Steam/Water Quality Control

ASHIS KUMER NATH

MANAGER (CHEMICAL), Addl. Charge
B. Sc.(Honors'), M. Sc. In Chemistry, Chittagong University.
MBA (Major in HRM), Southeast University
Necessity of Water Quality Control
■ Boiler water is required to be ultra pure
to prevent scale, corrosion and carry-over.
■ Water Treatment
● External water treatment : to remove impurities in water

● Internal boiler water treatment (chemical treatment)

: treatment for the feed and condensate lines and for boilers
- to prevent corrosion by the addition of an oxygen scavenger,
corrosion inhibitor and sludge dispersant to the lines,
- to supply water containing as little impurities as possible,
- to disperse the scale components in the feed water and
- to discharge the scale components from the boiler through blow-down.
Necessity of Water Quality Control

■ Potential Adverse Effects of Impurities

Sludge, scale, corrosion and so on

■ Typical Impurities
• Calcium and magnesium salts
• Sodium
• Silica
• Organic matter
• Suspended solids
• Phosphate
 Boiler Problems Caused by Water

■ Three major problems caused by impurities :

● Corrosion : a chemical attack on metal surface that leads to a

loss of metal
● Scale : an accumulation of impurities on metal surface
(results in a loss of heat transfer and a loss of
boiler output)
● Carry-over : a contaminant that leaves the boiler steam drum

with the steam

■ To promote a long and efficient boiler life

Eliminate or neutralize the effects of those substances
that can cause corrosion, scale and carry-over.
Boiler Problems Caused by Water

▣ Corrosion
■ Factors
● pH and dissolved oxygen
■ One of the keys to prevent corrosion is a chemical reaction
that takes place between tube metal and properly treated water.
■ Magnetite (a magnetic iron oxide, Fe3O4) : protective coating
● Effective water treatment ensures that the coating of
a magnetite remains intact.
● Improperly treated water (improper pH & dissolved gases)
destructs magnetite.
Boiler Problems Caused by Water

▣ The relationship between pH and the rate of

corrosion
■ pH
● The acidity or alkalinity of any solution
● pH : potential of hydrogen ion

= -log[H+]
, where [H+] is the hydrogen ion concentration.

Pure water dissociates slightly into hydrogen ions

and hydroxyl ions(at 25℃).
H2O ⇄ H+ + OH-
The concentration of hydrogen ions is 10-7 mol/ℓ.
So, the pH of pure water is 7(-log 10-7).
Boiler Problems Caused by Water

▣ The relationship between pH and the rate

of corrosion
■ A slightly alkaline solution in iron metal is most desirable.
■ Maintaining boiler water at a pH of approximately 10 results in
the lowest rate of corrosion.
Boiler Problems Caused by Water

▣ Corrosion Reaction
I

e-

Zn Cu
Zn 2+
Anode Zn Cathode

● Anode Reaction ● Cathode Reaction

M → Mn+ + n e- O2 + 4H+ + 4e- → 2H2O
2H+ + 2e - → H2 ↑ (in acidic)
O2 + 2H2O + 4e - → 4(OH)- (in neutral)
● Others
M+ + e - → M (reduction of metal)
2H2 O + 2e - → H2 ↑+ 2(OH)-
Boiler Problems Caused by Water

▣ Corrosion of Steel in Water (O2)

Rust Formation Reaction :

2Fe2+ + 1/2O2 + 4OH- → 2FeOOH + H2O
Boiler Problems Caused by Water

▣ The relationship between pH and the rate of corrosion

■ Acid Attack
● When the boiler water pH falls below 9
(excessively acidic water)
● The reaction procedure
•Acidic water combines with iron
Fe0 → Fe2+ + 2 e-
Iron Iron ion Electrons
• The electrons can combine with the hydrogen ions
2 H+ + 2 e- → H2
Hydrogen ions Electrons Hydrogen

■ The loss of iron causes leak or rupture of the tubes.

Boiler Problems Caused by Water
▣ The relationship between pH and the rate of corrosion
■ Caustic Attack
● When the boiler water pH rises above 10
(excessively alkaline water)
● The reaction procedure
• The caustic reacts with iron
Fe0 + 2 NaOH → Na2FeO2 + H2
Iron sodium hydroxides Sodium ferrate Hydrogen
(caustic) (soluble)
• The iron salt combines with the water
3 Na2FeO2 + 4 H2O → 6 NaOH + Fe3O4 + H2
Sodium ferrate Water Sodium hydroxides Ferric oxide Hydrogen
(Magnetite)
■ The loss of iron causes leak or rupture of the tubes.
Boiler Problems Caused by Water

▣ Oxygen
□ Procedure
● The iron gives up its electrons :
Fe0 → Fe++ + 2 e-
Iron Iron ion Electrons
●The electrons combine with oxygen and water :
2 e- + 1/2 O2 + H2O → 2 OH-
● The iron ion then combines with the hydroxyl ions :

Fe++ + 2 OH- → Fe(OH)2

● Ferrous hydroxide combines with water and oxygen :

2 Fe(OH)2 + H2O + 1/2 O2 → 2 Fe(OH)3

● Ferric hydroxide decomposes :

2 Fe(OH)3 → 3 H 2O + Fe2O3
Ferric hydroxide Water Ferrous oxide(Rust)
Boiler Problems Caused by Water

▣ Oxygen
□ The mechanism of forming magnetite(in the absence of oxygen)

- produces a black magnetite coating

3 Fe + 4 H2O → Fe3O4 + 4 H2
Iron Water Ferric oxide Hydrogen
(Magnetite)

□ Where dissolved gases enter the plant cycle

1) leaks in valve packing and pump seals

2) the makeup water tank
Boiler Problems Caused by Water
▣ Deposit(Scale) Problem
■ Common contaminants forming deposits
• Ca, Mg, Fe, Cu, Al, SiO2, Silt & Oil
■ Deposits
• Scale crystallized directly onto tube surfaces
• Sludge deposits
■ Scale
• Formed by salts that have limited solubility
but are not totally insoluble in boiler water.
• Reduces the efficiency of a boiler & leads to tube rupture
■ Sludge
• Accumulation of solids that precipitate in the boiler water
■ Deposits reduce heat transfer rate from boiler tube to boiler
water and increase the tube metal temperature.
• Tube metal overheating and tube rupture can occur.
Boiler Problems Caused by Water
▣ Deposit(Scale) Problem
■ Scale formation in a boiler
1) The boiler water is heated to produce steam.
2) The impurities remain in the water and tend to
concentrate.
3) The impurities accumulate on the surfaces of the boiler,
forming scale.
■ Scale problems in a boiler
1) reduce the efficiency of the boiler
2) lead directly to tube failure
■ Scale formation is minimized by
1) proper water treatment procedures
2) chemical cleanings
Boiler Problems Caused by Water
▣ Carry-over Problem
■ Carry-over
a process which suspended and dissolved solids are picked up by the
steam leaving the drum
● Entrainment
▶ Priming : the surging of water into the steam outlet (by
too high a water level)
▶ Foaming : the frothing of small steam bubbles that rise
through the steam outlet (by excessive dissolved
and suspended solids, high alkalinity, and organic
matters)
▶ Vaporization : a material becomes a gas
Ex) Silica in a high pressure boiler becomes a gas .
⇒ The silica plates out as a glassy substance.
⇒ Efficiency of the turbine drops.
Boiler Problems Caused by Water
▣ Carry-over Problem
■ Vaporization of Silica

• When impurities (such as SiO2) change from a solid to a

gas due to a high pressure and temperature

• Carry over with the steam leaving the boiler
• Gaseous silica reaches the turbine blade
• Gaseous silica changes to its solid form
(due to low pressure and temperature)
• SiO2 build-up (TBN) causing problems
- restricting the steam flow
Boiler Problems Caused by Water

▣ Relationship between Vaporization of Silica and

the pH of Boiler Water
Vaporization of Silica

Pressure
Boiler Problems Caused by Water

▣ Carry-over Problem
■ Prevention

1) The use of moisture separators

2) Careful monitoring control of the level of water in the boiler drum
(to prevent priming)
3) Reduce certain types of impurities (to prevent foaming)
● alkaline
● oil
● excessive amounts of dissolved solids
 Steam/Water Quality Control

▣ Boiler Water Treatment

■ The corrosion rate depends on the pH and O2 contents.

● High pH(approximately 10) values

● Low oxygen levels
■ The purpose of boiler water treatment

● to protect and maintain the magnetite coating on the

boiler tube surface
● to precipitate contaminants
■ Methods of boiler water treatment

1) Phosphate Treatment
2) All Volatile Treatment (AVT)
Steam/Water Quality Control

▣ Attack on mild steel by acid & alkali at 310℃

Steam/Water Quality Control
▣ Phosphate Treatment
■ The purpose of phosphate addition
● to control impurities
● to maintain pH

● to prevent scale
■ Trisodium phosphate is the most widely used chemical to remove hardness salts and
convert them to a sludge(can be removed by blow-down).
3 CaCO3 + 2 Na3PO4 → 3 Ca3(PO4)2 + 3 Na2CO3
Calcium Trisodium Tricalcium Sodium
carbonate phosphate phosphate carbonate
(hardness salt) (sludge)
■ pH control
Na3PO4 + H2O → Na2HPO4 + NaOH
Trisodium Water Disodium Sodium
phosphate phosphate hydroxide
(caustic)
Steam/Water Quality Control

▣ Phosphate Treatment
■ Caustic Attack
● caused by free caustic
● prevented by operating below the curve of pH vs. phosphate
concentration
Steam/Water Quality Control

▣ Phosphate Treatment
■ Hide-Out Problems
80
Solubility
40

0 100 200 300 350

Temperature(℃)
Steam/Water Quality Control

▣ Phosphate Treatment
■ Hide-Out Problems

Magnetite (Fe₃O₄)

Magnetite (Fe₃O₄)
Steam Extraction

Steam Extraction

Na₃PO₄
Na₃PO₄ Hot Spot

Hot Spot
Fe₃O₄
Fe₃O₄
N₂H₄
N₂H₄
Porous Scale

Porous Scale

Na₃PO₄

Na₃PO₄
Boier Water
Steam/Water Quality Control

▣ Phosphate Treatment
■ Congruent Control
Disodium phosphate + Trisodium phosphate
※ The Na/PO4 mole ratio has to be 2.6

• Na3PO4 : The Na/PO4 mole ratio is to be 3/1(=3).

• Na2HPO4 : The Na/PO4 mole ratio is to be 2/1(=2).

• Determination of the Na/PO4 mole ratio :

If Na3PO4 = x mole and Na2HPO4 = y mole,

Na = 3x + 2y, PO4 = x + y
Here, let’s assume x = 1, then y = ?
Ⅵ. Steam/Water Quality Control

▣ Volatile Treatment
■ Volatile chemicals
● Oxygen scavenger : Hydrazine(N2H4)
● pH control agents : Ammonia(NH3)

■ Volatile treatment merits and shortages

● Merits : not build up in the boiler as impurities
● Shortages : any accidental in-leakage of impurities could be dangerous (a standby
system available for injecting phosphate)
■ Maintain concentration of ammonia
● Analysis the concentration of ammonia
● Measure conductivity
Steam/Water Quality Control

▣ Volatile Treatment
■ The decomposition of hydrazine at higher temperature
(above 204℃)
3 N2H4 → 4 NH3 + N2
Steam/Water Quality Control
▣ Oxygen scavenger
■ The deaeration process is not completely effective particularly when oxygen
usually remains
■ In order to remove practically all of the remaining traces of oxygen : Inject a
chemical
1) Hydrazine : N2H4 + O2 → N2 + 2H2O
2) Sodium sulfite : 2 Na2SO3 + O2 → 2 Na2SO4
■ Oxygen scavenger injection
1) Injection points
● Outlet of the condensate pump

● Inlet of the boiler feed-water pump

2) Injection concentration
● N2H4 : a residual of 10~20 ppb(at inlet of the economizer)
Steam/Water Quality Control

▣ Boiler Blowdown Control

■ Purpose of boiler blowdown control

To control boiler water parameters within prescribed limits

in order to minimize scale, corrosion, carryover and other
specific problems

■ Blowdown methods

● Manual blowdown
● Continuous blowdown
Steam/Water Quality Control

▣ Boiler Blowdown Control

■ Blowdown equation
● Percentage of boiler blowdown

Quantity of Blowdown Water

 100  % Blowdown
Quantity of Feed Water

● Blowdown quantity : B(ton/hour)

X a
B
b
a : Chloride concentration in feed water(ppm)
b : Limited chloride concentration in boiler water(ppm)
X : Quantity feed water(ton/hour)
Protection During Outage
Conditions
Protection During Outage Conditions

■ Purpose of storage treatment

● To prevent corrosion due to air leak into the boiler

system during outage or storage period

■ Chemical used
● N2H4(Hydrazine) : Scavenger of dissolved oxygen

● NH3(Ammonia) : pH raising agent

● N2(Nitrogen) gas : Inert gas for pressurization

(to prevent air in-leakage)
Protection During Outage Conditions

■ Storage method
● All non-drainable sections
- Filled with demineralized or condensate quality water
( 10 ppm of NH3 and 200 ppm of N2H4 for a long term )
● Copper alloy metal
- Fill with the water containing 0.5 ppm of NH3 and 50 ppm of
N2H4
● All drainable sections
- nitrogen gas , 5 psig nitrogen pressure
● Freezing is a problem
- Drain portions of the steam generator
 Protection During Outage Conditions
■ The usually recommended lay-up procedure
Type of Procedure Note
shutdown

Preoperational
period post Fill the economizer, waterwall, superheater, and
hydro-test reheater with nitrogen to 5psig pressure.
(see note 1,2)
1. The hydrostatical test is
should be filled with
1. Fill the economizer, waterwall, superheater, and demineralized water
Preoperational reheater with nitrogen to 5psig pressure. containing 10ppm ammonia
period 2. Fill the economizer, waterwall, superheater, feed and 200ppm hydrazine.
post chemical water, and reheater with demineralized water
cleaning containing 10ppm ammonia and 200ppm 2. Hydrazine and ammonia
hydrazine.(note 2, 3) should be added in a
manner that results in a
uniform concentration
1. Maintain the same hydrazine and ammonia throughout.
Short outage concentrations as during normal operation.
4 days or less 2. Maintain a 5psig pressure nitrogen for 3. The tube side of copper
superheater and drum. alloy feedwater should be
filled with demineralized
water containing 0.5ppm
1. The economizer, waterwall and feedwater are ammonia and 50ppm
filled with demineralized water containing hydrazine.
Long outage 10ppm ammonia and 200ppm hydrazine.(note 1,
longer than
4 days 2, 3)
2. The drum, superheater, and reheater are filled
with nitrogen to 5psig pressure.
On-line Steam/water quality monitoring
On-line Steam/water quality monitoring
Thanks all