-water determines the degree of freedom available to operators within this range
Ref: Chemical guidelines for water/steam cycle of fossil fired units, Union of the Electricity Industry - EURELECTRIC, 2000
Chemical systems for conditioning feed-
water for boilers
Two general classes of boilers in use:
A) Once through boilers in which water is evaporated to a high steam content.
• not tolerant of nonvolatile dosing chemicals and
• operate without further dosing downward the feedwater chemical dosing.
B) Drum boilers in which steam separation takes place in an unheated vessel.
• boiling occurs in tubes
• water from the drum is re-circulated, preventing dryout at the boiling surfaces.
• boilers may be tolerant of addition of low levels of non-volatile alkalis to prevent any risk of acidic
corrosion.
Note: During initial operation or post chemical cleaning, the boiler steel reacts with the water and
steam forming a protective film of iron oxides. The rate of reaction decreases with time as the
thickness of the protective oxide film increases.
Ref: Chemical guidelines for water/steam cycle of fossil fired units, Union of the Electricity Industry - EURELECTRIC, 2000
Chemical systems for conditioning feed-water for
turbine, superheater and reheater
Steam purity - high - actual quality is determined by:
• concentration and solubility of salts in steam ( function of pressure, temperature and other chemicals)
• droplets of boiler water carried over from water
• contaminated feed-water injection into steam
Ref: Chemical guidelines for water/steam cycle of fossil fired units, Union of the Electricity Industry - EURELECTRIC, 2000
Key parameters for control of
water/steam cycle
Ref: Chemical guidelines for water/steam cycle of fossil fired units, Union of the Electricity Industry - EURELECTRIC, 2000
pH and oxygen values in feed water
pH vs. oxygen concentration defined by the Union of the Electricity Industry –
EURELECTRIC in the year 2000 for the feed water for Cu-free and Cu-alloys circuits
Ref: Chemical guidelines for water/steam cycle of fossil fired units, Union of the Electricity Industry - EURELECTRIC, 2000
Action Levels limit parameters for acid
conductivity
Ref: Chemical guidelines for water/steam cycle of fossil fired units, Union of the Electricity Industry - EURELECTRIC, 2000
Action levels for pH – boiler water
pH vs. solid alkaline concentration defined for Action Levels by the Union of the Electricity
Industry – EURELECTRIC in the year 2000 for the boiler feed water and solid alkalizer
Ref: Chemical guidelines for water/steam cycle of fossil fired units, Union of the Electricity Industry - EURELECTRIC, 2000
Assessment of water/steam chemistry by
quality indices
Union of the Electricity Industry – EURELECTRIC proposed QUALITY INDEX „I“ for
any control parameter „ p“ defined as :
𝐼𝑝 = 𝑑𝑇𝑃 /𝑑𝑇𝐿1𝑝
Ip – relative rate of component consumption normalized to operation at the limit for AL 1.
Tp – lifetime consumption of the component at the actual operating parameter
Tp – lifetime consumption of the component at the reference conditions
𝑑𝑇𝐿1𝑝
𝐼𝑝 = 𝐼0 = =1
𝑑𝑇𝐿1𝑝
Lifetime consumption at actual conditions Tp of defined component during operation
period t
𝑡
𝑇𝑝 = න 𝐼𝑃 ∗ 𝑑𝑡
0
Ref: Chemical guidelines for water/steam cycle of fossil fired units, Union of the Electricity Industry - EURELECTRIC, 2000
Assessment of water/steam chemistry by
quality indices
The exponential function is normalized for action level limits defining:
• at P = L1p I=1
• at P = L2p I = 10
• at P = L3p I = 100
• at P = 3xL3p I = 1000
for L1 < P ≤ L2
for L2 < P ≤L 3
for P > L3
Ref: Chemical guidelines for water/steam cycle of fossil fired units, Union of the Electricity Industry - EURELECTRIC, 2000
Example of lifetime evaluation