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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 S/cm 7000 2700 500
(25 C) (6000a) (2000a)
Salinity mmol/ 60 18 3
L
Alkalinity mmol/ 2 - 10 1-5 0.1 1.0
(evident) L
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: mass concentration, c molar concentration
Fe concentration : total concentration FeII + FeIII in water, total concentration of soluble Fe II + FeIII in water, conc. of soluble Fe II 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.Fe 3O4)
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 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: g/L, C: g/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: 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
ef: 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
) water from the drum is re-circulated, preventing dryout at the boiling surfaces.
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.
ef: 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
Acidic and alkaline contaminants - important :
NaOH, hydrogen sulphates and chlorides at certain concentrations present a stress corrosion
cracking risk to steels, particularly with austenitic structures.
Salts deposited in steam pipework
-on-load can result in the development of concentrated solutions
- off-load following condensation of residual steam - significant for reheaters and feedheaters.
Organic impurities decomposition products (organic and carbonate anions) - may damage turbine.
Low volatility contaminants - turbine early condensation zone is particularly sensitive to surfaces
and in the very first droplets of condensate to form an aggressive environment.
Silica - the most soluble at high pressure steam of the common boiler water contaminants -
supersaturated during expansion in the turbine resulting in deposition on the blades causing loss of
turbine efficiency.
Water/Steam Quality Monitoring
Basic parameter monitoring in the operating water-steam cycle
H+ O2 Na
Conductiv Phospha Redox
Parameter conductivi pH concentr concent
ity te potential
ty . r.
1 Make-up
YES
water
2 Condensate YES YES YES
3 After
treatment YES YES
condensate
4 Degassing
YES
input water
5 Feed water YES YES YES YES
6 Blow-down YE
asic quantities of quality: YES
S
H+ conductivity - defines ion impurities concentration
7 Steam
Na concentration YES
defines alkalinity and conductivity YES
pH measurement monitoring important for solid alkalization agents and for presence of Cu alloy mat
RedOx potential hydrazine alkalization agent monitoring
ef.: Pavel Hbner, Water treatment in heat-power engineering, VSCHT Prague, 2010 (cz), ISBN 978-80-7080-746-0
Guidelines for continuous operation and for plant
start-up
Chemistry out of Component failure. The unit should be shut down within 1 hour using
control. the normal shut down procedure if one of the key
parameters deteriorate to action level 3. If one of the
AL 3 diagnostic parameters deteriorates to this action
level, reduce load to prevent immediate damage and
to gain time to restore chemical control.
ef: 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
ef: 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
ef: 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 :
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
Index Ip - related to the selected Action levels is defined:
for L1 < P L2
for L2 < P L 3
for P > L3
Ip = index for parameter p, P = monitored value for parameter P,
L1 = threshold for AL1, L2 = threshold for AL2, L3 = threshold for AL3
Ref: Chemical guidelines for water/steam cycle of fossil fired units, Union of the Electricity Industry -
EURELECTRIC, 2000
Example of lifetime evaluation