Boiler Water Chemistry

Boiler Water Chemistry
Pre-Treatment
Boiler
Process
Process
Process
Blowdown Flash
Low
flash tank tank
pressure
steam Condensate
Receiver
Major Problems
 Corrosion
 Scale
Solubilities
Compound ppm as CaCO3
o o o o
32 F (0 C) 212 F (100 C)
Calcium
Bicarbonate 1620 decomposes
Carbonate 15 13
Sulfate 1290 1250
Magnesium
Bicarbonate 37,100 decomposes
Carbonate 101 75
Sulfate 170,000 356,000
Sodium
Bicarbonate 38,700 decomposes
Carbonate 61,400 290,000
Chloride 225,000 243,000
Hydroxide 370,000 970,000
Sulfate 33,600 210,000
Scale Formation Mechanisms
 Precipitation of insoluble hardness
Ca(HCO3 )2 + HEAT ---> CaCO3 + H2O + CO2
Mg+2 + OH- ---> MgOH+
H2SiO3 ---> H+ + HSiO3-
MgOH+ + HSiO3- ---> MgSiO3 + H2O
 Exceeding saturation through evaporation, resulting
in crystallization
eg. CaSO4, SiO2
Found in Boiler Deposits
Name Formula
Acmite Na2OFe2O34SiO2
Analcite Na2OAl2O34SiO22H2O
Anhydrite CaSO4
Aragonite CaCO3 (gamma form)
Basic magnesium phosphate Mg3(PO4)2Mg(OH)2
Brucite Mg(OH)2
Calcium hydroxide Ca(OH)2
Calcite CaCO3 (beta form)
Copper Cu
Cuprite Cu2O
Ferrous oxide FeO
Goetnite Fe2O3  H2O (alpha form)
Gypsum CaSO42 H2O
Hematite Fe2O3
Hydroxyapatite Ca10(PO4)6(OH)2
Magnetite Fe3O4
Serpentine (magnesium silicate) 3MgOSiO22 H2O
Sodium ferrous phosphate NaFePO4
Tenorite CuO
Thenardite Na2SO4
Xonotlite 5 CaO5 SiO2 H2O
Silica
 Forms deposits in boilers
Occurs as magnesium silicate or silicic acid
 Selective silica carryover

Cannot be controlled mechanically by steam
separators
Not usually a problem with boilers with less than
600 psig pressure
Selective Silica Carryover
 Silica is selectively dissolved into
the steam
 Controlled by limiting the silica
concentration in the boiler water
 Controlled by limiting boiler
pressure
 Controlled by maintaining high
pH
Forms of Iron Scale
Iron is usually found in a boiler as one or more of the following:
 A complex with calcium

 A complex with phosphate
 Hematite Fe2O3
 Magnetite Fe3O4
Effect of Scale on Heat Transfer
Effect of Scale on Tube Temperature
Effect of Scale - Example
Effect of Scale - Example
Temp Drop Across Water Film = 76o F. Max. Tube Temp (1004o F.) is above allowable
Temp Drop Across Internal Scale = 362oF. Oxidation Temp limit of SA-210 Carbon Steel
Temp Drop Across Tube Wall = 66o F.
Assume CaSO4 scale (0.024”)
Thermal Conductivity = 10 BTU/ft2-hr-o F/in
Scale Problems
 Boiler tube failure

Caused by reduced heat transfer and tube
overheating
 Under-deposit corrosion
Caused by high concentration of corrosive
agents (usually NaOH)
Scale Prevention
 Precipitation of hardness in the boiler

 Reduce amount of hardness entering boiler
 Keep the hardness soluble
Coagulation Treatments
Principles
 Calcium hardness is precipitated as Calcium
Carbonate
 Magnesium hardness is precipitated as
Magnesium Hydroxide or Magnesium
Silicate
Coagulation Treatment Applications
A Coagulation Program Can Be Used When:
 Boiler pressure < 350 psig

 Feedwater hardness > 60 ppm
 Boiler alkalinity < 500 ppm
Coagulation Treatments
Advantage
 Can treat very high feedwater hardness
Disadvantages
 Low cycles
 High boiler TDS
 High blowdown - wastes heat
 Scale formation
Treatment With Makeup Softening
Requirements for Success
 Proper Operation and Maintenance of Make-up Equipment
 Chemical Conditioning for Residual Hardness

Current Treatment Technologies
There are three technologies in common use today:
 Phosphate residual
 Chelants
 All-polymer treatment
Phosphate Residual
Chemistry
• Precipitates calcium as calcium phosphate
• Precipitates magnesium as magnesium hydroxide

Phosphate Technology
Types of Phosphates
Ortho phosphates
 Mono-, di-, trisodium phosphates
Poly Phosphates
 Sodium hexa meta phosphate
 Sodium hepta meta phosphate
 Sodium tripoly phosphate
 Tetra sodium pyro-phosphate
Feedpoints
 Ortho phosphate
Feed to boiler drum directly

 Poly phosphate
Feed to feedwater line
If feedwater hardness is > 3 ppm, feed both to steam drum

Detailed Chemistry
 (poly) Na5P3O10 + 4NaOH -> 3Na3PO4 + 2H2O

 (ortho) Na2HPO4 + NaOH -> Na3PO4 + H2O
 3CaCO3 + 2Na3PO4 -> Ca3(PO4)2 + 3Na2CO3
 3CaSO4 + 2Na3PO4 -> Ca3(PO4)2 +3Na2SO4
 Mg(HCO3)2 + 4NaOH -> Mg(OH)2 + 2Na2CO3 + 2H2O
 MgCl2 + 2NaOH -> Mg(OH)2 + 2NaCl
Advantages
 Easy to monitor and control
 Does not require high purity makeup
 Can be used at high pressure
 Well understood
 Can be FDA and/or USDA approved
 Can handle feedwater hardness fluctuations
 Residual PO4 is non corrosive
 Large PO4 residual - buffer for excursions
 Relatively low cost ingredients
Disadvantages
 Produces precipitates in boiler water
 Excess alkalinity can produce corrosion
 May require more blowdown
 If so, more heat lost, more chemical used
 Possibility of scaling
 Normally used with sludge dispersant
Sludge Conditioning
 Insoluble Calcium Phosphate and Magnesium
Hydroxide solids formed (Sludge)
 Particulate Iron Oxide returned in condensate
 Solids settle on hot boiler surfaces
 Heat transfer impaired, tube failure risk
Types of Sludge Conditioners
 Synthetic polymers
 Tannins
 Lignins
 Starches
Use of Sludge Conditioners
Starch Organic Products

 When Mg:SiO2 ratio < 2
 When oil contaminates the boiler

 In food processing plants
Lignin Organic Products

 To condition Calcium Phosphate & Iron Oxide
Feed & Control of Sludge Conditioners
Feed to feedwater as far ahead of boiler as possible. Preferred

addition points are:
 Deaerator storage
 Boiler feedwater line
 Direct to steam drum

Phosphate-Polymer Programs
 Affects Calcium & Magnesium precipitation
 Same precipitation chemistry as other phosphate

programs but different dosage requirements for sludge
conditioner & phosphate
 Provides cleaner boilers

Application of Phosphate-Polymer
Programs
 Feedwater hardness less than 3 ppm
 Softeners or naturally low hardness

Phosphate-Polymer Programs
Advantage
 Can provide much cleaner boilers than other
conventional Phosphate programs
Disadvantage
 Requires much stricter control of feedwater
hardness and chemical program
Boiler Corrosion
Types of Corrosion
 Oxygen corrosion
 Alkalinity concentration
 Caustic corrosion
 Acid corrosion
 Chelant corrosion
 Erosion/Corrosion
Oxygen Corrosion
 Can be found throughout the system
 Mechanism same as other oxygen corrosion cells
 Corrosion mechanisms affected by:
– Oxygen concentration
– Temperature
– pH
Boiler Metal Passivation
 Reduces general corrosion
 Forms protective barrier on metal
 Black magnetite film - Fe3O4
 Difficult to quantify results

Boiler Passivation Mechanisms
Reaction of Water With Boiler Metal:

Fe + 2 H2O -> Fe(OH)2 + H2
3Fe(OH)2 -> Fe3O4 + H2 + 2H2O
Rate of Magnetite Formation Is:

 Temperature dependent
 Spontaneous above 180 oC
Effect of pH on Boiler Corrosion
Types of Caustic Damage in Boilers
There are two forms of damage caused by caustic soda

to high pressure boilers, namely:
 Caustic corrosion
 Caustic embrittlement
Caustic Corrosion
 Usually found only in high pressure boilers
 Problem usually due to deposits
 Localized in boiler
 Also called crater attack or caustic gouging
 No embrittlement of metal
Requirements for Caustic Corrosion
Two conditions are necessary for caustic corrosion to occur:
 The presence of a corrosive material in the boiler water

(caustic soda)
 A mechanism for concentrating this material

Concentrating Mechanisms
The following conditions can result in dangerously
high localized caustic soda concentrations
 Porous metal oxide deposits

 Metal oxide deposits
 Operation above rated capacity
 Excessive rate of load increase
 Excessive localized heat input
 Localized pressure differentials
 Restrictions in generating tube(s)
Prevention of Caustic Corrosion
Prevention of caustic corrosion is achieved by minimizing
or eliminating the presence of ‘free’ caustic soda in the
boiler water.
 Coordinated phosphate
 Congruent sodium phosphate
 Phosphate-low hydroxide (tri-ad)
 Equilibrium phosphate control
 All-volatile treatment
Coordinated Phosphate
 Control of pH comes from hydrolysis of trisodium phosphate in
water
Na3PO4 + H2O -> Na2HPO4 + NaOH
 Molar ratio of sodium : phosphate is 3 : 1 in water
 Feedwater contamination usually dictates caustic-consuming

chemicals, such as disodium and trisodium phosphate
 Does not ensure absence of caustic under concentrating

conditions
Coordinated pH/ Phosphate
Control Limits
Congruent Control
 This program was developed to prevent free caustic in
boiler water during concentrating conditions
 At sodium:phosphate ratio of 2.85 in boiler water,

precipitated solids have same concentration
 Safe range is between ratio 2.3 - 2.6
 Control is based on pH and PO4 values

Caustic Embrittlement
 Should not be confused with caustic corrosion
 Embrittlement is a special form of stress corrosion cracking

 Three conditions must be present
– Concentrating mechanism present
– Metal under high stress
– Must contain silica
 Inhibited by improved fabrication techniques and by organic

and nitrate-based inhibitors
Other Causes of Boiler Corrosion
 Feedwater acid contamination
 Surface condenser leaks
 Acid leaks from demineralizer
 Organic materials
 Chelant corrosion

Boiler Water Chemistry

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Boiler Water Chemistry

 Selective silica carryover

 A complex with calcium

 Boiler tube failure

 Precipitation of hardness in the boiler

 Boiler pressure < 350 psig

 Can treat very high feedwater hardness

Requirements for Success

 Proper Operation and Maintenance of Make-up Equipment

 Chemical Conditioning for Residual Hardness

• Precipitates calcium as calcium phosphate

• Precipitates magnesium as magnesium hydroxide

Feed to boiler drum directly

Feed to feedwater line

If feedwater hardness is > 3 ppm, feed both to steam drum

 (poly) Na5P3O10 + 4NaOH -> 3Na3PO4 + 2H2O

Starch Organic Products

 When oil contaminates the boiler

Lignin Organic Products

Feed to feedwater as far ahead of boiler as possible. Preferred

 Boiler feedwater line

 Direct to steam drum

 Affects Calcium & Magnesium precipitation

 Same precipitation chemistry as other phosphate

 Provides cleaner boilers

 Feedwater hardness less than 3 ppm

 Softeners or naturally low hardness

 Reduces general corrosion

 Forms protective barrier on metal

 Black magnetite film - Fe3O4

 Difficult to quantify results

Reaction of Water With Boiler Metal:

3Fe(OH)2 -> Fe3O4 + H2 + 2H2O

Rate of Magnetite Formation Is:

There are two forms of damage caused by caustic soda

 Problem usually due to deposits

 Also called crater attack or caustic gouging

Two conditions are necessary for caustic corrosion to occur:

 The presence of a corrosive material in the boiler water

 A mechanism for concentrating this material

 Porous metal oxide deposits

Na3PO4 + H2O -> Na2HPO4 + NaOH

 Molar ratio of sodium : phosphate is 3 : 1 in water

 Feedwater contamination usually dictates caustic-consuming

 Does not ensure absence of caustic under concentrating

 At sodium:phosphate ratio of 2.85 in boiler water,

 Safe range is between ratio 2.3 - 2.6

 Control is based on pH and PO4 values

 Embrittlement is a special form of stress corrosion cracking

 Inhibited by improved fabrication techniques and by organic

 Feedwater acid contamination

 Surface condenser leaks

 Acid leaks from demineralizer

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