Documenti di Didattica
Documenti di Professioni
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K S Rajan
February 26, 2008
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“The Basics”
• Hydrologic Cycle
• Properties of Water
• pH and Alkalinity
• Langelier Saturation Index
• Analytical Expressions
• Water Analysis/Deposit Analysis
• Corrosion and Deposition & Monitoring
• Chemical Feed
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Properties of Water More Proof.
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• DISSOLVED GASES
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Hydrologic Cycle
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Impurities found in Water
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Water Impurities Water & Process Technologies
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Dissolved Solids
Cations Anions
Temporary HCO3- Total
Hardness Ca++ Mg++ Alkalinity
possibly OH- & CO3--
Permanent
Hardness Cl- F-
Mineral
Na+ NO3- PO4 --- Acidity
K+
NH4+
SO4--
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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, micro-
organisms
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Typical Water Analysis Water & Process Technologies
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Parameter Value
pH 7.3
Conductivity μS/cm 150
Alkalinity “P” as CaCO3, ppm 0
Alkalinity “M” as CaCO3, ppm 20
Sulfate as SO4, ppm 15
Chloride as Cl, ppm 10
Hardness, Total, as CaCO3, ppm 20
Calcium Hardness, as CaCO3, ppm 15
Magnesium Hardness, as CaCO3 ppm 5
Copper, Total as Cu, ppm 0.05
Iron, Total as Fe, ppm 1.5
Sodium, as Na, ppm 12
Phosphate, Total, as PO4, ppm <0.05
Silica (reactive), as SiO2, ppm 4
Turbidity, NTU 50
TSS, ppm 20
Color, Hazen 3
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Special Ions More Proof.
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• pH
• Hydrogen, H+
• Hydroxide, OH-
• Alkalinity
• Bicarbonate, HCO3-
• Carbonate, CO3--
• Hydroxide, OH-
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pH More Proof.
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Alkalinity
Relationships •M-Alkalinity = Total
– Titration to pH = 4.3
– Sum of: HCO3- + CO3- + OH-
•OH-Alkalinity = 2P - M or titration
– Neutral barium chloride precipitates CO3-
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Conductivity Water & Process Technologies
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Types of Solubility Water & Process Technologies
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Analytical Expressions Water & Process Technologies
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• “Concentration”
• units of solute per unit of solvent:
• PPM (parts per million)
– parts of solute per million parts of
solvent
• mg/l (milligrams per liter)
– 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
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Analytical Infrastructure
Expressions Water & Process Technologies
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• Different Conventions
• We use “ppm as CaCO3”
• ppm ppm
• as substance factors as CaCO3
• Ca 50 2.5 125
• Mg 20 4.1 82
•
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Boiler
Boiler Descriptions
Descriptions
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FIRETUBE BOILERS
ADVANTAGES DISADVANTAGES
High load swing capacity Low pressure
Ease of repair Capacity limit
Low space requirement Usually no superheater
Self contained package Usually no economizer
Relatively low cost Usually low efficiency
Ease of installation One fuel at a time
RISERS
DOWNCOMERS SUPERHEATER
STEAM SCREEN TUBES
DRUM
ECONOMIZER
WATER WALLS
MUD
AIR HEATER DRUM
Coal
140-150 C
To stack
Lower Water
BOILER DESIGN Walls Header
Comparison - Watertube vs. Firetube:
Steam
Feedwater Drum CBD Flue
Water
Risers Gases
Flue Mud
Drum Downcomers
Gases
IBD
WATERTUBE BOILERS
ADVANTAGES
Low to super critical WATERTUBE BOILER: A-TYPE
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
z Require Large Space
z Usually require higher quality
feedwater
z Sensitive to low load operation
Risers
Downcomers
Sidewall Problem
Area
Flue
Gas
Burner Path
Steam Drum
D-Frame
Package Boiler
Downcomers
Furnace Wall
Tubes
Risers
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Babcock & Wilcox
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Coal FiredMore
Boiler
Power.
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Power Utility Boiler
Hot Reheat Water & Process Technologies
Simplified Flow Diagram
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HP Turbine More Power.
HP SH Steam
Sat Steam
Condenser MB MU
IP Turbine LP Turbine
B&W Boiler
BD
Cold Reheat
LP Heaters
Cond Polisher
HP Heaters
Deaerator
BFW
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CAUSE AND EFFECT DIAGRAM FOR BOILER PROBLEMS
POOR CHEMICAL
FEED CONTROL MECHANICAL
INADEQUATE DEAERATOR
BLOWDOWN OXYGEN PERFORMANCE
CONTROL IN-LEAKAGE
DOWNTIME
POOR BOILER CORROSION
FEEDWATER
QUALITY SCAVENGER
UNDERFEED DOWNTIME
CONDENSATE POOR CORROSION
CONTAMINATION EXTERNAL
TREATMENT
BOILER
CORROSION
POOR BOILER
FEEDWATER
QUALITY
STRESSED
CONDENSATE CONCENTRATING AREA
CONTAMINATION MECHANISM
POOR EXTERNAL
TREATMENT POOR CHEMICAL
FEED CONTROL
INADEQUATE EMBRITTLING WATER
BLOWDOWN CHARACTERISTICS
CONTROL
FW= STM ( C )
C-1
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Determining Cycles of Concentration Infrastructure
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Steam, Feed Water & Blowdown Relationships More Proof.
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Oxygen Control
• Deaeration
• Chemical treatment
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Corrosion of Iron by Oxygen More Proof.
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O2
Fe(OH)3 O2
Fe2+ OH-
WATER
ELECTRON FLOW
ANODE CATHODE
ANODE REACTION CATHODE REACTION
Fe. = Fe++ 2e- 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
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Rapid Perforation ~ Equipment Failure More Proof.
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Oxygen Guidelines More Proof.
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ASME <7
TAPPI <7
ABMA NO RECOMMENDATION
EPRI <5
DEAERATOR 7
GUARANTEE
TYPICAL DEAERATOR 15 - 40
O2 LEVELS
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Types of Oxygen Scavengers
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• Solid
– Sodium Bisulfite
– Sodium Sulfite
• Non-Solids
– Hydrazine
– Hydroquinone
– Diethylhydroxlamine (DEHA)
– CARBOHYDRAZIDE
– ASCORBIC ACID
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RECOMMENDED
SULFITE CONTROL LIMITS
ATTEMPERATION / DESUPERHEATING: NO
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Hydrazine More Power.
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
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Hydrazine More Power.
• Advantages:
– Doesn’t 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 More Proof.
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HYDROQUINONE More Power.
OH
REACTION:
C6H6O2 + 1/2O2 H2O + C6H4O2
CONTROL LIMITS: OH
DISSOLVED OXYGEN TEST
IRON REDUCTION TEST
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HYDROQUINONE Water & Process Technologies
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ADVANTAGES More Power.
OH O
+ O2 =
OH O
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Carbohydrazide More Proof.
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H 3
O 2
-N
REACTION: -C
N 2
H 3
N4H6CO + O2 2 N2 + 3H2O + CO2
DECOMPOSITION REACTION:
N4H6CO + H2O + HEAT 2N2H4 + CO2
CORTROL-OS-5613
RESIDUAL(0.3-0.5 ppm product)
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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
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Variables Influencing More Proof.
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Scavenger Reaction
• Time
• Temperature
• pH
• Catalyst
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pH and Temperature Recommendations More Power.
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Monitoring
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Ideal
Point
1
ECONOMIZER
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MONITORING • pH
• Conductivity
• Hardness, silica
• Oxygen
• Corrosion
– metals analysis
– corrosion coupons
Millipore Iron Testing
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• Ammonia
• Amines
• Condensate polishing
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Condensate Treatment
In The Condensate:
• Carbon Dioxide
H2CO3 H+ + HCO3-
pH DECREASES
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Feedwater Alkalinity Water & Process Technologies
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Is a Source of CO2 in Condensate More Power.
IN THE BOILER:
2HCO3- CO3= + H20 + CO2
CO3= CO2 + 2OH-
STEAM
CO2
FEEDWATER OH-
HCO3-
CO3=
BLOWDOWN
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Relative Corrosion Rate of Water & Process Technologies
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Copper Alloys and Carbon Steel vs pH More Power.
CARBON
STEEL
CORROSION
RATE
COPPER
7 8 9 10
pH
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Fundamental Amine
Characteristics
• Distribution Ratio
• Neutralizing Capacity
• Basicity
• Thermal Stability
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NEUTRALIZING AMINES Water & Process Technologies
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10
9
CONDENSATE, pH
5 0 2 4 6 8 10 12 14 16
AMINE FEED (ppm)
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BASICITY
Morpholine 2
Ammonia 18
Ethanolamine 32
DEAE 66
MOPA 126
Cyclohexylamine 440
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DISTRIBUTION RATIOS More Proof.
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DR = Concentration in steam
Concentration in liquid
VAPOR
LIQUID
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DISTRIBUTION RATIOS More Proof.
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DR
AMINE 0 PSIG 200 PSIG 1000 PSIG
AMMONIA 10 7.1 3.6
CYCLOHEXYLAMINE 4.0 16.0 9.3
DEAE 1.7 4.5 3.4
MOPA 1.0 2.4 2.5
MORPHOLINE 0.4 1.6 1.0
ETHANOLAMINE 0.07 0.15 0.29
DIAMINE 0.45 1.9 2.7
CONTAMINANTS
CO2 5400 500 100
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Deposit Formation
Insulating
Scale
800°F
Fireside
Combustion
Gases
600°F
Fireside
500°F 500°F
Waterside Waterside
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Coordinated Phosphate/pH Programs More Power.
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Coordinated PO4/pH Boiler Treatment More Power.
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Under-Deposit Corrosion
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High or Low Boiler Water pH More Proof.
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Corrodes Boiler Steel
RELATIVE
CORROSIVE
ATTACK
8.5 pH 12.7 pH
SAFE RANGE
1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
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4Na + 1PO4
Na:PO4 = 4:1
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PREVENTING CAUSTIC More Proof.
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CONCENTRATION
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Coordinated Phosphate/pH Control More Power.
6Na + 2PO4
Na:PO4 = 3:1
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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
1 0 .4 ``F re e '' C a u s tic
R e g io n 2 .8 :1 N a /P O 4 C o n tr o l A r e a
1 0 .2 <900 psi
1 0 .0
2 .7 :1 N a /P O 4 C o n tr o l A r e a
9 .8 9 0 1 -1 5 0 0 p s i `` C a p tiv e ''
A lk a lin ity
pH AT 9 .6 R e g io n
2 .6 :1 N a /P O 4
25C 9 .4 C o n tr o l A r e a
1 5 0 1 -2 0 0 0 p s i C A U S T IC T R I-S O D IU M
9 .2 PHO SPHATE
9 .0
C o n tr o l A r e a V e c to r
2 0 0 1 -2 5 0 0 p s i
8 .8 C O N T R O L B O U N D A R Y C o n tro l D I-S O D IU M
C o n tr o l A r e a
>2600 psi
2 .2 :1 N a /P O 4 D ia g ra m PHO SPHATE
8 .6 M O L A R R A T IO
BLOW DOW N M O N O -S O D IU M
8 .4 CO NTRO L AR EA PHO SPHATE
2 5 0 1 -2 6 0 0 p s i
8 .2
1 .0 2 3 4 5 6 7 8 10 15 20 30 40 50 60
p p m O rth o p h o s p h a te , a s P O 4
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Caustic-Phosphate Equilibrium More Proof.
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Di-sodium PO4
Blowdown
Mono-sodium PO4
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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
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• 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 More Power.
Iron, ppb A A A 20 5
Copper, ppb A A A 2 1
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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
• 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
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Boiler Storage
• Most oxygen corrosion occurs or is
initiated when boiler is off-line (wet
storage)
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Boiler Storage
• Dry Storage with a desiccant is
recommended for long-term storage
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Wet Storage Methods
1. Volatile Chemicals
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General guidelines for wet More Proof.
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storage with chemicals
• Add chemicals to fill water as it is pumped
into boiler
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General guidelines for wet storage of high-pressure More Proof.
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Volatile Chemicals More Power.
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Suitable volatile More Power.
oxygen scavengers
• 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
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Suitable volatile More Power.
oxygen scavengers
• Hydrazine - 200 ppm as N2H4
– Excellent passivator at > 200 ppm as
N2H4, BUT:
– Not recommended - Safety hazard!
– Amine is not typically required
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Dry Lay-up with Desiccant (Long-term More Proof.
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storage)
• Drain boiler
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• 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
RIL-Hazira/BWT-Technical Training
GEWPT- Confidential Material
Infrastructure
Water & Process Technologies
More Proof.
More Power.
Thank You
RIL-Hazira/BWT-Technical Training
GEWPT- Confidential Material