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