Boiler Water Chemistry
Boiler Water Chemistry
Boiler Water Chemistry
Cations
Sodium Na+
Potassium K+
Calcium Ca2+
Magnesium Mg2+
MINERALS AIR EARTH
Ammonium NH4+
Iron Fe2+
Manganese Mn2+
Anions
Bicarbonate HCO3- Cations Oxygen Clay
Chloride Cl- Anions Carbon Monoxide Silt
Sulphate SO42-
Nitrate NO3-
Carbon Dioxide Sand
Silicate HSiO3-
ACIDIC BASIC
1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
Hydrogen Ions (H+) decrease pH; Hydroxyl (OH-) increase pH
Water Characteristics and quality
Three battles
20
Efficiency Loss in %
18
16
14
12
10
8
6
4
2
0
0.4
0.8
1.2
1.6
2.4
2.8
3.2
4.4
4.8
3.6
0
4
Deposit in mm
Increased
wall T4
Wall T2 Wal T2
T3
Resulting
boiler
water T0
A B C
Clean internal heat Scaled surface Scaled surface
transfer surface. resulting in lower T0 Fire side T2 is increased
T1 for needed while needed T1 to T4 to reach water T1
steam production T3 is critical for metal
structure
Deposition
Effect of scale on heat transfer
240 115
120
e)
at
li c
200 te 95
si
Tube metal temperature increase
100 ha
um
o sp
ph
in
um
um
Temperature [°C]
160 si 70
al
80 ne
ag
m
M ide
u
perature[°F]
ox
di
n
iro
o
120 50
(s
c
60 eti
gn
e
Ma te
t
a
sph
ci
p ho
al
An
80 ium
Tem
l c 25
40 Ca
40 5
20
0 0
0 0.002 0.004 0.006 0.008 0.01
Deposit thickness [mm]
Deposition
Factors
Most materials
are more soluble
Soluble at increasing
Amount temperature
Temperature
Deposition
Boiler deposits
Name Formula
Acmite Na2O·Fe2O3·4SiO2
Analcite Na2O·Al2O3·4SiO2·2H2O
Anhydrite CaSO4
Brucite Mg(OH)2
Copper Cu
Cuprite Cu2O
Hematite Fe2O3
Hydroxyapatite Ca10(PO4)6(OH)2
Magnetite Fe3O4
Tenorite CuO
Thenardite Na2SO4
Definition
• The deterioration of a material by the interaction with
it’s environment
Impact
• Feedwater piping
• Feedwater heaters
Oxygen corrosion in flame • Economizer
pipe (6 bar boiler)
• Boiler
• Condensate system
•…
Corrosion
Problems caused
Natural passivation:
• Formation of a protective barrier on metal surface by
reaction with water
Fe + 2 H2O Fe(OH)2 + H2
3Fe(OH)2 Fe3O4 + H2 + 2H2O
• Black magnetite film - Fe3O4
• Rate of Magnetite formation is
– Temperature dependent
– Spontaneous above 180 °C (360 °F)
• Reduces general corrosion
• Difficult to quantify results
Oxygen scavenging
Metal passivation
SHIKORR REACTION
T < 180 °C
• 3 Fe + 6 H2O 3 Fe(OH)2 + 3 H2
T > 180 °C
• 3 Fe + 4 H2O Fe3O4 + 4 H2
Corrosion
Solubility of magnetite in water
Corrosion
Effect of pH
Do we have a
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picture ??
Check
advanced
training
series
Corrosion
Types
Types of Corrosion
• Oxygen corrosion
• Alkalinity concentration
• Caustic corrosion
• Acid corrosion
• Chelant corrosion
• Erosion/Corrosion
CATHODE ANODE
Electron transport
5.5 ppm O2
2.5 ppm O2
50°C 85°C
(122 °F) (185 °F)
Corrosion
Oxygen Corrosion
Oxygen corrosion in
feed water line
Corrosion
Oxygen Corrosion
• Localized in boiler
• Also called crater attack or caustic gouging
• No embrittlement of metal
Corrosion
Caustic Embrittlement
Steam blanketing
Steam Out
NaOH
NaOH
Water In
NaOH
NaOH
Corrosion
Concentrating Mechanisms
Causes of acidity
• Feedwater acid contamination
• Acid leaks from demineralizer, e.g. acid regenerant
• Breakdown of organic materials
• Condenser leaks
– MgCl2 + 2 H2O Mg(OH)2 + 2 HCl
• Organic chlorides
– R-X + 2 H2O R-OH + HCl
Corrosion
Acid corrosion
% Conversion
Check
Etienne – TDS (max) 4000 3500 3000 2000 500 300
source??? Phosphate
(as PO4)
30-60 30-60 20-40 15-20 10-15 5-10
Total Iron 10 5 3 2 2 1
(as Fe. max)
Different for all boiler types. feed water quality and region
•ASME: USA
•Krachtwerktuigen: Holland
•TUV: Germany
•British Standard: UK
Water quality guidelines
High purity Feed water
Upto 600 900 (60) 120 (80) 1500 (100) 1800 (120) 2400 (160)
(40)
Check
Etienne –
source???
TDS (max) 500 500 300 200 100 50
Different for all boiler types. feed water quality and region
•ASME: USA
•Krachtwerktuigen: Holland
•TUV: Germany
•British Standard: UK
Water quality guidelines
general remarks
Water tube
Fire tube
Feedwater
Total Hardness [°F] < 0.5 < 0.2 < 0.2 < 0.1
Boiler water
Total dissoloved [Mg/L] < 4000 < 3000 < 2000 < 1500
solids
Feedwater
Boiler water
TAC [°F] ≤ 25 ≤ 10 ≤5
Silica [Mg/L] ≤ 15 ≤ 10 ≤5
Phosphate [Mg/L] 10 - 60 10 - 40 5 – 20
pH 10 - 11 10 - 11 9.5 – 10.5
Feedwater Quality requirements
France – Fire tube boilers
Operating bar ≤ 10 10 - 15 15 – 25
pressure
Feedwater
Boiler water
Conductivity (25 °C) [uS/cm] < 0.25 < 50 < 50 < 5 (for < 250 kW/m2) < 0.2
< 3 (for > 250 kW/m2)
Oxygen [mg/l]
Neutral operation 0.050 - 0.250
Combined operation 0.030 – 0.150
Alkaline operation < 0.100
Iron [mg/l]
Scope Softened Boiler water on softened feedwater Demin. Boiler water based on
feedwater feedwater demin. feedwater
Pressure area [bar] 1 <> 68 1 <> 22 22 <> 44 44 <> 68 < 68 < 68 < 68
Conductivity (25 °C) [µS/cm] < 10,000 < 5,000 < 2,500 < 0.2 < 150 <3
Scope
Appearance
Oxygen ppm
Phosphate [mg/l ]
PH (25 °C)
Iron ppm
Copper Ppm
Silica [mg/l]
Oil ppm
Boiler water Quality requirements
Spain – Firetube: UNE 9-075-92
≤ 0.5 bar > 0.5 bar ≤ 0.5 bar 0.5 <≥ 13 bar > 13 bar
Oil ppm ≤3 ≤1
Parameters
Krachtwerktuigen KEMA
TDS
Demineralized feedwater
Oxygen Mg/kg
Is there an Total M-alkalinity Mg/kg CaCO3 ≤ 1000 ≤ 100
update, have O- and P-alkalinity Mg/kg CaCO3 ≥ 350 ≥ 20
seen the Oil and grease Mg/kg ≤1
draft! Oxygen scavenger Mg/kg
Sulfite, or 30 – 70 Assess
Hydrazine, or 0.1 – 1.0 0.1 – 1.0
Tannin, or 120 – 160 Assess
Iso ascorbic acid, or 15 – 30 Assess
DEHA 0.1 – 1.0 (FW) 0.1 –1.0 (FW)
Phosphate Mg/kg 30 – 60 10 – 30
Feedwater
pH (25 °C) 8.5 – 9.5 8.5 – 9.5 8.5 – 9.5 8.5 – 9.5 8.5 – 9.5 8.5 – 9.5 8.5 – 9.5
Fe, Cu, and Ni Mg/kg ≤ 0.05 ≤ 0.05 ≤ 0.03 ≤ 0.02 ≤ 0.02 ≤ 0.02 ≤ 0.02
Boiler water
Feedwater
pH (25 °C) 9.3 – 9.8 9.3 – 9.8 9.3 – 9.8 8.5 – 9.5 8.5 – 9.5 8.5 – 9.5 7.5 – 9.5
Fe, Cu, and Ni Mg/kg ≤ 0.05 ≤ 0.03 ≤ 0.02 ≤ 0.005 ≤ 0.02 ≤ 0.2
Cond ≤ 400
Boiler water
Silica Mg/kg ≤ 20 ≤5 1-5 ≤ 0.02 < 0.4 X O&P alk < 0.4 X O&P alk
Conductivity (25 °C) uS/cm ≤ 2000 ≤ 400 ≤ 100 ≤ 0.2 400 – 2000
Boiler water Quality requirements
UK – Fired Water tube
Feedwater
Parameter Unit 0 - 20 21 – 40 41 - 60 61 - 80 81 - 100 101 - 120 ≥ 121
pH (25 °C) 8.5 – 9.5 8.5 – 9.5 8.5 – 9.5 8.5 – 9.5 8.5 – 9.5 8.5 – 9.5 8.5 – 9.5
Fe, Cu, and Ni Mg/kg ≤ 0.05 ≤ 0.05 ≤ 0.03 ≤ 0.02 ≤ 0.02 ≤ 0.02 ≤ 0.02