Boiler Water Chemistry

Pre-Treatment

Boiler
Process

Process

Process Low pressure steam Blowdown flash tank Flash tank Condensate Receiver

Nalco Chemical Co.

Major Problems

Corrosion

Scale

Solubilities
Compound Calcium Bicarbonate Carbonate Sulfate Magnesium Bicarbonate Carbonate Sulfate Sodium Bicarbonate Carbonate Chloride Hydroxide Sulfate ppm as CaCO3 o o o o 32 F (0 C) 212 F (100 C) 1620 15 1290 decomposes 13 1250

37,100 101 170,000

decomposes 75 356,000

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

Name Acmite Analcite Anhydrite Aragonite Basic magnesium phosphate Brucite Calcium hydroxide Calcite Copper Cuprite Ferrous oxide Goetnite Gypsum Hematite Hydroxyapatite Magnetite Serpentine (magnesium silicate) Sodium ferrous phosphate Tenorite Thenardite Xonotlite Formula Na2OFe2O34SiO2 Na2OAl2O34SiO22H2O CaSO4 CaCO3 (gamma form) Mg3(PO4)2Mg(OH)2 Mg(OH)2 Ca(OH)2 CaCO3 (beta form) Cu Cu2O FeO Fe2O3 H2O (alpha form) CaSO42 H2O Fe2O3 Ca10(PO4)6(OH)2 Fe3O4 3MgOSiO22 H2O NaFePO4 CuO Na2SO4 5 CaO5 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
Magnetite

Fe2O3
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. Temp Drop Across Internal Scale = 362oF. Temp Drop Across Tube Wall = 66o F.

Max. Tube Temp (1004o F.) is above allowable Oxidation Temp limit of SA-210 Carbon Steel

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)
(ortho)

Na5P3O10 + 4NaOH -> 3Na3PO4 + 2H2O

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) 400 401 - 600 601 - 1000 (30) (30 - 40) (40 - 70) Chelant Residual ppm as CaCO3 4-8 3-6 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