JCCP BoierWater

TS-011-15
November, 2015
MEDIUM TO HIGH PRESSURE BOILER TREATMENTS
For JCCP Training Course
Takashi Suzuki
Authorized Professional Engineer (Japan)
SUZUKI TECHNICAL CONSULTING LTD.
Ebina, Kanagawa, Japan
SUZUKI TECHNICAL CONSULTING LTD. 1

CONTENTS
Page
1. Outline of Boiler Systems 5
1.1 Definition of Boiler Systems 5
1.2 Classification of Boilers by Their Structures 6
1.3 A typical Water Flow of Boiler System 7
2. Troubles in Boiler System Operation and Their Causes 8
3. Outline of the Prevention Methods of Boiler Troubles Caused by Water 11
4. Scaling 12
4.1 Typical Scale Components Found in Boiler Systems 12
4.2 Formation of Scale 14
4.3 Thermal Conductivities of Boiler Scales and Metals 18
4.4 Influences of Scale Adhesion on Boiler Tubes 19
5. Scale Control Methods 24
5.1 External Treatments 24
5.1.1 Softening of feedwater (removal of hardness) 24
5.1.2 Demineralization of feedwater 26
5.2 Internal (Chemical) Treatments 32
5.2.1 Boiler compounds (phosphates) 32
6. Corrosion 33
6.1 Corrosion Reactions of Carbon Steel in Boiler Systems 33

Page
7. Corrosion Control Methods 35
7.1 External Treatments (Deaeration of Boiler Feedwater) 35
7.2 Internal (Chemical) Treatments 39
7.2.1 pH control of feedwater and boiler water 40
7.2.2 Use of oxygen scavengers 43
8. Carryover and Its Prevention Methods 49
8.1 Relationship between Boiler Pressure and the Allowable Maximum Silica
Concentration of Boiler Water 50
9. Management of Boiler Treatments 51
9.1 Determination of Feedwater and Boiler Water Quality Control Ranges 52
9.2 Determination of Blowdown Rate 53
9.3 Blowdown Methods 54
9.4 Determination of Chemical Treatment Program 55
9.5 Outline of Chemical Dosage Calculations 56
9.6 Chemical Injection Methods 57
9.6.1 Recommended chemical injection methods 57
9.6.2 Chemical injection points 58
9.7 Analytical Items for Feedwater and Boiler Water 59

Page
9.8 Preservation of Idle Boilers 60
9.8.1 Classification of preservation methods 60
9.9 Cleaning of Boilers 61
9.9.1 Critical scale thicknesses and amounts of high pressure boilers
required for their cleaning 62
9.9.2 Standard cleaning interval for heavy oil combustion water-tube
boilers 63
10. Energy and Water Savings in Boiler Systems 64
Appendix 69

1. Outline of Boiler Systems
1.1 Definition of Boiler Systems:
Boiler system is a system which is used to heat water and to generate
required steam or hot water.
The boiler system is generally composed of following units:
(a) Feedwater treatment unit*1 (demineralizer, etc.),
(b) Feedwater line,
(c) Deaerator,
(d) Boiler including preheater, superheater and desuperheater,
(e) Steam and condensate line,
(f) Condensate treatment unit,
(g) Wastewater treatment unit,
(g) Chemical injection unit.
*1 In case that the raw water is supplied from a river, a lake and so on, the raw water
treatment units (clarifier, filter, etc.) are required.

1.2 Classification of Boilers by Their Structures
(1) Cylindrical boilers (pressure : below 20 kgf/cm2) :
(a) Vertical boilers,
(b) Flue-tube boilers,
(c) Fire-tube boilers,
(d) Fire and flue-tube boilers.
(2) Water-tube boilers :
(a) Natural circulation boilers (pressure : low to high),
(b) Forced circulation boilers (pressure : low to high),
(c) Once-through boilers (pressure : above 75 kgf/cm2),
(d) Mini-circulation boilers (packaged type) (pressure :
below 30 kgf/cm2).
Note:
In this paper, treatment methods for medium to high pressure water tube
boilers except mini-circulation boilers are mainly discussed.

1.3 A typical Water Flow of Boiler System
Superheater Steam
Superheated
steam
To use points
Economizer Deaerator
Boiler
Blowdown water Feedwater Pump

preheater
Filter
Condensate
(from use points) Polisher
Condensate
Supply water tank
Filtered Feedwater Feedwater

Filter water tank Demineralizer Polisher tank pump

2. Troubles in Boiler System Operation and Their Causes
Kinds of Troubles in boiler system Causes of troubles

problems operation
Scaling Reduction of boiler efficiency, Leakage of hardness, silica, etc.,
Expansion or bursting of from softeners or demineralizers,
heating tubes by overheating Inadequate blowdown control,
Inadequate chemical treatment
Corrosion Corrosion damages of boiler Insufficient deaeration of feedwater,
systems including feedwater, Inadequate oxygen scavenger
steam and condensate lines, treatment,
Scaling troubles caused by Insufficient pH control of feedwater,
corrosion products boiler water and condensate
Carryover Reduction of steam quality, Excess concentration of boiler
Reduction of turbine efficiency water,
by scaling, Contamination of boiler water with
Reduction of product quality organic substances,
treated by the steam Fluctuation of boiler operation load,
Defects of steam separator
Carryover: Transferring of dissolved solids in boiler water into the steam line.
Expansion of boiler tube with scaling1)
1) KURITA WATER INDUSTRIES: KURITA HANDBOOK OF WATER TREATMENT,

The 2nd English Edition, p. 2-66 (1999)

Corrosion of boiler tube by dissolved oxygen1)


3. Outline of the Prevention Methods of Boiler Troubles
Caused by Water
Problems External treatment Internal (chemical) treatment
Scaling Demineralization or softening Use of boiler compounds

of feedwater including pH control agents
(and scale dispersants),
Adequate blowdown control
Corrosion Deaeration of feedwater Use of oxygen scavengers,

The pH control of feedwater,
boiler water and condensate,
Adequate blowdown control
Carryover *1 Removal of organic sub- Adequate blowdown control,

stances from feedwater, Minimization of boiler load
Sufficient silica removal from fluctuation
feedwater
*1 In case that a carryover trouble is caused by a defect of steam separator, the separator must be repaired
for preventing those troubles.
4. Scaling
4.1 Typical Scale Components Found in Boiler Systems
Mineral scales Metal oxide scales
Calcium carbonate : CaCO3 Ferric oxide : Fe2O3

Calcium silicate : CaSiO3 Magnetite : Fe3O4
Magnesium hydroxide : Mg(OH)2 Nickel oxide : NiO
Magnesium silicate : MgSiO3 Cupric oxide : CuO
Hydroxyapatite : 3Ca3(PO4)2.Ca(OH)2 Metallic copper : Cu
Zinc hydroxide : Zn(OH)2
Basic pyro-zinc-silicate : Zn4(OH)2Si2O7.H2O
Silica : (SiO2)n
Main scale components of medium to high pressure boilers are generally silica and
metal oxides (corrosion products).
Typical scale analyses of medium to high pressure boilers1)
Sample A B C
Boiler pressure (kgf/cm2) 113 92 69
Calcium oxide (CaO) Trace Trace 2.0
Magnesium oxide (MgO) Trace Trace Trace
Iron oxide (Fe2O3) 99.7 88.9 91.2
Copper oxide (CuO) Trace Trace Trace
Acid insoluble matters*1 0.2 4.9 0.5
Sulfuric acid anhydride (SO3) Trace Trace Trace
Carbonic acid anhydride (CO2) Trace Trace Trace
Phosphoric acid anhydride (P2O5) Trace 3.7 3.3
Ignition loss 3.3 2.5 2.2
Zinc oxide (ZnO) - Trace -
Aluminum oxide (Al2O3) Trace Trace Trace
(unit: w%)
*1 The main components of acid insoluble matters are silica (SiO2)n and silicates.

4.2 Formation of Scale
(1) Mineral scales (except silica):
(a) A violent evaporation of boiler water on boiler tubes leaves almost all
dissolved salts in water as deposits on the surfaces.
(b) The contact of boiler water with the deposits dissolves water soluble salts,
however, the hard soluble ones like calcium carbonate remain on the
surface.
(c) The repetition of (a) and (b) forms hard scales on boiler tube surfaces.
(2) Metal oxide scales:
(a) Most of the corrosion products (metallic oxides) of boiler tubes adhere to
their surfaces because of the high surface temperature and pH.
(b) When a part of corrosion products in feedwater, steam and condensate
lines comes into the boiler, they deposit on the boiler tube surfaces as
metal oxides because of the high surface temperature and pH.

(3) Silica scale (on turbine blades, etc.):
(a) As the high water temperature and pH increase the solubility of silica*1,
silica in boiler water dissolves into steam and transfers to the steam line.
(b) Temperature reduction of steam and the steam condensation at the use
points causes the silica deposition there because of the solubility reduction.
*1 Solubility of most mineral scales like calcium carbonate is reduced by pH
and water temperature increases. However, the solubility of silica is
increased by increasing pH and temperature.

(1) Relationship between the solubility of calcium
carbonate and temperature
100
80
Calcium hardness
(mg CaCO 3 /L)
60
Solubility of CaCO3
40
20
0
0 50 100 150 200
Temperature ()

(2) Relationship among the solubility of silicic acid,
pH and water temperature1)
Solubility of s ilicic a cid 1500
(1) 200 oC
1000
(m g SiO 2 /L)
(2) 155 oC
(3) 90 oC
500
(4) 22 oC
0
7 8 9 10
pH
1) K. Goto: J. Chem. Soc. Japan, Vol. 76, No12, p. 1364 (1955)

4.3 Thermal Conductivities of Boiler Scales and Metals
Substances Thermal conductivity

(kcal/m.h.oC)
Calcium carbonate 0.4 - 0.6
Calcium phosphate 0.5 - 0.7
Silica 0.2 - 0.4
Hematite (Fe2O3) 3-5
Magnetite (Fe3O4) 1
Carbon steels 40 - 60
Stainless steel (SUS304) 14
Copper 320 - 360
Thermal conductivities of scales are much smaller than those of metals. Therefore,
scale adhesion on boiler tubes widely reduces the thermal efficiency of boiler.

4.4 Influences of Scale Adhesion on Boiler Tubes
Tube Tube Scale
(5 mm) (5 mm) (1 mm)
TG TG
Combustion Boiler
gas water TTG TTW
TTG TTW TW
TW TS
Laminar layers
A scale adhesion on boiler tube water side disturbs the heat transfer from the tube to
boiler water, and increases the tube wall temperature. As the result, the heat transfer
efficiency is reduced.
(1) Increase of tube wall temperature by scale adhesion
(a typical calculation results)
Scale thickness Tube wall temperature (oC)

(mm) k* = 0.5 k* = 2.0
0 190 190
1 390 240
2 590 290
3 790 340
4 990 390
5 1190 440
* k : thermal conductivity of scale (kcal/m.h.oC)

Note : Heat flux ; 100,000 kcal/m2.h

(2) Reduction of the allowable tensile stress of carbon
steel tubes by tube wall temperature increase1)
12
Allowable tensile stress (kg/mm )

2
10 (1) STB 410 (JIS)
6 (2) STB 340 (JIS)
0
300 350 400 450 500
Temperature ()
An increase of tube wall temperature by scale adhesion reduces the mechanical strength
of tube. As the result, the allowable tensile strength of tube is also reduced.
1) H. Ishikawa, T. Kurosawa: Karyoku Hatsuden, Vol. 21, No. 4, p. 386 (1970) (in Japanese)

An extreme temperature increase changes crystal structure of metal, and
reduces the mechanical strength. Normal crystal structure of carbon steel
Tubes is pearlite structure. However, the structure is spheroidized by exposing
at a high temperature during a long time.
Following Table1) shows the temperatures changing the crystal structure of
carbon steels during 10,000 hours of their uses.
Kinds of steel (JIS) Composition Spheroidized

temperature ()
STB410 C: below 0.18 500 520
STBA12 Mo: 0.45 0.65 520 540
SYBA22 Cr: 0.80- 1.25, Mo: 0.45 0.65 550 580
STBA23 Cr: 1.0 1.5, Mo: 0.45 0.65 550 580
STBA24 Cr: 1.9 2.6, Mo: 0.87 1.13 550 590
1) T. Abe, et al.: Central Research Institute Electric Power Industry Report No. 277014, p. 8 (1973)

(3) An increase of boiler fuel consumption by scale adhesion
Increase of fuel consumption (%) Thermal conductivity of scale : 0.5 kcal/m.h.oC
0
0 0.2 0.4 0.6 0.8 1
Scale thickness (mm)
Since scale adhesion on boiler tubes reduces the thermal efficiency, it increases the fuel
consumption for keeping a constant steam generation.

5 Scale Control Methods
5.1 External Treatments
5.1.1 Softening of feedwater (removal of hardness):

In case of low pressure boilers, the main components of scales
are calcium and magnesium compounds like calcium carbonate
and magnesium hydroxide.
Therefore, the removal of calcium and magnesium ions (softening)
from the boiler feedwater is an effective scale prevention method.
Generally, cation exchange resins (Na-type) are used for removing
hardness from boiler feedwater. Such water treatment equipment
is called softener.
Softened feedwater is applicable for cylindrical boilers with the
operational pressure of below 30 kgf/cm2 and water tube boilers
with the pressure of below 20 kgf/cm2.

Ion exchange reactions in softener
(a) Softening :
R(-SO3Na)2 + Ca2+ R(-SO3)2Ca + 2Na+ ------------------------ (5.1)

R(-SO3Na)2 + Mg2+ R(-SO3)2Mg + 2Na+ ------------------------ (5.2)
(b) Regeneration (using around 10 % NaCl solution) :
R(-SO3)2Ca + 2Na+ R(-SO3Na)2 + Ca2+ -------------------------- (5.3)

R(-SO3)2Mg + 2Na+ R(-SO3Na)2 + Mg2+ ------------------------ (5.4)

5.1.2 Demineralization of feedwater
Removal of the all kinds of dissolved salts (cations and anions) from
water is called demineralization.
Cation and anion exchange resins (H-type and OH-type respectively)
are use for removing cations and anions.
Demineralized feedwater is applicable for low to high pressure
boilers of any types.
Demineralized feedwater must be used for boilers with the
operational pressure of 30 kgf/cm2 or more.
Equipment producing demineralized water is called demineralizer.
The details about demineralizers should be referred to the text book
of No. TS-002-15 for this seminar.
(1) Ion removing reactions
(a) Cation Exchange Resin :
R(-SO3H)2 + Ca2+ R(-SO3)2Ca + 2H+ ----------------- (5.5)
R(-SO3H)2 + Mg2+ R(-SO3)2Mg + 2H+ ---------------- (5.6)
R-SO3H + Na+ R-SO3Na + H+ -------------------------- (5.7)
R-SO3H + K+ R-SO3K + H+ ----------------------------- (5.8)
(b) Anion Exchange Resin :
RNOH + HCO3- RNHCO3 + OH- ------------------- (5.9)
R(NOH)2 + SO42- R(N)2SO4 + 2OH- --------------- (5.10)
RNOH + Cl- RNCl + OH- ---------------------------- (5.11)
RNOH + HSiO3- RNHSiO3 + OH- ------------------ (5.12)
27
SUZUKI TECHNICAL CONSULTING LTD.
(2) Regeneration Reactions
(a) Cation Exchange Resin :
R(-SO3)2Ca + 2H+ R(-SO3H)2 + Ca2+ ---------------------------- (5.13)
R(-SO3)2Mg + 2H+ R(-SO3H)2 + Mg2+ --------------------------- (5.14)
R-SO3Na + H+ R-SO3H + Na+ -------------------------------------- (5.15)
R-SO3K + H+ R-SO3H + K+ ----------------------------------------- (5.16)
(b) Anion Exchange Resin :
RNHCO3 + OH- RNOH + HCO3- ------------------------------- (5.17)
R(N)2SO4 + 2OH- R(NOH)2 + SO42- --------------------------- (5.18)
RNCl + OH- RNOH + Cl- ----------------------------------------- (5.19)
RNHSiO3 + OH- RNOH + HSiO3- ------------------------------ (5.20)
Note: The ion removing reaction and regeneration reaction are
reverse reactions each other.
(3) Schematic process of demineralization
Ca2+ HCO3-
HCO3- HCO3-
Mg2+ Cl- Cl- Cl-
Na+ SO42- H+ SO42- H2O
H+ SO42-
K+ HSiO3- HSiO3-
etc. HSiO3-
etc. etc.
etc.
CO2, H2CO3
CO2
Cation exchange unit Degasifier Anion exchange unit

(4) Flow sheet of typical demineralizers
Raw water
HCl NaOH
(Regenerant) (Regenerant)
Regeneration
wastewater
Product
Regeneration water
wastewater
Cation exchange unit Degasifier Anion exchange unit

(5) Operation of demineralizer
(a) Demineralization (water production),

(b) Back-washing,
(c) Settling of resins,
(d) Regeneration*1
(e) Displacement of regenerant solutions with water,
(f) Rinsing.
*1 : Generally, the 5 to 7 % of HCl or NaOH solution is used for the
regeneration of cation or anion exchange resins.
Note: The breakthrough capacity (operation capacity) of resin is generally
designed at the 50 to 60% of the total capacity*2 because the higher
breakthrough capacity makes the regeneration more difficult.
*2 :Total capacity of cation exchange resin: 100 g CaCO3/L resin or more
Total capacity of anion exchange resin: 65 g CaCO3/L resin or more

5.2 Internal (Chemical) Treatments
5.2.1 Boiler compounds (phosphates) :
Basically, the formation of mineral scale is prevented by using demineralized
water as boiler feedwater in case of medium to high pressure boilers.
However, an unexpected leakage of hardness and so on from demineralizers
or water cooled steam condensers causes their scaling in boilers.
Boiler compounds are used for preventing such scale formation.
Phosphates react with hardness components and rapidly form fine deposits of
calcium phosphate. Those deposits are discharged from the boiler together
with the blowdown water. Then the scaling on the heat transfer surfaces is
minimized.
3Ca2+ + 2PO43- Ca3(PO4)2 ------------------------------------------------------------ (5.21)

6. Corrosion Problems
6.1 Corrosion Reactions of Carbon Steel
In neutral to alkaline water like boiler systems, carbon steel is

electrochemically corroded by reacting with oxygen and water.
At anode : Fe Fe2+ + 2e- -------------------------------------------------------- (6.1)
At cathode : H2O + 1/2O2 + 2e- 2OH- ----------------------------------------- (6.2)
Then following reactions proceed :
Fe2+ + 2OH- Fe(OH)2 --------------------------------------------------------- (6.3)
2Fe(OH)2 + 1/2O2 + H2O 2Fe(OH)3 or Fe2O3.3H2O ---------------------- (6.4)
This corrosion product is dehydrated by heat :
Fe2O3.3H2O 2FeO.OH + 2H2O -------------------------------------------------- (6.5)
2FeO.OH Fe2O3 + H2O ----------------------------------------------------------- (6.6)
Alkaline corrosion (at the pressure of 90 kgf/cm2 or more) :

Fe + 2NaOH Na2FeO2 + H2 ------------------------------------------------------ (6.7)
3Na2FeO2 + 4H2O 6NaOH + Fe3O4 + H2 ------------------------------------ (6.8)

(1) Relationship between caustic alkali concentration and the
alkaline corrosion of carbon steel at elevated temperatures1)
40
30 Test period : 100 h

(1) 400 oC
(2) 310 oC
Weight loss
(mg/cm )
2
20
10 (1)
(2)
0
0.1 1 10 100 1000
NaOH (g/L)
A violent boiler water evaporation highly concentrates alkali on boiler tube surfaces and
causes the alkaline corrosion of boiler tubes in boiler water containing free alkali.
1) S. Fukui, M. Atsukawa: Karyoku Hatsuden, Vol. 11, No. 6, p. 537 (1960) (in Japanese)

7. Corrosion Control Methods
7.1 External Treatments (Deaeration of Boiler Feedwater)
Heating deaeration is generally applied for medium to high
pressure boilers.
Spray-tray type deaerators are widely used for removing the
dissolved oxygen from feedwater. A part of generated stream is
introduced into the deaerator to heat the water until the oxygen is
released.
The dissolved oxygen concentration is reduced to 7 ppb or less.
In a case of vacuum deaerator, the dissolved oxygen concentration
of treated water is around 100 ppb. This oxygen level is not enough
to prevent the corrosion problems of medium to high pressure
boilers.

Outline of spray tray type deaerator

(1) Relationship among the dissolved oxygen concentration
of water, atmospheric pressure and temperature
16
14 (1) 760 mmHg

(2) 60 mm Hg
12
Dissolved oxygen
10
(mg/L)
8
(1)
6
2 (2)
0
0 20 40 60 80 100 120
Temperature ( )
Generally, an increase of water temperature or a reduction of atmospheric pressure is

applied for removing dissolved oxygen from water.

(2) Carbon steel corrosion prevention by oxygen removal1)
0.15
Room temperature
Test period : 48 h
0.1
Weight loss
(mg/cm )
2
0.05
0
0.01 0.1 1 10
Dissolved oxygen (mg/L)
Oxygen removal effectively prevents the corrosion of various metals in closed water
systems like boilers.
1) H. H. Uhlig, et al.: J. Electrochem. Soc., Vol. 102, p. 59 (1955)
7.2 Internal (Chemical) Treatment
Following internal chemical treatments are widely applied for medium

to high pressure boilers:
(a) The pH control of feedwater and boiler water,
(b) Use of boiler water treatment chemicals:
(i) Coordinated phosphate treatment*1 (medium to high pressure),
(ii) Volatile treatment (high pressure),
(iii) Oxygen treatment*2 (high pressure).
*1 Use of boiler compounds with the Na/PO4 mole ratio of 2.8 or less
(no alkaline corrosion)
*2 Treatment controlling the dissolved oxygen concentration of boiler
feedwater at 0.02 to 0.2 mg/L to passivate steels composed of
boiler.

7.2.1 pH control of feedwater and boiler water
(1) Corrosion control of carbon steel by pH increase1)
1.2
Aerated softened water

1 Room temperature
0.8
Corrosion rate
(mm/y)
0.6
0.4
0.2
0
2 4 6 8 10 12 14
pH
The pH increase is an effective corrosion control method for steels. However, the
presence of free alkali may cause the alkali corrosion of high pressure boilers.
1) W. Whitman, et al.: Ind. Eng. Chem., Vol. 16, p. 665 (1924)

(2) Corrosion control of copper by pH control1)
0.8
Room temperature
0.6 Test period : 48 h
NH4OH
Weight loss
(mg/cm )
2
0.4 HCl
0.2
Morpholine
0
2 4 6 8 10 12
pH
The corrosion rates of copper and copper alloys are minimized in neutral to weakly
alkaline pH range. The increase or decrease of pH promotes their corrosion. In an
alkaline range, the corrosion rate is widely different by the kinds of alkaline
compounds applied. The influence of neutralizing amines on copper corrosion is quite
small comparing with ammonia.
1) T. Kondo, H. Ueki: Yosui-to-Haisui, Vol.9, No. 5, p. 364 (1967) (in Japanese)
(3) Required dosages of alkalis for controlling pH
(demineralized water)
(a) Non-volatile alkalis:
Chemicals Required dosage*1 for pH control
pH = 9 pH = 10 pH = 11
NaOH 0.4 4 40
Na3PO4 1 10 100
Na2HPO4 300 - -
(b) Volatile alkalis:

Chemicals Required dosage*1 for pH control Distribution ratio*2
pH = 8 pH = 9
Ammonia (NH3) 0.03 0.3 7 10
Hydrazine (N2H4) 0.5 5 0.05 0.2
Morpholine 0.5 5 0.5 1.3
Cyclohexylamine 0.1 1 29
*1 Approximate concentration (mg/L)

*2 Distribution ratio of chemical in steam and in water; The ratio is changed by temperature change.
7.2.2 Use of oxygen scavengers
(1) Features of typical oxygen scavengers
Chemicals Features
Hydrazine Volatile, excellent effect
Carcinogen, highly toxic
Diethylhydroxylamine (DEHA) Volatile,
Relatively high dosage, formation of acid
Methyl-ethyl-ketoxime (MEKO) Volatile,
Carcinogen, high dosage, formation of acid
Carbohydrazide Volatile,
Generation of hydrazine (in boiler)
Erythorbic or ascorbic acid salts Non-toxic, high reaction rate,
High dosage, non-volatile
Saccharides Non-toxic,
Low reaction rate, high dosage, non-volatile
Sodium sulfite Low toxicity, high reaction rate,
High dosage, non-volatile
Oxygen scavengers are chemicals removing dissolved oxygen in water.

(2) Oxygen removing reactions of typical oxygen scavengers
(a) Hydrazine : N2H4 + O2 N2 + 2H2O ------------------------------------- (7.1)
(b) DEHA : 4(C2H5)2NOH + 9O2 8CH3COOH + 2N2 + 6H2O -------- (7.2)
(c) Saccharide, Erithorbate and Ascorbate :

-C- -C-
C - OH + 1/2O2 - C = O + H2O --------------------------- (7.3)
C - OH -C=O
-C- -C-
(d) Sodium sulfite : Na2SO3 + 1/2O2 Na2SO4 -------------------------- (7.4)

(3) Decomposition reactions of hydrazine and sulfites
(a) Hydrazine at the temperature of 220 oC (25 kgf/cm2) or more :

3N2H4 4NH3 + N2 ----------------------------------------------------- (7.5)
An extreme excess dosing of hydrazine will cause the
corrosion of copper and copper alloys in condensate lines
because of ammonia generation.
(b) Sulfites at the temperature of 285 oC (65 kgf/cm2) or more :
4Na2SO3 Na2S + 3Na2SO4 ----------------------------------------- (7.6)
Na2SO3 + H2O 2NaOH + SO2 ------------------------------------- (7.7)
The sulfites are never used for boilers with the pressure of 65
kgf/cm2 or more to avoid the generation of corrosive gasses
shown above.

(4) Oxygen scavenging effects of various oxygen scavengers1)
7 Test boiler
Feedwater : Softened water(40)
Dissolved oxygen (mg/L)
6 Pressure : 20 kgf/cm2
Boiler water pH : 11.5 - 11.8
5
4
3 Sodium erythorbate
2 MEKO
1 DEHA
Hydrazine
0
0 10 20 30 40 50 60
Dosage (mg/L)
1) T. Suzuki: Corrosion and Fouling Control for Petroleum Refining Plants, Boilers and
Cooling Water Systems, p. 23, JCCP (2003)

(5) Required dosages of various oxygen scavengers
(experimental data)
Oxygen scavenger Required dosage*1 (mg/L)
Hydrazine 1.4
DEHA 2.8
MEKO 6.1
Sodium erythorbate 8.9
*1 Required dosage: The dosage which is required for removing the

1 mg/L of dissolved oxygen (experimental data)
(6) Toxicities of DEHA and hydrazine1)
Chemical Ames test Micronucleus LD50

test (mouse) (mouse, oral)
DEHA Negative - 2,150 mg/kg
Hydrazine Positive Positive 83 mg/kg
hydrate
Note: Fish toxicities of DEHA and hydrazine:

DEHA;
LC50, 96 h (Japanese dace) ; 1,393 mg/L
Hydrazine hydrate;
LC50, 96 h (golden orfe) ; 1.5 mg/L as N2H4
LC50, 24 h (killifish) ; 11.4 mg/L as N2H4
1) T. Suzuki: Corrosion and Fouling Control for Petroleum Refining Plants, Boilers and
Cooling Water Systems, p. 24, JCCP (2003)

8. Carryover and Its Prevention Methods
(1) Prevention of the carryover of organic substances:
(a) Chemical cleaning of new boilers;
Removal of oils and fats adhered to boilers during their manufacturing,
(b) Removal of organic substances by pretreatment of feedwater;
Removal of humic acid and so on by activated carbon, oxidation,
sedimentation treatments, etc.
(2) Prevention of the carryover of silica:
(a) Sufficient silica removal from feedwater with sufficient operation control
of demineralizers and polishers,
(b) Control of boiler water silica concentration and pH according to the
feedwater and boiler water quality control limits,
(3) Maintenance and operation control of boilers:
(a) Sufficient maintenance works for steam and water separator,
(b) Minimization of boiler load fluctuation.

8.1 Relationship between Boiler Pressure and the Allowable
Maximum Silica Concentration1)
60
(50)
(For water tube boilers)
Allowable silica conc.
40
(mg SiO2/L)
(20)
20
(5)
(2) (0.2)
(0.3)
0
0 50 100 150 200 250
Pressure (kgf/cm 2 )
1) Japan Society of Industrial Standards: JIS B8223-2006, Water conditioning for boiler
feed water and boiler water (2006)

9. Management of Boiler Treatments
(1) Determination of the control ranges of feedwater and boiler

water qualities according to the structure, pressure and so
on of an aimed boiler,
(2) Selection of a suitable water treatment method, blowdown
method, chemical injection method, etc., to maintain the
target water qualities,
(3) Monitoring of the water qualities and the treatment effects
by the water analyses, etc., and an improvement of the
operation control method if necessary.

9.1 Determination of Feedwater and Boiler Water Quality
Control Ranges
(1) Select a suitable feedwater and boiler water quality standard from the
national industrial standards*1, standards provided by the boiler
manufacturers and so on according to the aimed boiler structure,
pressure, etc.
(2) The selected standard generally shows the external feedwater treatment
method, the basic chemical boiler water treatment method and so on.
(3) When specialty chemicals developed by chemical suppliers, such as
oxygen scavengers and neutralizing amines, are used, apply the
suppliers water quality standard.
*1 Refer to JIS B8223-2006, Water conditioning for boiler feed water and
boiler water, attached with this technical bulletin.
(See the Appendixes 2 to 6 of this paper.)
9.2 Determination of Blowdown Rate
(1) Determination of cycles of concentration:

N = F/B ------------------------------------------------------------------------ (9.1)
where
N : cycles of concentration,
F, B : feedwater quantity and blowdown rate respectively (t/h)
Note : In case of water-tube boilers of demineralized water feeding, the
cycles of concentration is generally set at 50 to 100.
(2) Calculation of blowdown rate:
B = E/(N - 1) ------------------------------------------------------------------ (9.2)
where
E : evaporation rate (t/h),
(3) Calculation of feedwater quantity:
F = B + E ---------------------------------------------------------------------- (9.3)

9.3 Blowdown Methods
(1) Kinds of blowdown methods:

(a) Continuous blowdown,
(b) Intermittent blowdown.
(2) General blowdown points:
(a) Water tube boilers : from upper drum,
(b) Once-through boilers : from steam and water separator.
Note: Advantages of continuous blowdown;
(a) Easy to keep the boiler water quality within the control range,
(b) Able to reduce the blowdown rate comparing with that of
intermittent blowdown,
(c) Possible to recover the heat from the blowdown water by using a
heat exchanger, etc.

9.4 Determination of Chemical Water Treatment Program
(1) Determination of basic treatment program:
According to the selected feedwater and boiler water quality criteria and
the environmental requirement, an appropriate basic chemical water
treatment program (pH control agents for feedwater and boiler water,
and boiler compounds) is selected from following ones :
(a) Coordinated phosphate treatment, (b) Volatile treatment, and
(c) Oxygen treatment.
(2) Selection of oxygen scavenger:
According to the selected basic chemical treatment program and the
environmental requirement, appropriate kinds of oxygen scavenger is
selected.
(3) Determination of chemical dosages:
Dosages of selected chemicals are determined by referring to the selected
feedwater and boiler water criteria, and chemical suppliers guidelines.

9.5 Outline of Chemical Dosage Calculations
(1) pH control agents (caustic alkalis, phosphates, hydrazine, ammonia

and neutralizing amines):
Refer to the section 7.2.1 (3) (page 42).
(2) Oxygen scavengers :
DOS = FFDOCO K ---------------------------------------------------- (9.4)
where
DOS : dosing rate of oxygen scavenger (g/h)
F : amount of feedwater (t/h)
FDO : dissolved oxygen concentration in feedwater (g/t) or (mg/L)
CO : theoretical oxygen scavenger coefficient for removing 1 mg/L
of dissolved oxygen (-)
K : safety allowance (generally 1.5 to 2.0)

9.6 Chemical Injection Methods
9.6.1 Recommended chemical injection methods
(1) Automatically controlled chemical injection (proportionally to

feedwater amount) for all types of boilers,
(2) Continuous chemical injection for boilers under the constant and
stable operational conditions.
Note :
Intermittent chemical injection is scarcely recommended because it is
difficult to keep the feedwater and boiler water qualities in their
appropriate control ranges, and it will deteriorate the chemical water
treatment effect.

9.6.2 Chemical injection points
(1) Boiler compounds :

Feedwater line nearest to the boiler,
(2) Oxygen scavengers :
Boiler without deaerator : Feedwater line far from the boiler,
Boiler with deaerator : Volatile ones ; Before the deaerator,
Non-volatile ones ; After the deaerator,
(3) Neutralizing amines :
Feedwater line far from the boiler.
Note :
In case of a boiler equipped with a desuperheater, all non-volatile
chemicals must be injected into feedwater line after the branch
point to the desuperheater.

9.7 Analytical Items for Feedwater and Boiler Water
For feedwater For boiler water

pH pH
Electrical conductivity M-alkalinity
Hardness P-alkalinity
Oils and fats Total evaporation residue
Dissolved oxygen Electrical conductivity
Iron Chloride ion
Copper Phosphate ion
Silica Silica
Volatile oxygen scavengers*1 Oxygen scavengers*2
*1 Hydrazine, DEHA, etc.

*2 For all types of oxygen scavengers

9.8 Preservation of Idle Boilers
9.8.1 Classification of preservation methods
(1) Dry preservation (for a long term preservation) :

(a) Use of desiccants*1
*1 Synthetic zeolites, silica gels, activated alumina, quick lime, etc.
(b) Sealing with nitrogen gas,
(2) Wet preservation (for a short to medium term preservation) :
(a) Oxygen scavengers*2 + pH control agents,
*2 Hydrazine, DEHA, sodium sulfite, etc.
Note: Boilers are often attacked by corrosion during their preservation

because of air entering into their insides.

9.9 Cleaning of Boilers
Deaerated demineralized water is fed to medium to high pressure boilers.
Moreover, appropriate internal chemical treatments are applied for them to
minimize the problems caused by water.
However, metal oxides (corrosion products) are gradually adhered to the
inside of heating tubes, and reduce the boiler efficiency. The allowable scale
thickness is a very thin because of the high heat flux and high water
temperature of boiler. Therefore, a periodical boiler cleaning is required for
keeping the safe and efficient boiler operation. Chemical cleaning is generally
applied for the cleaning of boiler insides.
The furnace side of boiler is also fouled with ashes containing metal oxides,
sulfur compounds, etc. Those ashes must be periodically removed to keep
the boiler efficiency and to minimize corrosion.
Water jet cleaning is usually applied for furnace side cleaning.

9.9.1 Critical scale thicknesses and amounts of high pressure
boilers required for their cleaning1)
Fuel Pressure
80 kgf/cm2 120 kgf/cm2 180 kgf/cm2 > 218.3 kgf/cm2
Coal - 0.30 - 0.45*1 0.25 - 0.35 -
- (90 - 135)*2 (75 - 105) -
Mixture of coal 0.30 - 0.40 0.25 - 0.35 0.20 - 0.30 -
and heavy oil (90 - 120) (75 - 105) (45 - 60) -
Heavy oil 0.25 - 0.35 0.20 - 0.30 0.15 - 0.25 0.08 - 0.12
(75 - 105) (60 - 90) (45 - 75) (24 - 36)
*1 Critical scale thickness (mm)
*2 Critical scale amount (mg/cm2)
1) Karyoku Hatsuden Gijutsu Kyokai: Karyoku Hatsuden, Vo. 23, No. 4, p. 86 (1972)
(in Japanese)
9.9.2 Standard cleaning interval for heavy oil combustion
water-tube boilers1)
Type of boiler Operational pressure (kgf/cm2) Cleaning interval (year)

80 100 5-7
Circulation 120 class 3-5
180 class 2-3
120 class 2-5
Once-through 180 class 1-3
> 218.3 1-3
Since a boiler of the higher operational pressure has the thinner critical scale thickness,
its cleaning interval becomes the shorter.
1) Karyoku Hatsuden Gijutsu Kyokai: Karyoku Hatsuden, Vo. 23, No. 8, p. 106 (1972)
(in Japanese)

10. Energy and Water Savings in Boiler Systems
(1) Recovery of condensate as feedwater:
(a) Filtration of condensate,
(b) Polishing of condensate by using ion exchange resins.
(2) Reduction of blowdown:
(3) Heat recovery from blowdown water by using heat exchanger,
(4) Prevention of steam leakage:
(a) Repair of steam leaking points in steam lines,
(b) Use of advanced steam traps.
(5) Minimization of thermal efficiency drop by scaling:
(a) Keeping of the feedwater and boiler water qualities in appropriate
ranges.
(6) Appropriate control of boiler operation conditions:
(a) Keeping of appropriate boiler operation load,
(b) Appropriate control of the air and fuel ratio.
(1) Replacement of steam traps
Replacement of old mechanical type steam traps with advanced
orifice type steam traps remarkably reduces the steam leakage
from steam traps as shown below1).
Factory Pressure Mechanical steam trap Orifice steam trap

of piping Drain Steam leakage Drain Steam leakage
(kgf/cm2) (kg/h) (kg/h) (kg/h) (kg/h)
A 16 8.8 1.0 9.0 0
B 11 9.2 4.6 10.4 0
C 13 9.8 4.5 9.5 0
D 13 12.1 4.4 13.0 0
E 4 30.0 3.1 18.0 0
F 1 235 12.4 224 0
G 4 3.4 0.8 4.6 0
1) From the technical bulletin of TAS Corporation (2010)
(2) Relationship between drain ratio and the amount of steam
leakage under the application of an orifice steam trap1)
Steam leakage (%) 100

80
Application range
60
40
20
0
0 20 40 60 80 100
Drain ratio (%)
1) From the technical bulletin of TAS Corporation (2010)

(3) A typical relationship between boiler operation load and the
thermal efficiency
100
80
Efficiency (%)
60
40
20 40 60 80 100 120
Load (%)

(4) Recommended air ratio for various boilers
Boiler Recommended air ratio

Operation (ratio against the theoretical one)
capacity
load (%)
(ton steam/h) Liquid fuels Gaseous fuels
Above 30 50 100 1.1 1.25 1.1 1.2

10 30 50 100 1.15 1.3 1.15 1.3
5 10 50 100 1.2 1.3 1.2 1.3
Below 5 50 100 1.2 1.3 1.2 1.3

Appendix 1.
Relationship among boiler pressure, the saturation temperature
and the enthalpy (thermal energy)
Pressure Saturation Enthalpy Pressure Saturation Enthalpy

(atm) temp. (oC) (kcal/kg) (atm) temp. (oC) (kcal/kg)
1 99.09 99.17 70 284.47 301.0
5 151.11 152.1 80 293.61 312.8
7 164.17 165.7 100 309.53 334.3
10 179.04 181.3 120 323.15 354.0
20 211.39 215.9 140 335.10 372.8
30 232.76 239.6 160 345.75 391.3
40 249.18 258.4 180 355.53 410.8
50 262.69 274.3 200 364.07 431.6
60 274,28 288.3 225.56 374.15 503.3

Appendix 2
Feedwater and boiler water qualities of water tube boilers (circulation boilers) (JIS B8223-2006)
*1 Keep possibly low.

Appendix 3
Feedwater and boiler water qualities of water tube boilers (circulation boilers) (JIS B-8223-2006)
*1 Keep possibly low.

Appendix 4
Feed water quality of once-through boilers (JIS B8223-2006)
Operating pressure Above 75 to 100 Above 100 to 150 Above 150 to 200 Above 200
Division
(kfg/cm)
Treatment method Volatile Oxygen Volatile Oxygen Volatile Oxygen Volatile Oxygen
treatment treatment treatment treatment treatment treatment treatment treatment
pH (at 25 ) 8.5 9.7 6.5 9.3 8.5 9.7 6.5 9.3 8.5 9.7 6.5 9.3 8.5 9.7 6.5 9.3
Electrical
conductivity Below 0.3 Below Below 0.3 Below 0.2 Below 0.3 Below 0.2 Below 0.25 Below 0.2
(S/cm) (at 25 ) 0.2
Dissolved oxygen
Feedwater
Below 7 20 - 200 Below 7 20 - 200 Below 7 20 - 200 Below 7 20 200

(g O/L)
Iron (g Fe/L) Below 30 Below 20 Below 20 Below 10 Below 20 Below 5 Below 10 Below 5
Copper (g Cu/L) Below 10 Below 10 Below 5 Below 10 Below 3 Below 5 Below 2 Below 2
Above 10 - Above 10 - Above 10 - Above 10 -
Below 40* Below 20 Below 30* Below 20 Below 20 Below 20 Below 20 Below 20
Below 20** Below 20**
* Apply for a boiler with water and steam separator.

**Apply for a boiler without water and steam separator.
Note: Steam quality for electric power generation: (a) Electrical conductivity; Below 0.3 S/cm,
(b) Silica; Below 20 g SiO2/L
Appendix 5
Feed water quality of once-through boilers for the operation start-up under
the volatile treatment (JIS B8223-2006)
Water circulation before Water circulation during

Operation process ignition (cold cleanup of temperature and pressure Normal operation
Division
boiler) raising (hot cleanup of boiler)
Normal operation pressure Above 150 Above 200 Above 150 Above 200 Above 150 Above 200
(kfg/cm) to 200 to 200 to 200
pH (at 25 ) 8.5 9.7 8.5 9.7 8.5 9.7 8.5 9.7 8.5 9.7 8.5 9.7
Electrical conductivity Below 1 Below 1 Below 1 Below 1 Below 1 Below 1
(S/cm) (at 25 )
Dissolved oxygen Below 40 Below 20 Below 10 Below 10 Below 7 Below 7
Feedwater
Economizer (mg O/L)

inlet
Iron (g Fe/L) Below 200 Below 100 Below 100 Below 50 Below 30 Below 30
Copper (g Fe/L) Below 20 Below 20 Below 20 Below 10 Below 5 Below 5
Hydrazine (g N2H4/L) Above 20 Above 20 Above 20 Above 20 Above 10 Above 10
Silica (g SiO2/L) Below 30 Below 30 Below 30 Below 30 Below 30 Below 30
Furnace Electrical conductivity Below 1 Below 1 Below 1 Below 1 - -
water tube (S/cm) (at 25 )
wall outlet
Iron (g Fe/L) Below 300 Below 300 Below 200 Below 100 - -

Appendix 6
Feed water quality of once-through boilers for the operation start-up under
the oxygen treatment (JIS B8223-2006)
Process Ignition and water circulation Water circulation during Normal operation
Division
under heating temperature and pressure raising

Normal operation Above 150 to Above 200 Above 150 to Above 200 Above 150 to Above 200
pressure (kfg/cm)* 200 200 200
pH (at 25 ) 6.5 9.3 6.5 9.3 6.5 0.3 6.5 9.3 6.5 9.3 6.5 9.3
Electrical conductivity Below 5 Below 5 Below 3 Below 3 Below 2 Below 2

(S/cm) (at 25 )
Feedwater
Dissolved oxygen 20 500 20 500 20 500 20 500 20 200 20 200

(g O/L)
Iron (g Fe/L) Below 100 Below 100 Below 100 Below 50 Below 30 Below 30
Copper (g Cu/L) Below 20 Below 20 Below 20 Below 10 Below 10 Below 10
Silica (mg SiO2/L) Below 30 Below 30 Below 30 Below 30 Below 30 Below 20
*For a boiler with the pressure of above 100 to 150 kfg/cm, apply the water quality for the boiler
with the pressure of above 150 to 200 kgf/cm.

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TS-011-15

MEDIUM TO HIGH PRESSURE BOILER TREATMENTS

For JCCP Training Course

SUZUKI TECHNICAL CONSULTING LTD. 1

SUZUKI TECHNICAL CONSULTING LTD. 2

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Blowdown water Feedwater Pump

Filtered Feedwater Feedwater

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Kinds of Troubles in boiler system Causes of troubles

1) KURITA WATER INDUSTRIES: KURITA HANDBOOK OF WATER TREATMENT,

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1) KURITA WATER INDUSTRIES: KURITA HANDBOOK OF WATER TREATMENT,

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Scaling Demineralization or softening Use of boiler compounds

Corrosion Deaeration of feedwater Use of oxygen scavengers,

Carryover *1 Removal of organic sub- Adequate blowdown control,

Mineral scales Metal oxide scales

Calcium carbonate : CaCO3 Ferric oxide : Fe2O3

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1) K. Goto: J. Chem. Soc. Japan, Vol. 76, No12, p. 1364 (1955)

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Substances Thermal conductivity

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Scale thickness Tube wall temperature (oC)

* k : thermal conductivity of scale (kcal/m.h.oC)

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Allowable tensile stress (kg/mm )

6 (2) STB 340 (JIS)

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Kinds of steel (JIS) Composition Spheroidized

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Increase of fuel consumption (%) Thermal conductivity of scale : 0.5 kcal/m.h.oC

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5.1.1 Softening of feedwater (removal of hardness):

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R(-SO3Na)2 + Ca2+ R(-SO3)2Ca + 2Na+ ------------------------ (5.1)

(b) Regeneration (using around 10 % NaCl solution) :

R(-SO3)2Ca + 2Na+ R(-SO3Na)2 + Ca2+ -------------------------- (5.3)

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Cation exchange unit Degasifier Anion exchange unit

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(a) Demineralization (water production),

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3Ca2+ + 2PO43- Ca3(PO4)2 ------------------------------------------------------------ (5.21)

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In neutral to alkaline water like boiler systems, carbon steel is

Alkaline corrosion (at the pressure of 90 kgf/cm2 or more) :

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30 Test period : 100 h

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14 (1) 760 mmHg

Generally, an increase of water temperature or a reduction of atmospheric pressure is

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