Boiler Water Chemistry
By
B.A.Chemmannoor
STEAG-encotec
Pre-Treatment
Boiler
Process
Process
Process
Low
pressure
steam
Nalco Chemical Co.
Blowdown
flash tank
Flash
tank
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
Carbonate
Sulfate
1620
15
1290
decomposes
13
1250
Magnesium
Bicarbonate
Carbonate
Sulfate
37,100
101
170,000
decomposes
75
356,000
Sodium
Bicarbonate
Carbonate
Chloride
Hydroxide
Sulfate
38,700
61,400
225,000
370,000
33,600
decomposes
290,000
243,000
970,000
210,000
Scale Formation Mechanisms
Precipitation of insoluble hardness
Ca(HCO3 )2 + HEAT ---> CaCO3 + H2O + CO2
Mg+2 + OH- ---> MgOH+
H2SiO3 ---> H+ + HSiO3MgOH+ + HSiO3- ---> MgSiO3 + H2O
Exceeding saturation through evaporation, resulting
in crystallization
eg. CaSO4, SiO2
Found in Boiler Deposits
N am e
A cm ite
A nalcite
A nhydrite
A ragonite
B asic m agnesium phosphate
B rucite
C alcium hydroxide
C alcite
C opper
C uprite
Ferrous oxide
G oetnite
G ypsum
H em atite
H ydroxyapatite
M agnetite
S erpentine (m agnesium silicate)
S odium ferrous phosphate
Tenorite
Thenardite
X onotlite
Form ula
N a 2 O Fe 2 O 3 4S iO 2
N a 2 O A l 2 O 3 4S iO 2 2H 2 O
C aS O 4
C aC O 3
(gam m a form )
M g 3 (P O 4 ) 2 M g(O H ) 2
M g(O H ) 2
C a(O H ) 2
C aC O 3
(beta form )
Cu
C u 2O
FeO
Fe 2 O 3 H 2 O (alpha form )
C aS O 4 2 H 2 O
Fe 2 O 3
C a 10 (P O 4 ) 6 (O H ) 2
Fe 3 O 4
3M gO S iO 2 2 H 2 O
N aFeP O 4
C uO
N a 2S O 4
5 C aO 5 S iO 2 H 2 O
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-, tri- sodium phosphates
Poly Phosphates
Sodium hexa meta phosphate
Sodium hepta meta phosphate
Sodium tripoly phosphate
Tetra sodium pyro-phosphate
Phosphate Technology
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
Phosphate Technology
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
Phosphate Technology
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
Phosphate Technology
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
Chelants
Act on dissolved metal ions
Create very soluble complexes
Competing ions (PO4, SiO2, OH) reduce effectiveness
Common Chelants
EDTA
(Ethylene diamine tetracetic acid)
Has 6 metal complexing sites which
include nitrogen and oxygen atoms
NTA
(Nitrilo triacetic acid)
Has 4 metal complexing sites
Comparison of Chelants
NTA is more thermally stable
900 psig max. for NTA,
600 psig max. for EDTA
NTA has lower cost than EDTA
EDTA chelates Magnesium better than NTA
EDTA chelates ferrous iron better than NTA
EDTA has full FDA approval
Application of Chelants
Must be fed continuously to feedwater using a
stainless steel injection quill & piping
Oxygen must be absent
Residual concentration must be kept below 10
ppm as CaCO3 in boiler water to minimize
corrosion
Accurate feed control is required
Chelant Control Ranges
Boiler Pressure
psig
(Bar)
Chelant Residual
ppm as CaCO3
400
(30)
4-8
401 - 600
(30 - 40)
3-6
601 - 1000
(40 - 70)
3-5
Chelant Advantages
No precipitates formed
Heat transfer surfaces cleaner
Less frequent acid cleaning
Can sometimes reduce blowdown
Chelant Disadvantages
Cost more than phosphates
Require stricter control of feedwater quality
More difficult control test
Excessive residuals are corrosive
Competing ions can form deposits
All-Organic Polymer Programs
All-polymer program, polymeric blend
Contains no chelants or phosphates, does not require
supplemental dispersants
Functions by solubilization for Calcium and Magnesium
and by dispersancy for iron and other particulates
Non-aggressive to boiler metals
All-Organic Polymer Programs
Feed to deaerator storage for boilers at < 600 psig and
using softened water
Use other feed points for high pressure boilers using
high purity (e.g. demineralized) makeup
Feed program based on statistical upper control limit
for hardness and iron, not average values
Under dosing (<20% of requirement) can produce
Calcium Acrylate deposits in boiler
All-Organic Polymer Programs
Non corrosive to boiler internals
Offers clean boilers - enhanced heat transfer
Transports 100% of hardness
Non-volatile - safe for turbines
Can test for boiler hardness
Simple product test - easy to test for product
Good passivating program
All-Organic Polymer Programs
Limited to boiler pressures <1000 psig
Requires low hardness feedwater
Some formulations contribute ammonia to steam
Cannot be used as a clean-up 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
Nalco Chemical Co.
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
Tri-Ad Programs
Boiler water contains low level of caustic soda
Also called PRECISION CONTROL
Useful when traces of hardness in feedwater
Greater risk of caustic corrosion
Not for high heat flux boilers
Not for pressure greater than 1800 psig
Equilibrium Treatment
Coordinated and congruent treatments can be difficult
to control
Phosphate hideout interferes
PO4 levels kept between 1 - 5 ppm
Controlled by pH, OH and PO4 in boiler water
Phosphate Hideout
Shows as drop in boiler water phosphate under high load
Under concentrating condition, phosphate precipitates from
boiler water
Further addition of chemical to compensate can cause increased
deposition
Can cause localized corrosion
Phenomenon reverses when heat load drops
All-Volatile Treatment
Creates a non-corrosive pH without adding dissolved solids
Can be used at pressures above 600 psig
Useful in boilers with severe phosphate hideout
Has no buffering for feedwater contamination
Useful when ultrapure steam is needed
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
