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pH Hardness Conductivity Total Dissolved Solids Alkalinity p-alkalinity m-alkalinity Total Suspended Solids
important parameter (acidity. alkalinity) combination of Ca and Mg uS/cm (relationship with dissolved solids) amount of dissolved ions (mg/l) amount of buffering titration until pH=8.3 total alkalinity (pH=4.3) everything that is not dissolved and can be filtered out
MINERALS
AIR
EARTH
HCO3ClSO42NO3HSiO3-
Cations Anions
a. Dissolved solids
b. Dissolved gases
c. Suspended matter
Deposition
Deposition What is
Result of insolubility of inorganic scale formers Hardness Based Deposits Metal Oxide Based Deposits Can occur as a result of contaminated condensate or feedwater components Unlikely with demineralized makeup water Good pretreatment may limit deposition potential Develops at areas of highest heat input Issue becomes more critical as boiler pressure goes up
Under-deposit Corrosion
Caused by high localized concentration of corrosive molecules
20
Efficiency Loss in %
18 16 14 12 10 8
6
4 2 0.4 1.6 2.8 3.6 0.8 1.2 2.4 3.2 4.4 4.8 0 2
Deposit in mm
Water tube boiler, 95 % of Scale CaCO3. No heat recovery 20 bar [290 psi], 11.3 ton/h
Wall T2
Wal T2 T3
Boiler water T1
Boiler water T1
C Scaled surface Fire side T2 is increased to T4 to reach water T1 T3 is critical for metal structure
120
240 200
Temperature [F]
115
100
95
Temperature [C]
80
160 120 80 40 0 0 0.002 0.004 0.006 0.008 0.01 Deposit thickness [mm]
70
60
50
40
25
20
Deposition Factors
Deposition Solubilities
Compound Calcium Bicarbonate Carbonate Sulfate Magnesium Bicarbonate Carbonate Sulfate Sodium Bicarbonate Carbonate Chloride Hydroxide Sulfate
ppm as CaCO3 0 C [32 F] 1620 15 1290 37.000 101 170.000 30.700 61.400 225.000 370.000 33.600 100 C [212 F] Decomposes 13 1250 Decomposes 75 356.000 Decomposes 290.000 243.000 970.000 210.000
Precipitation of insoluble hardness 2 HCO3- CO32- + CO2+ H2O CO32- + H2O CO2 + 2OH Ca2+ + CO32- CaCO3
Soluble Amount
Temperature
Deposition Silica
Corrosion
Corrosion What is
Definition
The deterioration of a material by the interaction with its environment
Impact
Feedwater piping Feedwater heaters Economizer Boiler Condensate system
Natural passivation:
Formation of a protective barrier on metal surface by reaction with water Fe + 2 H2O Fe(OH)2 + H2 3Fe(OH)2 Fe3O4 + H2 + 2H2O Black magnetite film - Fe3O4 Rate of Magnetite formation is Temperature dependent Spontaneous above 180 C (360 F) Reduces general corrosion Difficult to quantify results
SHIKORR REACTION
T < 180 C
3 Fe + 6 H2O 3 Fe(OH)2 + 3 H2
2 Fe(OH)2 + 2 H2O
Fe(OH)2 + 2 Fe(OH)3
2 Fe(OH)3 + H2
Fe3O4 + 4 H2O
T > 180 C
3 Fe + 4 H2O Fe3O4 + 4 H2
Corrosion Effect of pH
Corrosion Types
Types of Corrosion
Oxygen corrosion Alkalinity concentration Caustic corrosion Acid corrosion Chelant corrosion Erosion/Corrosion
Condensate return pipe with deep attack due to the combined effect of CO2 and O2
Oxygen. O2
Hydroxide OH-
Corrosion products
CATHODE
Electron transport
ANODE
ANODE:
CATHODE:
1/2 O2 Oxygen
H2O Water
Can be found throughout the system Mechanism same as other oxygen corrosion cells Corrosion mechanisms affected by: pH
Minimize corrosion: pH >9.0
Temperature
Higher temperatures reduce O2 solubility, but significantly increase corrosivity
Fluid velocity
Enhances effect of other corrodents More diffusion - better mass transport
5.5 ppm O2
2.5 ppm O2
50C (122 F)
85C (185 F)
Increased blowdown due to turbidity water Increased conductivity due to addition of oxygen scavengers (e.g. sulfite) requires increased blowdown
There are two forms of damage caused by caustic soda to high pressure boilers, namely:
Do we have a picture Steef??
Caustic corrosion Caustic embrittlement
Two conditions are necessary for caustic corrosion to occur: Presence of a corrosive material in the boiler water (caustic soda) Mechanism for concentrating this material, usually due to deposits Usually found only in high pressure boilers
Fe3O4 Fe2O3 + FeO (Magnetite dissolution) Fe2O3 + 2 NaOH 2 NaFeO2 + H2O (soluble) FeO + 2 NaOH Na2FeO2 + H2O (soluble)
Localized in boiler Also called crater attack or caustic gouging No embrittlement of metal
Steam blanketing
Under deposit / concentration to dryness
Excessive heat input Insufficient coolant flow Deposits
Elongated gouge caused by steam blanketing
Magnetite NaOH
NaOH
The following conditions can result in dangerously high localized caustic soda concentrations
(Porous) metal oxide deposits Operation above rated capacity Excessive rate of load increase Excessive localized heat input Localized pressure differentials Restrictions in generating tube(s)
Causes of acidity
Feedwater acid contamination Acid leaks from demineralizer, e.g. acid regenerant Breakdown of organic materials Condenser leaks MgCl2 + 2 H2O Mg(OH)2 + 2 HCl Organic chlorides R-X + 2 H2O R-OH + HCl
CO2 leaves with steam and reacts with condensed water droplets to Carbonic Acid
CO2 + H2O H2CO3
Steam purity
Sulfite
30-60
30-40
20-30
15-20
Not recommende d
5 2 50-70
Not recommende d
3 1
Silica (as SiO2. max) Total Iron (as Fe. max) Organics
100 10 70-100
50 5 70-100
30 3 50-70
10 2 50-70
Different for all boiler types. feed water quality and region ASME: USA Krachtwerktuigen: Holland TUV: Germany British Standard: UK
900 (60)
120 (80)
1500 (100)
1800 (120)
2400 (160)
Different for all boiler types. feed water quality and region ASME: USA Krachtwerktuigen: Holland TUV: Germany British Standard: UK
Limits on TDS will vary with the design of the boiler and with the needs of the system Despite TDS maximums. industrial type boilers (as opposed to utility type) should not be operated above 100 cycles of concentration Silica may be carried at higher levels if there are no condensing turbines in the cycle. In any case. maintain an "O"/SiOratio of at least 3/1 to inhibit silica deposition. Iron levels shown are theoretical levels based on feedwater iron multiplied by cycles of feed water concentration
Water tube
Boiler Pressure [psi] 0 300 301 450 451 600 601 750 751 900 901 1500
21 - 31 32 - 41 42 51 52 62 63 - 103
bar
< 15
15 - 25
25 - 35
35 45
Boiler water TAC TA Silica SiO2 / TAC Total dissoloved solids Chlorine Phosphate pH [Mg/L] [Mg/L] [Mg/L] [F] [F] [Mg/L] 100 0.7 TAC 200 2.5 < 4000 800 30 - 100 10.5 - 12 80 0.7 TAC 150 2 < 3000 600 30 - 100 10.5 - 12 60 0.7 TAC 90 1.5 < 2000 400 20 - 80 10.5 - 12 40 0.7 TAC 40 1 < 1500 300 20 80 10.5 - 12
bar
40 - 60
60 - 75
75 - 100
8.5 [F] < 0.05 remove Mg/l Mg/l Mg/L < 0.05 < 0.05 < 0.03
8.5 < 0.05 remove < 0.05 < 0.05 < 0.03
8.5 < 0.05 Remove < 0.05 < 0.03 < 0.01
Boiler water TAC TA Silica SiO2 / TAC Total dissoloved solids Free NaOH Phosphate pH [Mg/L] [Mg/L] [Mg/L] [F] [F] [Mg/L] 25 0.5 TAC 15 <1 < 500 < 20 10 - 60 10 - 11 10 0.5 TAC 10 <1 < 300 < 300 10 - 40 10 - 11 5 0.5 TAC 5 <1 < 100 < 100 5 20 9.5 10.5
bar
10
10 - 15
15 25
Boiler water TAC TA Silica SiO2 / TAC Total dissoloved solids [Mg/L] [F] [F] [Mg/L] 120 0.7 TAC 200 2.5 5000 100 0.7 TAC 200 2.5 4000 80 0.7 TAC 150 2 3000
Free NaOH
Phosphate pH
[Mg/L]
[Mg/L]
< 20
30 - 100 10.5 - 12
< 300
30 - 100 10.5 - 12
< 100
30 - 100 10.5 - 12
[mg/l] 0.050 - 0.250 0.030 0.150 < 0.100 [mg/l] [mg/l] [mg/l] [mg/l] [mg/L] < 0.02 < 0.03 < 0.01 < 0.02 <6 <3 NA < 0.020 < 0.030 < 0.010 < 0.020
Scope Pressure area Appearance Conductivity (25 C) Hardness Oxygen Phosphate PH (25 C) p-alkalinity CO2 fixed Iron Copper Silica Organic carbon Oil [ppm CaCO3] [mg/l ] ppm Ppm [mg/l] [ppm as KMnO4] ppm [S/cm] [ppm CaCO3] ppm [mg/l ] [bar]
Colourless, free from suspended matter < 10,000 < 1.0 < 0.02 10 20 10.5 12 50 600 < 25 < 0.03 < 0.005 NR < 10 <1 Graph Graph < 10 < 0.03 < 0.005 < 0.02 <3 <1 <4 <4 5 - 15 10 11.8 25 - 300 5 - 15 10 11 5 50 >9 < 0.1 <6 9.5 10.5 >7 < 5,000 < 2,500 < 0.2 < 150 <3
Scope Pressure area Appearance Conductivity (25 C) Hardness Oxygen Phosphate [S/cm] [ppm CaCO3] ppm [mg/l ] [bar]
PH (25 C)
p-alkalinity CO2 fixed Iron Copper Silica Organic carbon [ppm CaCO3] [mg/l ] ppm Ppm [mg/l] [ppm as KMnO4]
Oil
ppm
Feedwater 0.5 bar Appearance Colourless and without suspended solids [ppm CaCO3] [mg/L] 10 8-9
CO2 fixed
Organic carbon Oil Conductivity ( 40 kg/m2) Conductivity (> 40 kg/m2 p-alkalinity Phosphate Silica
[mg/l ]
[ppm as KMnO4] ppm [mg/L] [mg/L] [ppm CaCO3] [mg/l P2O5 ] [mg/l SiO2]
25
10 3
25
10 1 6,000 5,000 1,000 30 250 6,000 5,000 800 25 200 4,000 3,000 600 20 150
Hardness [mg/L]
pH (20 C)
< 20 21- 32 33 40 41 53 54 64 65 70 71 126 127 165 166 180 181 203 > 98 < 20 20 - 40
Natural circulation Natural circulation Natural circulation Natural circulation Natural circulation Natural circulation Natural circulation Natural circulation Natural circulation Natural circulation Forced circulation Forced circulation with continuous steam formation Forced circulation with continuous steam formation
3,500 3,000 2,500 2,000 1,500 1,250 100 50 25 15 0.05 2,000 1,000
9.5 - 11 9.5 - 11 9.5 - 11 9.5 - 11 9.5 - 11 9.5 - 11 9.5 10.5 9.5 10.5 9.5 10.5 9.5 10.5 9.5 10.5
25 25 10 10 10 3 3 3 3 3 3 -
400 200
100 50
Waterpijp
0.5-20 30-80
9.8-10.2 250-750
<2 <5
TDS Conductivity [S/cm] Organic carbon [ppm CZV] Iso ascorbic acid [mg/l] < 6000 (pH=8.3) <150 <2500 (after cation filter)
Parameter
Unit
Feedwater
Boiler water
Heat flux
300 Clear, no foam 8.5 9.5 Mg/kg CaCO3 Mg/kg Mg/kg CaCO3 Mg/kg CaCO3 Mg/kg Mg/kg 30 70 0.1 1.0 120 160 15 30 0.1 1.0 (FW) Mg/kg Mg/kg Mg/kg Mg/kg uS/cm 30 60 150 200 3500 7000 1 1000 350 2 10.5 12.0
> 300
Appearance pH (25 C) Total Hardness Oxygen Total M-alkalinity O- and P-alkalinity Oil and grease Oxygen scavenger Sulfite, or Hydrazine, or Tannin, or Iso ascorbic acid, or DEHA Phosphate Silica Suspended solids Dissolved solids Conductivity (25 C)
9.5 10.5
100 20
Assess 0.1 1.0 Assess Assess 0.1 1.0 (FW) 10 30 5 20 1000 2000
Boiler water O- and P-alkalinity Oxygen scavenger Sulfite, or Hydrazine, or Tannin, or Iso ascorbic acid, or DEHA in FW Chloride Phosphate Silica Dissolved solids Conductivity (25 C) Mg/kg Mg/kg Mg/kg uS/cm 30 70 0.4 x O & P alkalinity 3000 6000 20 50 0.4 x O & P alkalinity 2500 5000 20 40 20 1000 2000 Mg/kg CaCO3 Mg/kg 50 - 300 50 - 150 25 50 10 20 5 - 10 2-5 1-5
Feedwater
pH (25 C) Total Hardness Oxygen Fe, Cu, and Ni Mg/kg CaCO3 Mg/kg Mg/kg 9.3 9.8 ND 0.02 0.05 9.3 9.8 ND 0.01 0.03 9.3 9.8 ND 0.005 0.02 0.005 0.005 0.02 8.5 9.5 8.5 9.5 1 8.5 9.5 ND 7.5 9.5 1 Nil 0.2 Cond 400 Boiler water
Mg/kg CaCO3
Mg/kg
25 - 50
10 - 50
25
300
150
300 600
50 100 pH > 9.5 Hardness 0 - 10
15 - 20 0.1 0.5 120 160 15 30 0.1 0.25 Mg/kg Mg/kg Mg/kg uS/cm 20 - 40 20 1000 2000
10 - 20 0.05 0.1 NR NR 0.1 0.25 Assess < 0.4 X O&P alk 8000
NR 0.02 0.05 NR NR 0.02 0.05 3-5 < 0.4 X O&P alk 5000
400 2000
Pressure Appearance
300
pH (25 C)
Total Hardness Oxygen Fe, Cu, and Ni Mg/kg CaCO3 Mg/kg Mg/kg
8.5 9.5
2 0.02 0.05
8.5 9.5
1 0.02 0.05
8.5 9.5
ND 0.01 0.03
8.5 9.5
ND 0.005 0.02
8.5 9.5
ND 0.005 0.02
8.5 9.5
ND 0.005 0.02
8.5 9.5
ND 0.005 0.02