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November, 2015
Takashi Suzuki
Authorized Professional Engineer (Japan)
SUZUKI TECHNICAL CONSULTING LTD.
Ebina, Kanagawa, Japan
Superheated
steam
To use points
Economizer Deaerator
Boiler
Filter
Condensate
(from use points) Polisher
Condensate
Supply water tank
*1 In case that a carryover trouble is caused by a defect of steam separator, the separator must be repaired
for preventing those troubles.
SUZUKI TECHNICAL CONSULTING LTD. 11
4. Scaling
4.1 Typical Scale Components Found in Boiler Systems
Main scale components of medium to high pressure boilers are generally silica and
metal oxides (corrosion products).
SUZUKI TECHNICAL CONSULTING LTD. 12
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.
1) KURITA WATER INDUSTRIES: KURITA HANDBOOK OF WATER TREATMENT,
The 2nd English Edition, p. 2-8 (1999)
80
Calcium hardness
(mg CaCO 3 /L)
60
Solubility of CaCO3
40
20
0
0 50 100 150 200
Temperature ()
(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
Thermal conductivities of scales are much smaller than those of metals. Therefore,
scale adhesion on boiler tubes widely reduces the thermal efficiency of boiler.
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.
SUZUKI TECHNICAL CONSULTING LTD. 19
(1) Increase of tube wall temperature by scale adhesion
(a typical calculation results)
12
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)
1) T. Abe, et al.: Central Research Institute Electric Power Industry Report No. 277014, p. 8 (1973)
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.
(a) Softening :
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.
SUZUKI TECHNICAL CONSULTING LTD. 26
(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.
SUZUKI TECHNICAL CONSULTING LTD. 28
(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
Raw water
HCl NaOH
(Regenerant) (Regenerant)
Regeneration
wastewater
Product
Regeneration water
wastewater
Cation exchange unit Degasifier Anion exchange unit
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)
16
10
(mg/L)
8
(1)
6
2 (2)
0
0 20 40 60 80 100 120
Temperature ( )
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)
SUZUKI TECHNICAL CONSULTING LTD. 38
7.2 Internal (Chemical) Treatment
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)
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)
SUZUKI TECHNICAL CONSULTING LTD. 41
(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 - -
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)
Hydrazine 1.4
DEHA 2.8
MEKO 6.1
(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)
*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.)
SUZUKI TECHNICAL CONSULTING LTD. 50
9.2 Determination of Blowdown Rate
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.
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.
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)
SUZUKI TECHNICAL CONSULTING LTD. 62
9.9.2 Standard cleaning interval for heavy oil combustion
water-tube boilers1)
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)
100
80
Efficiency (%)
60
40
20 40 60 80 100 120
Load (%)
(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
Copper (g Cu/L) Below 10 Below 10 Below 5 Below 10 Below 3 Below 5 Below 2 Below 2
Below 40* Below 20 Below 30* Below 20 Below 20 Below 20 Below 20 Below 20
Below 20** Below 20**
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
Process Ignition and water circulation Water circulation during Normal operation
Division
*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.