Boiler Water Training PDF

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Water & Process Technologies
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Boiler Technical Training

At
Reliance Industries Limited
Hazira Manufacturing Division
K S Rajan
RIL-Hazira/BWT-Technical Training
GEWPT- Confidential Material
February 26, 2008
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BOILER WATER TREATMENT
BASIC WATER CHEMISTRY

BOILER DESCRIPTION
OXYGEN PITTING & CONTROL
CONDENSATE TREATMENT
INTERNAL TREATMENT, COORDINATED
pH/PO4
STEAM PURITY
BOILER STORAGE
DISCUSSION, Q&A
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Basics & Interpretation of Water Analysis
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The Basics
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Hydrologic Cycle
Properties of Water
pH and Alkalinity
Langelier Saturation Index
Analytical Expressions
Water Analysis/Deposit Analysis
Corrosion and Deposition & Monitoring
Chemical Feed
Properties of Water
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Density - 1 kg/l @ 4 oC ; 0.998 kg/l @ ambient temperature and

varies inversely with temperature
Boiling point = 100 oC and freezing point @ 0 oC
Viscosity ~ 1 cps at ambient temperature and varies inversely
with temperature
Specific heat - 1 BTU/lb-deg F or 1 kcal/kg-deg C or 4.2 kJ/kgdeg C
Universal solvent - dissolves most substances to some extent
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Impurities found in Water
3 Categories
SUSPENDED SOLIDS (Silt)
DISSOLVED SOLIDS (Minerals)

DISSOLVED GASES
Where do these things come from?

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Hydrologic
Cycle
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Impurities found in Water
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Dissolved solids present as ions
Cations - Ions that carry net positive charges e.g. Calcium (Ca2+), Magnesium
(Mg2+), Sodium (Na+), Iron (Fe2+), Aluminium (Al3+)
Anions - Ions that carry net negative charges e.g. Bicarbonates (HCO3-),
Carbonates (CO32-), Sulfate (SO42-), Chlorides (Cl-), Oxides (O2-), Hydroxides (OH-)
Water Impurities
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Impurity
Concern
Removal
Suspended Solids
Silt, Iron,
Microbiogical
Fouling
Erosion
Underdeposit corrosion
Clarification
Filtration
Dissolved Solids
Minerals,
Organics
Scaling
Corrosion
Ion Exchange
Reverse Osmosis
Evaporation
Dissolved Gases
O2, CO2, NH3
Pitting
General Corrosion
Corrosion products
Deaeration
Steam Stripping
Dissolved Solids
Cations
Temporary
Hardness
Ca++
Anions
Mg++
Permanent
Hardness
HCO3possibly OH- & CO3-Cl-
Na+
K+
NH4+
F-
NO3- PO4 --SO4--
SiO2, possibly free CO2

Organic acids
Total
Alkalinity
Mineral
Acidity
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Dissolved Solids Commonly Found in Water
Cation
Anion
Calcium
Bicarbonate
Sulfate
Ca(HCO3)2
CaSO4
Magnesium
Bicarbonate
Sulfate
Mg(HCO3)2
MgSO4
Sodium
Bicarbonate
Sulfate
Chloride
NaHCO3
Na2SO4
NaCl
Silica
Oxide
SiO2
Iron
Bicarbonate
Hydroxide
Sulfate
Fe(HCO3)2
Fe(OH)3
FeSO4
Chemical Name
Factors Affecting Solubility
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Temperature - Most salts increases except for Ca and Mg Salts

with increasing temperature
Alkalinity - Most salt solubility increases with decreasing
alkalinity with the exception of Silica
pH - most salts solubility increases as the pH drops
Oxidation state - Fe and Mn salt solubility increases with
decreasing oxidation state
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Impurities found in
Water
Turbidity - suspended solids

silt, organic matters, precipitated
salts
Color - suspended solids and
dissolved solids
Dissolved gases e.g. CO2, O2, NH3,
H2S
Organics - humus, vegetation, microorganisms
Typical Water Analysis
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Parameter
Value
pH
7.3
150
0
20
15
10
20
15
5
0.05
1.5
12
<0.05
4
50
20
3
1
Conductivity S/cm
Alkalinity P as CaCO3, ppm
Alkalinity M as CaCO3, ppm
Sulfate as SO4, ppm
Chloride as Cl, ppm
Hardness, Total, as CaCO3, ppm
Calcium Hardness, as CaCO3, ppm
Magnesium Hardness, as CaCO3 ppm
Copper, Total as Cu, ppm
Iron, Total as Fe, ppm
Sodium, as Na, ppm
Phosphate, Total, as PO4, ppm
Silica (reactive), as SiO2, ppm
Turbidity, NTU
TSS, ppm
Color, Hazen
RIL-Hazira/BWT-Technical
Training
TOC, as C, ppm
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Special Ions
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pH
Hydrogen, H+
Hydroxide, OH-
Alkalinity
Bicarbonate, HCO3 Carbonate, CO3- Hydroxide, OH-
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pH
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Hydrogen Ion Concentration

Logarithmic Scale
pH = -log [H+]
Unit change in log scale
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How Does pH Apply

to Us?
pH < 7: Acidic (corrosion)

pH > 7: Alkaline (deposition)
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Alkalinity
Relationships
M-Alkalinity = Total
Titration to pH = 4.3
Sum of: HCO3- + CO3- + OHP-Alkalinity = OH- + 1/2 CO3 Titration to pH 8.3
OH-Alkalinity = 2P - M or titration
Neutral barium chloride precipitates CO3-
Conductivity
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Inverse of Resistance [mho]

Measure of concentration of ions in solution
Types of Solubility
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Normal: Increases with Temperature

Table Salt (NaCl)
Sugar
Retrograde: Decreases with

Temperature
Calcium Carbonate
Calcium Phosphate
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How Do We Quantify What Is in the Water?
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Concentration
units of solute per unit of solvent:
PPM (parts per million)
mg/l (milligrams per liter)
parts of solute per million parts of

solvent
1 gram solute/1,000,000 grams
solvent
PPB (Parts Per Billion)
parts of solute per Billion parts of solvent
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Mg as CaCO3
Magnesium expressed as its Equivalent weight

in Calcium Carbonate
100 (MW CaCO3) = 4.1
24 (MW Mg)
Analytical
Expressions
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Different Conventions
We use ppm as CaCO3
ppm
as substance factors
Ca
50
2.5
Mg
20
4.1
ppm
as CaCO3
125
82
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Boiler
Boiler Descriptions
Descriptions
FIRETUBE BOILERS
ADVANTAGES
High load swing capacity
Ease of repair
Low space requirement
Self contained package
Relatively low cost
Ease of installation
DISADVANTAGES
Low pressure
Capacity limit
Usually no superheater
Usually no economizer
Usually low efficiency
One fuel at a time
FOUR-PASS FIRETUBE BOILER
WATERTUBE BOILERS
Typical Parts of a
Water Tube
Boiler Includes:
Economizer
Steam drum
Mud Drum
Headers
Boiler Bank
Downcomers - Risers
Waterwalls
Screen tubes
Arches
Floor tubes
Roof tubes
Superheater
Air Heater
WATERTUBE BOILERS
RISERS
SUPERHEATER
DOWNCOMERS
STEAM
DRUM
SCREEN TUBES
ECONOMIZER
WATER WALLS
AIR HEATER
MUD
DRUM
Coal
140-150 C
To stack
BOILER DESIGN
Lower Water
Walls Header
Comparison - Watertube vs. Firetube:

Water Tube
Fire Tube
Steam
Feedwater
Steam
Drum
CBD
Risers
Flue
Gases
Mud
Drum
Downcomers
IBD
Water
Flue
Gases
WATERTUBE BOILERS
ADVANTAGES
Low to super critical

pressure
z Virtually unlimited capacity
z Typically high efficiency
z Superheaters
zEconomizers
z Multiple fuels
z Drum or once-through
z Package or field-erected
DISADVANTAGES
z High Cost
Require Large Space

z Usually require higher quality
feedwater
z Sensitive to low load operation
z
WATERTUBE BOILER: A-TYPE
Risers
Steam Exit Drum
W
BF
Downcomers
Burner
Flue
Gas
Path
Sidewall Problem
Area
Steam Drum
D-Frame
Package Boiler
Downcomers
Furnace Wall
Tubes
Risers
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Babcock & Wilcox
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Coal FiredMore
Boiler
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Power Utility Boiler
Simplified Flow Diagram
Hot Reheat
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HP Turbine
HP SH Steam
Sat Steam
Condenser
IP Turbine
LP Turbine
B&W Boiler
BD
Cold Reheat
LP Heaters
Cond Polisher
HP Heaters
Deaerator
BFW
MB MU
CAUSE AND EFFECT DIAGRAM FOR BOILER PROBLEMS

POOR pH CONTROL
OXYGEN PITTING
POOR CHEMICAL
FEED CONTROL
INADEQUATE
BLOWDOWN
CONTROL
OXYGEN
IN-LEAKAGE
MECHANICAL
DEAERATOR
PERFORMANCE
DOWNTIME
CORROSION
POOR BOILER
FEEDWATER
QUALITY
SCAVENGER
UNDERFEED
CONDENSATE
CONTAMINATION
DOWNTIME
CORROSION
POOR
EXTERNAL
TREATMENT
BOILER
CORROSION
POOR BOILER
FEEDWATER
QUALITY
CONDENSATE
CONTAMINATION
POOR EXTERNAL
TREATMENT
INADEQUATE
BLOWDOWN
CONTROL
STRESSED
AREA
CONCENTRATING
MECHANISM
POOR CHEMICAL
FEED CONTROL
EMBRITTLING WATER
CHARACTERISTICS
DEPOSITION
STRESS CORROSION CRACKING
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Boiler Calculations
FeedWater = Steam + Blowdown

% Blowdown =
1 X 100
Cycles
FeedWater (kg/hr) = Steam Generation (kg/hr)

1 (%blowdown)
100
FW= STM ( C )
C-1
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Determining Cycles of Concentration
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Feedwater vs. Boiler Water analysis

BFW Cycles = [Boiler Conc.] / [FW Conc.]
Cycles =
Neutralized Boiler Water Cond. (umhos at 25C)

___________________________________________
Feedwater Cond. (umhos at 25C)
Check via Chlorides, Silica
Do not use compounds that routinely precipitate (phosphate,

hardness) or that are part of treatment (sulfite/sulfate)
Demineralized or RO make-up Tracer methods

Molybdate
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Steam, Feed Water & Blowdown Relationships
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% Blowdown = 100 / FW Cycles

% BD at 20 FW cycles = 100/20 = 5%
Feedwater = Steam X [Cycles / (Cycles 1)]

FW = 100 MM ppy steam X [20 / (20 1)] = 105.3
Feedwater = Steam + Blowdown

BD = FW ST = (105.3 100) MM ppy = 5.3 MM
ppy
Feedwater = Make-up + Condensate
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Oxygen Control
Deaeration
Chemical treatment
Corrosion of Iron by Oxygen
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O2
Fe(OH)3
Fe2+
OH-
O2
WATER
ELECTRON FLOW
ANODE
CATHODE
ANODE REACTION
Fe. = Fe++ 2e-
CATHODE REACTION
1/2 O2 + H2O + 2e- = 20H-
MECHANISM
Iron Is Oxidized on the Surface (Anode) - Metal Loss

Oxygen Is Reduced (Cathode)
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Oxygen Corrosion
Corrosion Rate Doubles With Every
10 C Increase in Water Temperature
Metal Loss is low
Localized attack
Pit Formation
Rapid Failure
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Rapid Perforation ~ Equipment Failure
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Oxygen Guidelines
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Organization
Dissolved O2 Level, ppb

ASME
<7
TAPPI
<7
ABMA
NO RECOMMENDATION
EPRI
<5
DEAERATOR
GUARANTEE
TYPICAL DEAERATOR
O2 LEVELS
15 - 40
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Types of Oxygen Scavengers

Solid
Sodium Bisulfite
Sodium Sulfite
Non-Solids
Hydrazine
Hydroquinone
Diethylhydroxlamine (DEHA)
CARBOHYDRAZIDE
ASCORBIC ACID
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RECOMMENDED
SULFITE CONTROL LIMITS
Residual (ppm SO3-)

30 - 60
10 - 20
Pressure
< 40 bar
40 - 60 bar
ATTEMPERATION / DESUPERHEATING: NO
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Hydrazine
Reaction:
N2H4 + O2
N2 + 2H2O
Decomposition Reaction:
2N2H4 + HEAT + 2H2O
4NH3 + O2
Feedrates:
3 x (ppm O2 + Residual)
Control Limits:
0.1 ppm Residual N2H4 at Economizer Inlet
Attemperation / Desuperheating:
Yes
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Hydrazine
Hydrazine
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Advantages:
Doesnt contribute to TDS
True residual test
Disadvantages:
Poor reactivity with low temperature
Expensive compared to Sulfite
Suspect carcinogen
Requires special handling / feed
equipment
Decomposes to NH3, which can lead to
copper corrosion
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Organic O2 Scavengers
Pressure > 900 psig (60 bar)

BFW used for superheat attemperation
Condensing turbine present
High-Purity Makeup (Demin./RO)
Coordinated PO4 / pH control
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HYDROQUINONE
OH
REACTION:
C6H6O2 + 1/2O2
CONTROL LIMITS:
DISSOLVED OXYGEN TEST
IRON REDUCTION TEST
H2O + C6H4O2
OH
HYDROQUINONE
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ADVANTAGES
DOES NOT CONTRIBUTE TO TDS

FASTEST ORGANIC OXYGEN SCAVENGER
REQUIRES NO SPECIAL HANDLING
EXCELLENT FOR WET LAY-UP
AVOIDS SULFUR CATALYST POISON
NOT A LISTED CARCINOGENIC
OH
+ O2 =
OH
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Carbohydrazide
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O
REACTION:
-C
N4H6CO + O2
2 N2
+ 3H2O + CO2
DECOMPOSITION REACTION:
N4H6CO + H2O + HEAT
2N2H4 + CO2
2N2H4 + HEAT + 2H2O
4NH3
+ O2
CORTROL-OS-5613
RESIDUAL(0.3-0.5 ppm product)
2
N
3
-N
3
H
2
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Carbohydrazide
Advantages
Low/no cation conductivity
contribution
Does not form LMW organic
acids
CO2 contribute to non degassed
cationic conductivity
Well-accepted in Industry
Much safer than hydrazine
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Variables Influencing
Scavenger Reaction
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Time
Temperature
pH
Catalyst
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pH and Temperature Recommendations

OXYGEN SCAVENGER
MINIMUM TEMP*
MINIMUM pH*
SULFITES
80 OF (27 C)
>8.5
HYDRAZINE
190 OF (88 C)
>8.5
HYDROQUINONE (HQ)
80 OF (27 C)
>8.5
>200 OF (> 93 C)
>8.5
180 OF (82 C)
>8.5
>200 oF(> 93 C)
>8.5
HYDROXYLAMINES (HA)
ASCORBIC ACID
CARBOHYDRAZIDE
*FOR EFFICIENT OXYGEN SCAVENGING

PERFORMANCE
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Monitoring
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Ideal
Point
1
ECONOMIZER
2
1)
2)
Primary sample point for oxygen testing

Sample point necessary for deaerator studies and for
troubleshooting oxygen intrusion through the pump
MONITORING
pH
Conductivity
Hardness, silica
Oxygen
Corrosion
metals analysis
corrosion coupons
Millipore Iron Testing
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Feed Water and Condensate

System Treatment
Ammonia
Amines
Condensate polishing
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Condensate Treatment
In The Condensate:
Carbon Dioxide
CO2 + H2O
H2CO3
H2CO3
H+ + HCO3-
pH DECREASES
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Feedwater Alkalinity
Is a Source of CO2 in Condensate
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IN THE BOILER:
2HCO3CO3=
CO3= + H20 + CO2

CO2 + 2OHSTEAM
CO2
FEEDWATER
HCO3CO3=
OH-
BLOWDOWN
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Relative Corrosion Rate of

Copper Alloys and Carbon Steel vs pH
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CARBON
STEEL
CORROSION
RATE
COPPER
9
pH
10
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Fundamental Amine
Characteristics
Distribution Ratio
Neutralizing Capacity
Basicity
Thermal Stability
NEUTRALIZING AMINES
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R - NH3+ + HCO3-
R - NH2 + H2CO3
R - NH3+ + OH-
R - NH2 + H2O
CONDENSATE, pH
10
6
8
10
AMINE FEED (ppm)
12
14
16
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BASICITY
Neutralizing Basicity Constant

Morpholine
Ammonia
Ethanolamine
DEAE
MOPA
Cyclohexylamine
2
18
32
66
126
440
DISTRIBUTION RATIOS
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DR = Concentration in steam
Concentration in liquid
VAPOR
LIQUID
HIGH DISTRIBUTION
RATIO
LOW DISTRIBUTION
RATIO
DISTRIBUTION RATIOS
AMINE
AMMONIA
CYCLOHEXYLAMINE
DEAE
MOPA
MORPHOLINE
ETHANOLAMINE
DIAMINE
CONTAMINANTS
CO2
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0 PSIG
10
4.0
1.7
1.0
0.4
0.07
0.45
5400
DR
200 PSIG 1000 PSIG
7.1
3.6
16.0
9.3
4.5
3.4
2.4
2.5
1.6
1.0
0.15
0.29
1.9
2.7
500
100
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Boiler Internal Treatment

& Steam Purity
Coordinated PO4 /pH
Steam purity
Deposit Formation
Deposition rate increases with heat flux (Btu/Ft2)

Reduces Heat Transfer
Increases tube wall temperature
Induces corrosion
Ultimately - Tube failure
Effect of Deposition on Heat Transfer

Tube Metal
Insulating
Scale
800F
Fireside
Combustion
Gases
600F
Fireside
500F
Waterside
Scaled Tube
Surface
500F
Waterside
Clean Tube
Surface
Cause and Effect Diagram for Boiler Deposition

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Monitoring Tools
1. Monitor NaZ Performance:
2. Monitoring Boiler Feedwater/
Condensate Hardness
3. On-Line Hardness Analyzers
4. Equipment Inspections
5. Routine Blowdown Testing
6. Data Tracking
Monitoring Tools
1. Boiler Feedwater/ Condensate
Iron Monitoring
2. Turbidity Monitoring
Hardness Salts
Iron
Intermittent
Contamination
Intermittent
Contamination
Condensate Hardness
Contamination
Condensate Corrosion
Poor NaZ Performance

Chemical Underfeed
Poor Blowdown Control
Chemical Underfeed
Poor Storage Practices
Deposition
Fouling
Poor Chemical Feed Control

Condensate Hydrocarbon
Contamination
High Boiler Silica

Poor Separation
Equipment Performance
Rapid Load Swings
Hydrocarbon Contamination
Hydrocarbon
Monitoring Tools
1. On-Line Total Analyzer
2. Boiler Feedwater Inspection
Header Pressure Swings
Superheater/Turbine Fouling
Monitoring Tools
1. Steam Purity Monitoring
2. Routine Boiler Testing
3. On-Line Sodium Analyzer
5. Data Tracking
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Coordinated Phosphate/pH Programs
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Used Primarily in high pressure boilers to

protect against caustic gouging
Applicable for lower pressure boiler

systems on demin quality makeup
Sodium (caustic) is primary feedwater

contaminant
Iron may also be a problem polymers used

for iron control
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Coordinated PO4/pH Boiler Treatment

To control boiler water pH......
......Create a buffer system
between PO4 and NaOH
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Under-Deposit Corrosion
High or Low Boiler Water pH

Corrodes Boiler Steel
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RELATIVE
CORROSIVE
ATTACK
8.5 pH
12.7 pH
SAFE RANGE
pH
10 11 12 13 14
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Na: PO4 RATIO OUT OF CONTROL

EXCESS SODIUM LEAKAGE
Na2 HPO4 + 2NaOH
Na3PO4 + NaOH + H2O
Low DSP Fed
Free Caustic
4Na + 1PO4
Na:PO4 = 4:1
PREVENTING CAUSTIC
CONCENTRATION
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NaOH + Na2HPO4
Caustic
Disodium
Phosphate
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Na3PO4 + H2O
Trisodium
Phosphate
Water
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Coordinated Phosphate/pH Control
2Na2 HPO4 + 2NaOH

Exact DSP Fed
6Na + 2PO4
Na:PO4 = 3:1
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2Na3PO4 + 2H2O
Under-Deposit Neutralization
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C O O R D IN A T E D p H /P H O S P H A T E C O N T R O L
1 0 .8
1 0 .6
M A X IM U M B O U N D A R Y 3 .0 :1 M O L A R R A T IO
``F re e '' C a u s tic
1 0 .4
R e g io n
1 0 .2
2 .8 :1 N a /P O 4
C o n tr o l A r e a
<900 psi
1 0 .0
2 .7 :1 N a /P O 4
9 .8
pH AT
25C
`` C a p tiv e ''
9 0 1 -1 5 0 0 p s i
A lk a lin ity
R e g io n
9 .6
9 .4
2 .6 :1 N a /P O 4
1 5 0 1 -2 0 0 0 p s i
9 .0
V e c to r
2 0 0 1 -2 5 0 0 p s i
C O N T R O L B O U N D A R Y C o n tro l
8 .8
8 .6
T R I-S O D IU M
PHO SPHATE
C A U S T IC
9 .2
>2600 psi
8 .4
8 .2
1 .0
2 .2 :1 N a /P O 4
M O L A R R A T IO
D I-S O D IU M
PHO SPHATE
D ia g ra m
BLOW DOW N
M O N O -S O D IU M
PHO SPHATE
CO NTRO L AR EA
2 5 0 1 -2 6 0 0 p s i
2
5 6
10
15
20
30
p p m O rth o p h o s p h a te , a s P O 4
40
50
60
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Caustic-Phosphate Equilibrium
Caustic
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Tri-sodium PO4
Di-sodium PO4
Blowdown
Mono-sodium PO4
Reality Check
Your 90 bar boiler has a pH 9.5 and PO4 of 30 ppm.
Boiler PO4 control range is 10 - 20 ppm
How should we respond?
[A]
Reality Check
Your readings for this 100 bar boiler are pH 10.2 and PO4 of 6. PO4
control range is 4 - 8 ppm.
What actions will put you back into control?
[A]
Acid Phosphate Corrosion

zAcid
PO4 corrosion potential exists when

boiler water Na/PO4 ratio is less than 2.3
zSodium
PO4 (Di or Mono) can react with

Magnetite or Iron to form Maricite (NaFePO4)
under high temperature (>300 C)
Steam Purity
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Importance of Steam Purity

z
Protect Capital Investments, such

as:
Superheaters
Turbines
Steam lines and valves
Maintain Production
Prevent Process Contamination
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Definitions
Steam Purity
Solid, liquid or vaporous
contamination in the steam
Steam Quality
A measure of the moisture in
the steam
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Steam Purity
Guidelines
Turbine manufacturer (ppb

levels)
Boiler manufacturer (ppm
levels)
Industry professional
organizations
Operations
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Turbine Manufacturers Steam Purity Limits
PARAMETER
General
Electric
NORMAL
100 HR.
24 HR.
Westing
house
NORMAL
2 WEEK
24 HR.
Allis
Chalmers
NORMAL
Cation Cond.
uS/cm
Sodium, ppb
0.2
0.5
0.3
0.3-0.5
0.5-1.1
0.1
10
5-10
10-20
10
Chloride, ppb
5-10
10-20
10
Silica, ppb
10
10-20
20-50
10
Iron, ppb
20
Copper, ppb
Oxygen, ppb
10
A - Governed by requirements of the steam-generator manufactureer
10-30
30-100
Steam Turbine - Problems

Deposition
Deposit thickness 0.1 mm reduces stage efficiency by

3%
Surface Roughness
Affects flow passage width

Reduce stage efficiency
LP Blade corrosion
Stress corrosion cracking (NaOH, Cl)

Pitting
Erosion
Industrial Steam Turbines

Typical Sources of Impurities
Chemical Cleaning
Makeup Water
Air In-Leakage
Demineralizers
Water
and
Steam
Condenser Leaks
Corrosion Products
Water Treatment
Chemicals
Process Chemicals
STEAM PURITY
Steam Purity vs Steam Quality
Steam purity is the solid, liquid, or vaporous contamination
in the steam
Steam quality is the measurement of moisture in steam
Steam Purity Guidelines

Turbine & Boiler Manufacturers
Industry Professional Organizations
(ASME, ABMA, EPRI, VGB, BS )

Boiler Manufacturers
Operations
Steam Purity
Guidelines
Normal Operation
Parameter
ABB
GE
Na,
ppb
< 10
<20
< 10
< 10
SiO2,
ppb
< 20
< 20
< 20
< 15
Total Fe, ppb
< 20
< 20
<5
Cu,
ppb
<3
<2
Cl,
ppb
Cationic
Cond. us/cm
<0.2
< 0.2
Westinghouse Mitsubishi
< 15
<2
< 0.3
< 0.2
Steam Purity Guidelines

Abnormal Operation (Westinghouse)
* Time refers to continuous time in the range and also to total time in a 12-month period in the
range
Parameter
2-week *
24-Hour *
Immediate
Shut Down
Cation Cond.
us/cm
Na, ppb
0.3 - 0.5
0.5 - 1.0
> 1.0
10 - 20
20 - 35
> 35
SiO 2, ppb
20 - 40
40 - 80
> 80
Cl, ppb
15 -30
30 - 50
> 50
SO 4, ppb
15 -30
30 - 50
> 50
CARRYOVER: MECHANICAL CAUSES
STEAM SEPARATION EQUIPMENT

STEAM DRUM LEVEL
STEAM LOAD
OVERFIRING
CARRYOVER:
CHEMICAL CAUSES
FOAMING
TDS
Alkalinity
Organics/ Polymer Overfeeding
Antifoam
SELECTIVE VAPOROUS CARRYOVER (GOVERNED BY DRUM
pH, PRESSURE AND TEMPERATURE
Silica
Others - Cl, SO4, Fe
ATTEMPERATION
WATER
FEEDWATER
Quality of Feed water

Chemical Treatment
SWEET WATER CONDENSER
Source of Coolant
Purity of Steam Source
CONDENSATE
MONITORING STEAM PURITY
SODIUM
On Line Analyzer
Isokinetic Sampling
Bottle Study (Na free
bottles)
Saturated Steam
Infrastructure
Boiler Storage
More Proof.
More Power.
Most oxygen corrosion occurs or is

initiated when boiler is off-line (wet
storage)
Key to Success - Alkaline & oxygen-free
during wet storage
Infrastructure
Boiler Storage
More Proof.
More Power.
Dry Storage with a desiccant is

recommended for long-term storage
What constitutes long-term?
Off-season storage
Rule-of-thumb: Normally recommend
dry storage if lay-up will be >1 month
and boiler will not be needed on short
notice
Infrastructure
Boiler Storage
More Proof.
More Power.
Wet storage is recommended when:

Boiler is required for emergency
stand-by or on short notice
Capacity required to meet peak
demand
Unit will be out-of-service for
< 1 month
Infrastructure
More Proof.
More Power.
Wet Storage Methods

1. Volatile Chemicals
2. Sulfite & Caustic
3. Cascade lay-up / Hot standby
4. Dry lay-up with desiccant
General guidelines for wet

storage with chemicals
Infrastructure
More Proof.
More Power.
Add chemicals to fill water as it is pumped

into boiler
Fire boiler moderately after chemical
addition to circulate & distribute or utilize
external circulation pump
Always follow boiler manufacturers
recommendations for firing the boiler
Adjust pH/alkalinity with amine or caustic
consistent with the lay-up chemical being
used.
Infrastructure
General guidelines for wet storage of high-pressure

boilers with chemicals
More Proof.
More Power.
Weekly testing during wet storage

Measure pH/Alkalinity
Test dissolved oxygen and/or
scavenger residual
Maintain dissolved oxygen level below
10 ppb
Supplement scavenger/amine as
required
Preventing oxygen ingress during storage:
Connect surge tank (drum) filled with
lay-up solution to upper vent
Alternative - 5 psig (0.34 bar) nitrogen
cap
Infrastructure
More Proof.
More Power.
Volatile Chemicals
Required when:
Above 900 psig (60 bar)
Non-drainable superheaters
Turbines
High-purity make-up
Sulfite is NOT suitable
Infrastructure
Volatile Chemicals
More Proof.
More Power.
Acceptable water for preparation of highpressure boiler lay-up solutions:

Good-quality demineralized H2O
Good quality condensate (no solids)
No softened-quality, RO or raw water
with appreciable TDS
Add chemicals to fill water as it is pumped
into boiler
Infrastructure
Suitable volatile
oxygen scavengers
More Proof.
More Power.
Hydroquinone
Fastest reaction with oxygen at
ambient temp
Must use neutralizing amine with HQ
Important - Amine MUST be
compatible
with HQ (or will develop sludge):
Hydroxylamines
Most volatile & compatible with
amines
Infrastructure
More Proof.
More Power.
Suitable volatile
oxygen scavengers
Hydrazine - 200 ppm as N2H4

Excellent passivator at > 200 ppm as
N2H4, BUT:
Not recommended - Safety hazard!
Amine is not typically required
Ascorbic acid - Not recommended:
Poor thermal stability
Acidic decomposition products
Non-volatile
Infrastructure
Volatile Chemicals
More Proof.
More Power.
Special lay-up product - CorTrol OS7700

HQ plus special low-volatility amine
package
Avoids low pH excursions on re-start
Feedrate: 2000 ppm product
4000 ppm in new systems (nonpassivated)
Maintain pH above 10.5 throughout
Infrastructure
Dry Lay-up with Desiccant (Long-term

storage)
More Proof.
More Power.
Drain boiler
Hot air/heat to remove all moisture
Use desiccant (with color indicator)
Silica gel
Quick lime
Activated alumina
Infrastructure
PRESENT TREATMENT PROGRAM AT HAZIRA
CORTROL-5613-OXYGEN SCAVENGER
FEED RATE 0.5-1.0 PPM
RESIDUAL MONITORING.
STEAMATE-NA8590
CONDENSATE TREATMENT
LOW DR AMINE
TRI SODIUM PHOSPHATE
FOR pH/PO4 coordination
AMMONIA
FEED WATER & STEAM pH CONTROL
More Proof.
More Power.
Infrastructure
More Proof.
More Power.
Thank You

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Infrastructure

Water & Process Technologies

Boiler Technical Training

February 26, 2008

BOILER WATER TREATMENT

BASIC WATER CHEMISTRY

Basics & Interpretation of Water Analysis

Density - 1 kg/l @ 4 oC ; 0.998 kg/l @ ambient temperature and

Impurities found in Water

SUSPENDED SOLIDS (Silt)

DISSOLVED SOLIDS (Minerals)

Where do these things come from?

Impurities found in Water

Dissolved solids present as ions

HCO3possibly OH- & CO3-Cl-

NO3- PO4 --SO4--

SiO2, possibly free CO2

Dissolved Solids Commonly Found in Water

Factors Affecting Solubility

Temperature - Most salts increases except for Ca and Mg Salts

Turbidity - suspended solids

Typical Water Analysis

Hydrogen Ion Concentration

How Does pH Apply

pH < 7: Acidic (corrosion)

Inverse of Resistance [mho]

Normal: Increases with Temperature

Retrograde: Decreases with

How Do We Quantify What Is in the Water?

PPM (parts per million)

mg/l (milligrams per liter)

parts of solute per million parts of

Magnesium expressed as its Equivalent weight

Comparison - Watertube vs. Firetube:

Low to super critical

Require Large Space

WATERTUBE BOILER: A-TYPE

Steam Exit Drum

CAUSE AND EFFECT DIAGRAM FOR BOILER PROBLEMS

STRESS CORROSION CRACKING

FeedWater = Steam + Blowdown

FeedWater (kg/hr) = Steam Generation (kg/hr)

Determining Cycles of Concentration

Feedwater vs. Boiler Water analysis

Neutralized Boiler Water Cond. (umhos at 25C)

Check via Chlorides, Silica

Do not use compounds that routinely precipitate (phosphate,

Demineralized or RO make-up Tracer methods

Steam, Feed Water & Blowdown Relationships

% Blowdown = 100 / FW Cycles

Feedwater = Steam X [Cycles / (Cycles 1)]

Feedwater = Steam + Blowdown

Feedwater = Make-up + Condensate

Corrosion of Iron by Oxygen

Iron Is Oxidized on the Surface (Anode) - Metal Loss

Rapid Perforation ~ Equipment Failure

Dissolved O2 Level, ppb

Types of Oxygen Scavengers

Residual (ppm SO3-)

Pressure > 900 psig (60 bar)

DOES NOT CONTRIBUTE TO TDS

2N2H4 + HEAT + 2H2O

pH and Temperature Recommendations