Boiler Water Chemistry

Pre-Treatment
Boiler
Process

Process

Process

Blowdown Flash
Low
flash tank tank
pressure
steam Condensate
Receiver

Nalco Chemical Co.

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-, 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 Chelant Residual

psig (Bar) 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