II.

BASICBOILERWATERPROBLEMS,OXYGEN
CONTROL EQUIPMENT and CHEMISTRIES
CONTROLEQUIPMENTandCHEMISTRIES

1
 IndustrialBoilerWaterTreatment

BOILER WATER TREATMENT -

A SPECIALIZED STEAM SYSTEM MANAGEMENT
SERVICE
1. Utilizes External Water Pretreatment Equipment
and Internal Feedwater Management Chemicals.
2. Water Analyses, Problem Solving, and Technical
Advice.
3. Serious Problems Occur in the Absence of
Adequate Treatment and Control!

2
 Boiler Water Treatment contd
BoilerWaterTreatment,contd.
OBJECTIVES:

1. Keep All Boiler Steam and Waterside Surfaces Clean

and Free of Foulants, Deposits, and Corrosion.

2. Maximize Heat Transfer Rates and Minimize Fuel

Consumption.
p

3. Limit Unnecessary Downtime and Maintenance.

4. Preserve and Extend Equipment Asset Life.

3
 Observations
Boiler Plants Operate Most Effectively When the
Feedwater and Boiler Water Chemistries are Constant
and Predictable.
Pretreatment Equipment is Needed to Level Out Daily
Variations in Feedwater Qualities.
Q
A Water Softener is the Minimum Requirement.
IIn Most
M Plant
Pl Operations,
O i More
M Extensive
E i Pretreatment
P
Equipment is Required, Especially at Higher Operating
Pressures.
Mechanical Deaeration is Required in Virtually All Steam
Plant Operations, Especially Those At Higher Pressures.

4
 Observations,contd.
Higher Feedwater and Boiler Water Qualities can be
Achieved by Improving Makeup Water Quality and
g More Condensate.
Returning
BENEFITS INCLUDE
Less Blowdown Saving Heat and Treated Water
Reduced
R d d Chemical
Ch i l Consumption
C ti
Higher Quality Steam
Reduced Risk of Corrosion and Deposition
p
Higher Cycles of Concentration

Boiler Water Cycles

y are determined based on Operating
p g
Pressures, Silica, Alkalinity, and Total Dissolved Solids,
and Steam Purity Demands.

5
 Observations,contd.
FEEDWATER QUALITY dictated by Boiler
Pressure, Design, Application, and Heat Flux.
HIGHER PRESSURE / HIGHER OUTPUT / SPECIAL
USE BOILERS require Greater Feed Water Purities
f More
for M Effi i t Steam/Water
Efficient St /W t Separation
S ti without
ith t the
th
Risk of Carryover!
DEMINERALIZATION Required When a Lower
Total Dissolved Solids, Silica or Sodium Feedwater is
Needed.
CONDENSATE POLISHING May be Required to
Reduce a Feed water's Metal Content (Iron, Copper,
Nickel Chromium,
Nickel, Chromium etc.).
etc )

6
BoilerOperationalProblems

7
 Combustion / Gas Side Problems
Combustion/GasSideProblems

TUBE TIES BROKEN BUCKLED TUBES

8
9
 FireSideTemperaturesandProblems
LOCATION GAS TEMP OUTER DEPOSIT PROBLEMS
METAL TEMP TEMP

FLAME 2500-3100 Combustion

FURNACE 2000-2800 800 2000-2500 High temp

corrosion, slag,
spalling

SUPER 1200-2000 1000 1000-2000 High Temp

HEATERS & corrosion, slag,
REHEATERS fouling

CONVECTION 900-1200 500-900 1000 Fouling

ECONOMIZER 600-1200 200-600 Low Temp

corrosion,
corrosion
fouling

AIR HEATER 300-600 200-500 Low Temp

corrosion,,
fouling

10
 Cavitation FeedWaterExplosion

Cavitation the explosive conversion of Feedwater to

Steam in the Feedwater Pump causing physical damage
to the pump internals.
Feedwater Pumps are designed to pump liquids,
liquids not
steam.

11
 Oxygen
yg ThePrincipleCauseofCorrosi
p on
Inmostcasesthepresenceof
Oxygen will initiate corrosion.
Oxygenwillinitiatecorrosion.
HeatinaFeedwatersystem
acceleratescorrosion.
MechanicalDeaeration
removesmostoftheoxygen.
TheadditionofaChemical
The addition of a Chemical
OxygenScavengerremoves
theremainingoxygen.
Whenproperlyapplied,
When properly applied
OxygenScavengerswill
preventoxygencorrosionand
pitting.

12
 CausesofOxygenPitting
yg g
The ability for oxygen
to attack a metal and
f
form a pit
it increases
i by
b
a factor of two for
every 10 C (18 F)
temperature increase
increase.
Oxygen is 512 times
more aggressive at
212 F (100 C) th
than att
50 F(10 C).
Oxygen
yg must be
vented out of a system
or removed with a
Chemical Oxygen
Scavenger.
13
 OxygenPittingCorrosion
yg g

ACTIVE
PITS

FEED WATER LINE

CORROSION
FEED WATER
IMPELLER

14
BoilerWaterTreatment Protection
Against Corrosion and Scale
AgainstCorrosionandScale

15
 CalciumCarbonateScalesandDeposits
Once Scale has formed on a metal surface, the Deposit
will attract other charged particles in the Boiler Water.

16
 TricalciumPhosphateDeposits
Tricalcium Phosphate is formed from inadequate control
of Internal Phosphate Treatment Programs.

17
IronDeposits DenserThanCalcium
DepositsandHardertoRemove
Boiler Iron
Iron-Based
Based Deposits
are more Insulating than
Calcium Carbonate and more
difficult to remove.
remove
Iron originates from
Condensate or Feedwater
System Corrosion.
The corrosion must be
stopped before the Iron
Deposition can be
controlled!

18
 TubeFailures Bursts

Boiler Tube deposits can

result in Thin- or Thick-Lip
Bursts. An over-heated tube
results in bulging and
eventual bursting.
A high temperature Stress
Crack caused by over-heating
over heating
led to the failure on the right.
19
 Other Problems
OtherProblems
Flow Assisted Corrosion (FAC) very prevalent in
Combined-Cycle
Combined Cycle Heat Recovery Steam Generators
(HRSGs). Controlled by materials selection, changes
in Feedwater quality, approach temperature, flow
rate, etc.
Hydrogen Embrittlement, Caustic Gouging, Stress
Corrosion Cracking, Short/Long Term Overheating.
SO2 Emissions - controlled by burner modifications,
wet/dry scrubbing, atmospheric circulating fluidized
bed (ACFB).
NOx Emissions controlled by coal gasification/
selective non-catalytic reduction (SNCR), fuel
g etc.
switching,

20
 OtherProblems,contd.

Accelerated Corrosion Due Carbon in Gas Pipe

p
to Water Leakage
21
 Steam/WatersideProblems
/

Broken Chemical Feed Line in Steam Drum Oxygen Corrosion in Steam Drum

22
InternalChemicalTreatmentisNeeded
toCleanUpaBoiler!

23
CyclesofConcentrationand
Cycles of Concentration and
BlowdownCalculations

24
 CyclesofConcentration
y COC
TheConcentrationof
Dissolved Solids in the
DissolvedSolidsinthe
BoilerWater.
Aswaterisevaporated,
alldissolvedsolids
originallypresentstayin
theBoilerWater.These
mineralsbecomemore
concentrated.
COC
COCmustbebalanced
tb b l d
versushighalkalinities
andtheriskofcarryover!

25
 CalculationsandNotes
CYCLESFeedwater =[ClBoilerwater] [ClFeedwater]

%CONDENSATERETURN=100 %MAKEUP

FEEDWATER(ppd)=STEAM(ppd)+BLOWDOWN(ppd)

STEAMRATE=BHPx%LOADx34.5pph/BHP

BLOWDOWN=[STEAMRATE] [COC 1]

BLOWDOWN=[TDSFeedwater x100] [TDSBoilerWater TDSFeedwater]

26
 BlowdownCalculationExamples
Where: TDS is expressed in ppm or mg/l.
E = 10,000 pph.
TDSFW = 200 ppm; TDSBW = 3,000 ppm.
COC = Boiler Water Cycles of Concentration.
COC = 3,000 200 = 15.0.

Blowdown = [TDSFW x 100] [TDSBW - TDSFW]

= [200 x 100] 2,800 = 7.14%
Feedwater = [TDSFW x 100] [TDSBW]
= [200 x 100] 3,000 = 6.67%
Blowdown = E [COC 1]
= 10,000 [15 1] = 714 pph

27
FeedwaterandBoilerWaterControl

28
ASMEBoilerandFeedWaterRequirements
q

D r u m O p e r a tin g P r e s s u r e p s ig (M P a ) 0 3 0 0 ( 0 2 .0 7 )
F e e d w a te r
D O p p m (m g /l) O 2 b e fo re o x y g e n s c a v e n g e r < 0 .0 0 7
T o ta l iro n p p m (m g /l) F e < 0 .1
T o ta l c o p p e r p p m (m g /l) C u < 0 .0 5
T o ta l h a rd n e s s p p m a s C a C O 3 < 1 .0
p H @ 2 5 oC 8 .3 t o 1 0 .5
N o n -v o la tile T O C p p m (m g /l) C <10
O ily m a tte r p p m (m g /l) < 0 .1
B o ile r W a te r
S ilic a p p m (m g /l) S iO 2 <150
T o ta l a lk a lin ity p p m a s C a C O 3 <700
F re e O H a lk a lin ity p p m a s C a C O 3 n o t s p e c ifie d
C o n d u c ta n c e S /c m ) @ 2 5 oC <7000

29
 BritishStandard2486:RecommendedWater
CharacteristicsforShellBoilers(<25Bar)
Total hardness in feed water, mg/l CaCO3 max. 2 20 40
Feed water
ppH value 7.5 to 9.5 7.5 to 9.5 7.5 to 9.5
Oxygen
Total solids, alkalinity, silica
Organic
g matter
Boiler water
Total hardness, mg/l in terms of CaCO3 max. ND ND ND
Sodium phosphate, mg/l as Na3PO4 50 to 100 50 to 100 50 to 100
Caustic alkalinity, mg/l in terms of CaCO3 min. 350 300 200
Total alkalinity, mg/l in terms of CaCO3 max. 1200 700 700
Silica mg/l as SiO2 max.
Silica, max Less than 0.4
0 4 of the caustic alkalinity
Sodium sulfite, mg/l as Na2SO3 30 to 70 30 to 70 30 to 70
Or Hydrazine, mg/l as N2H2 0.1 to 1.0 0.1 to 1.0 0.1 to 1.0
Suspended solids, mg/l max. 50 200 300
Dissolved solids, mg/l max. 3500 3000 2000
30
 Feed Water pH
FeedWaterpH

Feed Water p
pH should be above 8.5 to prevent
p
corrosion of iron within the system.

Feed Water pH should be below 9.2 to prevent

copper loss within the system.

Optimum Feed Water pH should be 8

8.5-9.2.
5-9 2

31
 BoilerWaterTreatmentAreas
Requiring Control
RequiringControl
OXYGEN SCAVENGING
pH and ALKALINITY
HARDNESS and SCALE DEPOSITION
SUPERSATURATION of DISSOLVED SOLIDS
SLUDGE and FOULANT
PASSIVATION and CORROSION
STEAM and CONDENSATE SYSTEM CORROSION
PRIMING and/or CARRYOVER
CONTROL of SPECIFIC PROBLEMS
(Silica; Process Contamination; Iron; Sodium;
Chlorides; Stress and Short
Short-/Long-Term
/Long Term Overheating)
32
 InternalBoilerWaterTreatments
ANODICPROGRAMS NITRITE,SILICATE,andMOLYBDATE
TANNIN PROGRAMS
PRECIPITATING CARBONATE PROGRAMS
PRECIPITATING PHOSPHATE PROGRAMS
COORDINATED PHOSPHATE PROGRAMS
CONJUNCTIONAL/EQUILIBRIUM PHOSPHATE PROGRAMS
ALL
ALLVOLATILE
VOLATILE TREATMENTS
AMMONIA and AMINES
CHELANT PROGRAMS (EDTA and NTA)
ALLPOLYMER PROGRAMS
COMBINATIONS PROGRAMS (CHELANT/PHOSPHATE;
PHOSPHATE/POLYMER; CHELANT/POLYMER)

33
 BasicBoilerChemistry
CATIONS (Positive Charge) ANIONS (Negative Charge)
HYDROGEN H+ ORTHOPHOSPHATE PO43-
SODIUM Na+ SULFITE SO322-
CALCIUM Ca2+ SULFATE SO42-
MAGNESIUM Mg2+ CARBONATE CO32-
IRON (FERROUS) Fe2+ BICARBONATE HCO3-
IRON (FERRIC) Fe33+ HYDROXIDE OH-
ALUMINUM Al3+ CHLORIDE Cl-
REACTIONS
Bicarbonate Decomp: NaHCO3 + HEAT Na2CO3 + CO2 + H2O
Developed Alkalinity: Na2CO3 + HEAT + 2H2O 2NaOH + CO2 + H2O
Brining Reactions: CaCl2 + Boiler Water CaSO4 + CaSiO3
Phosphate Reaction: Ca3(PO4)2 Tricalcium Phosphate [Low Alkalinity]
Phosphate Reaction: Ca10(OH)2(PO4)6 Hydroxyapetite [Adequate Alkalinity]
Magnesium Reaction: Mg3(PO4)2 Trimagnesium Phosphate [Low Alkalinity]
Magnesium Reaction: Mg(OH)2 Magnesium Hydroxide [Adequate Alkalinity]

34
 CureForCavitationofFeedWaterPumps
Cavitationiscausedbythe
suddenreleaseofsteamin
theFeedWaterandiscured
b h
bythepreventionofsteam
i f
formation.
Deaeratorsystemsareplaced
up to 30 ft (9 m) above the
upto30ft(9m)abovethe
FeedWaterpumpcreatinga
HeadPressureoverthe
pump.At1psiofHeadfor
every2.3ft(68cm)ofheight,
2 3 ft (68 ) f h i ht
33feetofheightwillyield
approximately15psi(1bar) Anothermethodforthepreventionof
ofHeadPressure. Cavitation is the use of a slip stream.
Cavitationistheuseofaslipstream.
Inasystemwithafeedwater Thissystemusesasidestreamto
tankinsteadofaDA,maintain recirculatefeedwaterbacktothe
thetemperaturebelow200F
(93oC).
C) suction side of the pump. This
suctionsideofthepump. This
alleviatessteamreleaseinthefeed
waterpump. 35
Passivation andOxygenRemoval
yg

36
OxygenSaturationInTheFeedWater

37
 Passivation inaBoiler
in a Boiler

In the absence of Oxygen and at higher temperatures,

temperatures
corrosion is often self-limiting as a Passivated (Non-
Corrosive) surface layer of Magnetite is formed.

3 Fe(OH)2 Fe3O4 + 2 H2O + H2

Ferrous Magnetite Water Hydrogen
Hydroxide (black)

38
DeaerationIsVital!

39
 SaturatedSteamTablesandDeaerators
A Feedwater Systems efficiency is measured in
its ability to mechanically bring the Feedwater up
to the Saturated Steam Temperature
Temperature.

The Saturated Steam Temperature is the point

where the Feedwater exists as liquid and gas.
gas
SaturatedSteamTable
(lb/sq in) Temperature (oF)HeatContent(BTU/lb)
Pressure(lb/sqin)Temperature(
Pressure F) Heat Content (BTU/lb)
0 212 180
2 218 187
4 224 190
6 230 198
8 235 203
10 239 208
12 244 210

40
 IntheAbsenceofaDeaerator
F d k andOxygenScavengers
Feedtanks d O S

Oxygen Scavengers chemically remove oxygen from

water:
Catalyzed Sodium Sulfite (Powders or Liquids).
Liquids)
DEHA a Volatile Organic Oxygen Scavenger
transported throughout the steam system.
Erythorbate a GRAS approved product.
Carbohydrazide, MEKO, and other organic oxygen
scavengers.
scavengers

41
 AtmosphericFeedwaterTankSpecifications
Oxygen scavenger is to be fed to the water section of the
tank using g a Stainless Steel Quill.
The higher the temperature, the more efficient oxygen
removal.
In this type of system, if the tank temperature is held above
190F (90oC) there exists the potential for Feedwater pump
cavitation.
Temperature gauges invariably fail, so holding the tank
( oC)) may
at 200F(94 y actually
y equate
q to higher
g
temperatures.
When the Feedwater pump comes on, the boiling point
of the water is reduced.
Deaerators use head pressure (1 psi for every 2 2.3
3 ft of
height above the pump), whereas a Feedwater Tank is
nominally 3 ft above the Feedwater pumps.
Closely y monitor temperatures
p to p
prevent pump
p p loss due
to cavitation.
42
 OxygenRemoval
Oxygen Content of Water
= 6.0 ml/L (8.6ppm) @ 50OF (10OC)
= 4.3 ml/L (6.1ppm) @ 110OF (43OC)
= 2.5 ml/L (3.5 ppm) @ 160OF (71OC)
= 1.6 ml/L (2.3 ppm) @ 190OF (88OC)
Mechanically Deaerated Water = 0.007 ppm
Sulfite Requirements = [O2 ppm x 7.88 + Residual] COC
(as dry Sodium Sulfite)
Typical Low Pressure Boiler Water Sulfite Residuals of
30-70 ppm as sulfite.

43
 Oxygen Scavengers
OxygenScavengers

1.SULFITE ((including
g Bisulfite and Metabisulfite))
Na2SO3 + O2 = Na2SO4
Sodium Sulfite at 7.88 ppm per 1.0 ppm O2
Catalyzed with 0.03-0.05% Cobalt Salts
Residual = 20-40 ppm (sometimes 50-100 ppm)
Sulfites add TDS to the Boiler Water
100% Powder or 30
30-40%
40% Aqueous Solutions

44
 OxygenScavengers,contd.

2. HYDRAZINE, N2H4
Available as 15-, 35-, and 65% Solutions
Need 100% in excess of Stoichiometric Dose
Feedwater: N2H4 + O2 2 H2O + N2
Boiler: 6 Fe2O3 + N2H4 N2 + 2 H2O + 4 Fe3O4
Steam: 3 N2H4 4 NH3 + N2

Ammonia Liberated @ 334OF (100 psi)

Slow Reaction Times, even when Catalyzed!
Potential Carcinogen Risk
Residual = <0.5 PPM
Does not contribute to Boiler Water TDS

45
 OxygenScavengers,contd.
yg g ,

3. DIETHYLHYDROXYLAMINE (DEHA)
1.24 ppm DEHA per 1 ppm O2
Practical Ratio is 3 : 1
No Ammonia @ 534OF (900psi)
Safe as a Neutralizing
g Amine Corrosion Inhibitor
Typically 25% Active
When Catalyzed, Reacts Rapidly
Desired Residual = <0.5ppm

46
 Oxygen Scavengers contd
OxygenScavengers,contd.

4 OTHER ORGANIC O2 SCAVENGERS:

4.

Erythorbic Acid
Hydroquinone
Methylethylketoxime
Gallic Acid
y
Carbohydrazide

47
OxygenScavengerComparisons

48
 Oxygen Scavengers contd
OxygenScavengers,contd.

5. SODIUM NITRITE
An Anodic Passivating Agent
Enhances the Formation of Magnetite Films
NaNO2 typically Buffered with Sodium Borate
May include Yellow Metal Inhibitors
Reducing Environment @ 500-700 ppm NO2
Simple to Test
High Dosages Restrict to Small Boiler Systems

49
 OxygenScavengers,contd.
yg g ,

6. TANNINS
Querqus (Oak), Acacia (Wattle), Schinopsis (Quebracho),
etc.
Hydrolyzable Tannins when heated degrade into
Polyhydroxyphenols, Gallic Acid, and Ellagic Acid all
Oxygen Scavengers
Non-Hydrolyzable (Condensed) Tannins when heated
degrade into ortho-, meta-, and para- Dihydroxy
Flavenoids ((Anionic Polyelectrolyte
y y Sludgeg
Conditioners)
Residual @10-15 ppm Tannin Reserve (Brown Color)
G
Good Performance
f Under Poor Conditions
C
50