Boiler Water Treatment

Training Course

Yokohama Tires Philippines, Inc.

July 2008
Agenda
 General definition and types

 Boiler problems caused by water

 External boiler water treatment

 Internal boiler water treatment

What are Boilers?
 Used to heat water to generate steam
or hot water
 Classified according to
 structures
 methods of water circulation
 types of fuel
 kinds of the materials used
 Types of Boilers
Cylindrical
Burner Steam valve
 Safety valve

Vertical boiler
Steam and
 water
separator

 Flue-tube boiler
 Fire-tube boiler Water tube
Pressure

Fire and flue-tube boiler

gauge
 Insulation

Water-tube
Level
 gauge
Chimney

 Natural circulation boiler

Fireproof
 Forced circulation boiler bricks

 Once-though boiler Blowdown

valve

• Structure of a typical mini-circulation boiler

Types of Boilers
 According to pressure

Low pressure below 20 kgf/cm2

Medium pressure 20-75 kgf/cm2

High pressure above 75 kgf/cm2

Boiler Problems Caused by Water

 Scaling

 Corrosion

 Carryover
Scaling

 Dissolved solids

 Corrosion products

 Organic substances
 Scaling Problem
 Dissolved solids Substance
Thermal
conductivity
 Hardness components (kcal/m.h.oC)
and silica Silica scale 0.2-0.4
 Substances with low Calcium carbonate scale 0.4-0.6
solubilities deposit and
Calcium sulfate scale 0.5-2.0
form the scale
Calcium phosphate scale 0.5-0.7
 Concentrates on the
heating surfaces Iron oxide (hematite)
3-5
scale
 Low thermal conductivity Iron oxide (magnetite)
1
scale component reduces scale
the thermal efficiency of Carbon steel 40-60
boiler
Copper 320-360
Solution
 Removal of hardness using softener
 Use of boiler compounds and sludge
dispersants
 Control of the boiler water
concentration
 Scaling Problem
Thermal conductivity of scale: 1 kcal/m.h.oC

 Corrosion products 600

Heat flux (Q) (kcal/m2.h)

Scale components are usually

Inner skin temperature of tube (oC)



iron oxide
500
 In case of copper and copper
alloy as auxiliary equipment;
Scale contains cu, Ni and Zn 400

 Adhere more on the tube surface

of the fire side with higher heat 300
0 10 20 30 40 50 60 70 80 90 100 110
flux Scale amount (mg/cm2)

 Raises tube skin temperature 0 0.1 0.2 0.3 0.4

and disturbs heat transfer Scale thickness (mm)

• Relationship between the iron oxide scale thickness and

inner skin temperature of a boiler tube
Solution
 Reduction of the impurities from feed water &
recovered condensate
 Ph control
 Iron removal
 Demineralization
 Determination of the time for the chemical
cleaning and the application of the cleaning
by periodically inspecting the scale adhesion
condition of evaporation tubes sampled from
high heat load part of the boiler
 Scaling Problem
 Organic substances Fire side
 Humic acid and fulvic Q
acid
t1
 Partly decompose to
organic acids in the boiler
which reduces the ph of
the boiler water t2
Ds

 Partly carbonize on the Water side

Dc

heating surface to form Carbon scale

carbon scale Iron oxide scale

 Disturbs the heat transfer • Model of heating surface covered with

and increase the skin a scale composed of double layers
temperature of tubes
Solution
 Removal of organic substances from raw
water
 Coagulation
 Filtration
 Oxidation, adsorption treatments, etc
 Strict control of boiler water ph
 Periodic scale sampling and the carbon
content analysis for determining the time of
chemical cleaning
Corrosion
 Factors influence corrosion reaction on
metal
 Corrosion of feedwater line
 Corrosion of boiler
 Corrosion of condensate line
Corrosion
 Factors influence corrosion reaction on
metal
 pH
 Dissolved gases (oxygen, carbon dioxide,
etc.)
 Concentration of dissolved matters
 Temperature
 Water flow rate
 Corrosion
Corrosion of Feedwater Line
 At anode: Corrosion Inhibition Mechanism
 Fe  Fe2+ + 2e- WATER

 At cathode: H2O ½O2

 ½ O2+ H2O + 2e-  2OH- _

2OH
 In water: Fe 2+
_
2e
 Fe2+ + 2OH-  Fe(OH)2 Anode Cathode
Ferrous hydroxide further reacts
with dissolved oxygen to produce
ferric hydroxide
 4Fe(OH)2 + O2 + 2H2O  4Fe(OH)3
 Corrosion
H2O, 1/2O2 2OH- 2OH- H2O, 1/2O2

Corrosion of boiler Cathode Fe2+ Fe2+ Cathode

 Iron oxide
film
 Due to dissolved oxygen
Anode
Due to precipitation of
2e- 2e-

Carbon steel
corrosion products • Formation of a local cell due to the partial destruction
of oxide film on carbon steel
 Due to alkali
concentration Corrosion product
H2O, 1/2O2 2OH- 2OH- H2O, 1/2O2
Cathode Cathode
Fe2+
Protective
film

2e- Anode 2e-

Carbon steel
• Formation of an oxygen concentration cell due to the
deposition of corrosion product
 Corrosion
0.225

Corrosion of Condensate Line 0.200

 Bicarbonate and carbonate 0.175

ions thermally decompose to 0.150

carbon dioxide gas 0.125

 2HCO3-  CO32- + CO2 + H2O 0.100

 CO32- + H2O  2OH- + CO2
0.075

 Carbon dioxide gas transfers to

the steam and condensate line
0.050

along with steam, and .0.025

dissolves into the condensate 0

as carbonic acid
8 7 6 5 4 3 2
pH

 CO2 + H2O  H2CO3 • Relationship between the corrosion rate of

carbon steel and pH under the presence of
 H2CO3  H+ + HCO3- oxygen and carbon dioxide
 HCO3-  H+ + CO32-
Carryover
 Steam generated in boilers essentially
includes no dissolved solids, however,
the dissolved solids in boiler water
sometimes transfer to the steam due to
various causes. This phenomenon is
called “carryover.”
 Factors and Causes of Carryover
Factors related to the boiler
quality control
Factors related to the operating
control of boiler
Factors related to the mechanical
structure of boiler
Excess concentration of the boiler
water, the contamination of boiler
water with oils and fats, the
dissolution of silica to steam
Operation at the high water level,
the rapid fluctuation of heat load
Poor condition of the water and
steam separator
Priming and Foaming
 Priming is an occurrence of abnormal violent
evaporation caused by a rapid increase of the heat
load. Large amount of boiler water droplets and
foams from the boiler water transfer to the steam
line together with the steam.
 Foaming is a phenomenon which a large amount
of foams are produced on the boiler water surface
by the water contamination with fats and oils or
by an excess concentration of dissolved solids in
the boiler water. Bubbles containing the dissolved
solids transfer to the steam line.
External Boiler Water
Treatment

 Raw water and feedwater treatments

 Condensate treatment
Raw Water and Feedwater
Treatments
 Ion Exchange Treatment
 Dissolved ions in raw water are removed or
exchanged by using ion exchange resins to
obtain the appropriate quality of treated
water for each boiler system.
 Demineralization – the removal of all
dissolved ions
 Softening – the exchange of calcium and
magnesium ions with sodium ions
 Softening
Softening Reactions Raw Water

R(-SO2Na)2 + Ca2+  R(-SO3)2Ca + 2Na+ Ca2+

HCO3-
Cl-
Mg2+ NaCl (regenerant)
SO42-
Na+
R(-SO2Na)2 + Mg2+  R(-SO3)2Mg + 2Na+ etc.
HSiO3-
etc.

Regeneration Softened water

HCO3-
R(-SO3)2Ca + 2Na+  R(-SO2Na)2 + Ca2+ Cl-
Na+ SO42-
R(-SO3)2Mg + 2Na+  R(-SO2Na)2 + Mg2+ • Softening treatment HSiO3-
etc.
 Demineralization
Demineralization Reactions Regeneration
H-Bed:
R(-SO3H)2 + Ca2+  R(-SO3)2Ca + 2H+
R(-SO3H)2 + Mg2+  R(-SO3)2Mg + 2H+
R-SO3H + Na+  R-SO3Na + H+
OH-Bed
RNOH + HCO3-  RNHCO3 + OH-
R(NOH)2 + SO42-  R(N)2SO4 + 2OH-
RNOH + Cl-  RNCl + OH-
RNOH + HSiO3-  RNHSiO3 + OH-
H-Bed:
R(-SO3)2Ca + 2H+  R(-SO3H)2 + Ca2+
R(-SO3)2Mg + 2H+  R(-SO3H)2 + Mg2+
R-SO3Na + H+  R-SO3H + Na+
OH-Bed
RNHCO3 + OH-  RNOH + HCO3-
R(N)2SO4 + 2OH-  R(NOH)2 + SO42-
RNCl + OH-  RNOH + Cl-
RNHSiO3 + OH-  RNOH + HSiO3-
 Demineralization
HCO3-
Ca2+
Cl-
Mg2+
SO42- CO2
Na+ HCl (regenerant) NaOH (regenerant)
HSiO3-
etc.
etc.

HCO3-
Cl- HCO3-
H+ SO42- Cl-
H-Bed OH-Bed
HSiO3- H+ SO42- H2O
etc. HSiO3-
etc.
CO2, H2CO3

• Demineralization treatment (2-beds and 1-degasifier type)

Raw Water and Feedwater
Treatments
 Deaeration
 The deaeration of boiler feedwater is carried out
to remove the corrosive dissolved gasses (oxygen
and carbon dioxide) for preventing corrosion
problems in boiler systems.
 Heating deaerator – dissolved gasses are removed
by heating feedwater up to the saturation
temperature (boiling point) under the inner
pressure of the deaerator
 Vacuum deaerator – dissolved gasses are removed
by reducing the pressure in the inside to the vapor
pressure of the water corresponding to the water
temperature.
Condensate Treatment
 Mechanical Treatment
 Filtration
 Used for removing corrosion products such as iron
oxides from condensate
 Types
 Cartridge type filter – removes corrosion products of 1 to
5 m or more in the particle size
 Precoat type filter – removes the suspended solids of
more than 0.5 m in the particle size
Condensate Treatment
 Mechanical Treatment
 Demineralization
 Removes the small amounts of dissolved
solids in condensate by using mixed bed
demineralizers (condensate polishers).
Internal Boiler Water
Treatment
 Boiler compounds

 Sludge dispersant

 Oxygen scavenger

 Corrosion inhibitors
Boiler Compounds
 Prevent scale formation and adjust ph
of boiler water to inhibit corrosion
 Phosphate based
 Non-phosphate
 Polymer based
 Chelating agents
 Sludge Dispersants
 Sludge dispersants
 Boiler sludge conditioners
 Applied for preventing the
accumulation of the
sludges on the bottom of • Precipitate of hydroxyapatite (without
polymer dispersant)
boiler drum and scaling on
the heating surface
 Application of synthetic
polymer dispersant

• Precipitate of hydroxyapatite distorted

under polymer treatment
 Oxygen Scavengers
 Oxygen scavengers
Type Chemical names
 Chemicals which
Hydrazine hydrate
remove dissolved Hydrazine based
Hydrazine sulfate
oxygen scavengers
oxygen from water Hydrazine phosphate

by their reduction Sodium sulfite

Sulfite based oxygen Sodium hydrogen
reactions, and scavengers sulfite
thereby inhibit the Sodium pyrosulfite
Saccharides
corrosion caused by Tannins
oxygen and water Other oxygen Hydrazide
scavengers L-ascorbic acid
Hydroquinone
Alkanolamines
 Corrosion Inhibitors
Corrosion Inhibitor Filming Mechanism
 Corrosion inhibitors Condensed water Inhibitor molecules
droplet
 Neutralizing amines
and filming amines Fe ++ 22

are used to prevent H++ Cl

the feed water or Corrosion deposit film

steam and Pipe wall

condensate lines
from corrosion