Measurements used for assessing feed

water and boiler water quality and their

effect on boiler efficiency and lifetime
Dr. Dusan Kordik,
Office of Standardization Metrology and Testing,
Slovak Republic, Bratislava, Slovakia
E-mail: dd.kordik@gmail.com
 Concept of water treatment

Steam generator and heating systems :

Factors influencing heating system operation:
Correct selection of construction materials in steam circuit
Treatment of made-up water
Optimized chemical treatment
Design, quality of construction and operation process

Feed water = condensate flux in the system +made-up water to compensate

losses
Refluxed condensate:
Heat power plant over 70 %
Power stations with condensing steam turbine- over 97%
Made-up water pretreatment
Physical (sedimentation, filtration, steam degassing)
Chemical (demineralization, alkalization, degassing
 Objectives of chemical control of the
water/steam circuit
The objectives of chemical control are to minimize:
corrosion damage and
deposition on the internal surfaces of water/steam circuit as far as is economically prudent:

The basic principles involved in minimizing corrosion and deposition are:

a) minimization of the ingress of impurities into the water/steam circuit.
b) Redox potential control to stabilize oxide films and to minimize transport of metal oxides
(control of oxygen).
c) pH control of the to counter corrosion effects, to stabilize oxide films and to minimize
transport of metal oxides.

Control of the corrosion and deposition processes areas:

Feed-water and condensate system
Boiler
Turbine and steam circuits

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 S 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) S/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)

Notes: a) For neutralized samples, b) for power plant steam generators

 Methods to asses the feed water
parameters
Range of
ISO Water Quality standards Code Method Measure
application
Determination of the sum of calcium and ISO 6059, titration
1 magnesium. EDTA titrimetric method. extend of decarbonization
ISO 7980 AAS
Determination of iron. Spectrometric method
2 using 1,10 Phenantroline ISO 6332 spectrometry (0.1 - 5.0) mg/L residuals after coagulation

Determination of alkalinity. Part 1:

3 Determination of total and composite alkalinity EN ISO 9963-1 titration (0.4 - 20) mmol/L level of alkalinity

Determination of Cobalt, Nickel, Copper, Zinc,

4 Cadmium and Lead. Flame AAS method. ISO 8288 AAS dissolution of metals, corrosion

Determination of Phosphorus. Part 1: residuals of hardness removal and

5 Ammonium molybdate spectrometric method. ISO 6878-1 spectrometry
passivation
Determination of Sodium and Potassium. Part
6 1: Determination of Sodium by AAS. ISO 9964-1 AAS (5 -50) mg/L alkalization

Determination of Sodium and Potassium. Part

7 2: Determination of Potassium by AAS. ISO 9964-2 AAS alkalization

8 Determination of pH. ISO 10523 pH-metry 2.0 - 12.0 corrosion

Determination of dissolved oxygen.

9 Electrochemical probe method. ISO 5814 ISE (1-100)% of satur. corrosion

Ionized inorganic and organic compounds

10 Determination of electrical conductivity ISO 7888 condutometry
(cations + anions)
Guidelines for the determination of total
11 organic carbon (TOC) and dissolved organic ISO 8245
carbon (DOC)
 Quantities of water quality
Electrolytic conductivity:
Symbol
Conductivity of 1m3 (water) between two parallel electrodes of 1 m 2 area, distant 1m one from the other.
SI unit = S m-1, in analysis of water mS m-1 , S cm-1 (1 S cm-1 = 0.1 mS m-1)
Measuring instrument: conductivity meter, calibrated with solution of KCL + electrolytic cell
Parameter of quality: approximate measure of electrolyte in water, highly temperature dependent: 1C

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.)

Calcium and magnesium content

Symbol: mass concentration, c molar concentration
Total Ca and Mg concentration form of carbonates hardness of water (historic name)
SI unit: mg / L-1, mmol / L-1
Measuring instrument: burette for titration method, AAS spectroscopic method
Parameter of quality: stability of water equilibria of H2CO3, HCO3-, CO32-, Ca2+, H+, OH- , aggression, corrosion, incrusts and sediment
deposits

Iron
Symbol: 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 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

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

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 Redox
Parameter Conductivity pH Phosphate
conductivity concentr. concentr. potential
1 Make-up water YES
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
YES
S
7 Steam YES YES
Basic quantities of quality:
H+ conductivity - defines ion impurities concentration
Na concentration defines alkalinity and conductivity
pH measurement monitoring important for solid alkalization agents and for presence of Cu alloy materials
RedOx potential hydrazine alkalization agent monitoring
Ref.: 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
The guidelines recommend conditions for both continuous operation and for
plant start-up.
Target range - no action required; this range covers the practicable values
which plant managers will
normally achieve without excessive cost.
Action level 1 (AL 1) - minor disturbance requiring investigation, diagnosis and
optimization.
Action level 2 (AL 2) - serious disturbance in chemical control requiring
diagnosis and action to eliminate the cause.
Action level 3 (AL 3) - very serious disturbance requiring substantial operator
intervention, such as load reduction, or plant shut-down.
 Definitions and characteristic of Action Levels

Action Action during operation

Characterization Risk
level (specific actions on condensate)
Normal stable operation, The maintenance of chemical control through the
Target where everything is monitoring of key parameters should be continued.
under control
Periodic or minor Long term damage and Monitoring of the circuit chemistry should be
disturbances in chemical reduction in remaining extended to diagnostic components to identify the
AL 1 control. life of power cycle source of the problem. Strategic considerations
components. should be made to avoid similar occurrences in the
future.
Serious loss of chemical Serious damage to Immediate action should be taken to find and
control. components due to eliminate the cause within hours and/or actions
deposition and should be taken to minimize the damage (e.g.
AL 2
corrosion. Significant decrease load).
reduction in the
component life
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.

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

Circuit Sampling point Conditioning Key parameter

Drum Boiler Boiler Water- AVT Conductivity after cation exchange

Drum Boiler Boiler Water NaOH Conductivity after cation exchange

Specific conductivity or pH
Drum Boiler Boiler Water Phosphate Strong mineral acids and pH

Drum Boiler Feed-water AVT pH

Once through boiler Feed-water All Conductivity after cation exchange

All Steam All Conductivity after cation exchange

and sodium

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 :

= /1
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
1
= 0 = =1
1
Lifetime consumption at actual conditions Tp of defined component during operation
period t

=
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

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

operation mode (1. base load, 2. cycling load,

3. peak
load)

A. Ideal purity, B. Good practice, C. Unattended control

Operation mode = 1. base load, 2. cycling load, 3. peak load
Ref: Chemical guidelines for water/steam cycle of fossil fired units, Union of the Electricity Industry - EURELECTRIC, 2000