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WATER TECHNOLOGY

FOR HP BOILERS
OVERVIEW

EFFECTS OF WATER TREATMENT

WATER CHEMISTRY GUIDELINES

CORROSION MECHANISMS
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Waterwall deposit analysis


CHEMICAL COMPOSITION
Parameter % by weight
Sample 1 Sample 2 Sample 3 Sample 4
Silica , SiO2 14.7 8.7 0.5 0.8
Iron oxide, Fe3O4 58.6 55.0 95.1 88.6
Copper , Cu 4.9 1.8 3.2 7.7
Calcium oxide,CaO 19.1 29.8 0.5 1.1
Magnesium oxide,MgO 1.8 3.0 0.1 0.4
Sodium oxide, Na2O 0.2 0.1 0.2 0.1
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QUANTITY OF DEPOSIT (mg / sq.cm.)

Sample 1 Sample 2 Sample 3 Sample 4

Front waterwall 53.7 55.0 21.9 80.5

Rear waterwall 47.4 58.6 22.1 54.8

LHS waterwall 64.4 --- 28.1 80.9

RHS waterwall 38.5 --- 25.5 38.5


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Quantity of deposit and unit cleanliness

Quantity of deposit Surface cleanliness

Less than 15 mg /sq.cm. Clean surface


15 to 40 mg / sq.cm. Moderately dirty
more than 40 mg/sq.cm. Dirty

Chemical cleaning should be done whenever deposits


are more than 40 mg / sq.cm .
once in 4 years as a mandatory maintenance practice
( guidelines only / not a rule or code ) BIS : 10391
HEAT TRANSFER GRADIENTS
AND EFFECT OF DEPOSITS

1-2 .. TUBE METAL RESISTANCE FIRESIDE


( ~ 30O C FOR 2.5mm WALL ) 1
2-3 .. INTERNAL DEPOSIT 2
RESISTANCE
3
3-4 .. WATER STEAM FILM
RESISTANCE 4

Tube metal and water film resistance


*** more or less constant
the temperature of the inner & outer wall
rises due to changes in the deposit
thickness & nature ( thermal conductivity
of the deposit ) Silica , Ca , Mg salts very poor thermal conductivity
EFFECT OF DEPOSIT ON HEAT TRANSFER
SCALE THICKNESS

250 m 500 m 750 m


1
410OC 478OC 550OC

360OC 428OC 500OC 2

3
297OC 297OC 297OC
285OC
4
285OC 285OC 285OC

1-2..TUBE METAL RESISTANCE


2-3.. INTERNAL SCALE & DEPOSIT
RESISTANCE
3-4.. WATER / STEAM FILM RESISTANCE
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Method of tube sampling


location of tube samples very important
( since deposits may vary appreciably in different parts
of a boiler )
tube samples to be taken from locations representing
heaviest deposit (corrosion product ) formation
Band starting the central line of the uppermost burner
and extending up the furnace by about 2 to 3 metres
Operating experience in specific units
- problem areas : arch tubes in natural circulation units
or other horizontal or low-sloped circuits
Three adjacent tubes to be removed for comparison ;
samples should be 600 mm in length and ends sealed
EFFECT OF IMPROPER WATER
CHEMISTRY FOR FEED WATER SYSTEMS
Storage tanks :
** general corrosion , pitting

Condensers and feed water heaters :


** pitting , erosion , corrosion , exfoliation,
galvanic corrosion

Dearators :
** corrosion , pitting
Economizer :
** pitting , corrosion , hydrogen damage
EFFECT OF IMPROPER WATER
CHEMISTRY FOR BOILER SYSTEMS
** general corrosion , pitting ,caustic gouging ,
hydrogen damage , deposit induced overheating
EFFECT OF IMPROPER WATER
CHEMISTRY FOR STEAM SYSTEMS
Reheaters and Superheaters
** pitting , corrosion , overheating (SHS), exfoliation (RH)
Turbine :
** corrosion , stress corrosion cracking , pitting , galvanic
corrosion , crevice corrosion , deposition & fouling
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*** GUIDELINES
---- normal operation
---- critical periods
~~ start up
~~ condenser leakage
. ~~ shutdown ( lay-up)

*** MONITORING

*** MEASUREMENT
Bharat
Bharat HeavyElectricals
Heavy Electricals Limited
Limited, Tiruchirapalli
TIRUCHIRAPALLI

CRITERIA

boiler design
pressure of operation
thermodynamic & engineering principles
type of water treatment ( boiler )
*** phosphate , AVT , etc
objectives
To achieve the expected steam purity
To minimize corrosion
To reduce deposition
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Cycle chemistry guidelines


Most sensitive part in the plant cycle

TURBINE
Chemistry limits established for steam
. leading to the basis for establishing
boiler water chemistry limits and hence
the feedwater and condensate chemistry limits
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Objectives of water treatment

To reduce corrosion of metals

To prevent formation of deposits

To produce good quality steam


Water Treatment ?

3 FACTORS OF CORROSION

Metal

Oxygen / force

Medium / water / air /


( product removal )

Controlling any of the three is the aim of water treatment


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Steam purity recommendations


substance Phosphate All-volatile Once-through
treatment ,ppb treatment, ppb treatment, ppb
Sodium 5 3 3
Cation cond. 0.3 0.15 0.15
S/cm
Silica 10 10 10
Chloride 3 3 3
Sulphate 3 3 3
TOC 100 100 100
Condensate
storage tank

HP IP Turbine LP Turbine
Turbine

Attemperation
Condenser

Blowdown
Makeup
treatment
Deaerator system

Condensate
polisher
Boiler
LP Heaters
HP Heaters

BFP

Steam-Water cycle diagram for reheat type boilers


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New units
Internal surfaces of heat exchanger tubes to
be clean --- before put into service
Oil, grease , sand etc removed by alkali boilout
Chemical cleaning ( acid pickling ) for removal
of rust and millscale
Thin , dense , uniform layer of magnetite to be
formed on the internal surfaces of the tubes to
protect from corrosion ( passivation )
Saponification of oil
O
||
H2C O CCH2 CH3
O
||
H C O CCH2 CH3 oil
molecule
O
||
H2C O CCH2 CH3

O
||
H2C O H NaOCCH2 CH3

O
||
H COH NaO CCH2 CH 3
O
||
H2 C O H NaO CCH2 CH3
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Why passivation ?
Magnetite , Fe3O4 Ferric oxide , Fe2O3
colour black brownish red
binding nature tightly binds to flakes off easily
base metal from base metal
Significance protects the does not protect
w.r.to corrosion base metal the base metal
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Feed water chemistry


Condensate plus make-up water
Virtually all impurities are carried into the boiler in the
feedwater
Pre-boiler (condenser, feedwater heaters , dearators)
corrosion --- most prevalent form of corrosion in
modern h-p boilers
Corrosion products formed in the pre-boiler section
transported to the boiler waterwall tubes
get deposited preferably on high heat transfer zones
results in overheating and subsequent tube failure
Deposits contain
oxides of iron , copper and its oxides , traces of Zn,Ni ,
etc.
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Feedwater guidelines
Drum Pr. 61- 100 101-165 166 - 205 Once-thro
Kg / sq.cm ugh units
Hardness, ppm, max nil nil nil nil

pH at 25oC 8.8 - 9.2 8.8 9.2 8.8 9.2 8.8 9.2

Diss.Oxygen,ppm,max 0.007 0.007 0.007 0.007

Cond. ( H+ ), S/cm, max 0.5 0.3 0.3 0.2

Silica, ppm, max 0.02 0.02 0.01 0.01

Iron , ppm , max 0.01 0.01 0.005 0.005

Copper , ppm , max 0.01 0.005 0.003 0.003

Hydrazine , ppm , residual 0.01 0.02 0.01-0.02 0.01-0.02 0.01-0.02


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Solubility of oxygen vs temperature

Temperature ( 0C ) Temperature ( 0F ) Oxygen ( cc per litre )


22 70 6.2
33 90 5.1
44 110 4.4
55 130 3.8
66 150 3.1
77 170 2.4
88 190 1.5
99 210 0.1
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Condensate chemistry -- dissolved oxygen


Magnetite , Fe3O4 , protective film for iron
Cuprous oxide , Cu2O , protective film for copper
Oxygen , if excess , in feedwater oxidizes both the
protective layers
2 Fe3O4 + O2 3 Fe2O3
Cu2O + O2 2 CuO
Nodules of corrosion products & pits form at the
corrosion site
Corrosion products enter the solution , transported
to the boiler higher heat loads cause deposition
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Copper & Iron --- during startup


Time ( hour ) after Copper , ppb Iron , ppb
startup
0 500 260
4 230 210
8 160 180
16 70 120
20 40 75
24 30 50
28 20 35
36 <5 < 10
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Pre boiler corrosion


Dissolved oxygen attacks copper in the presence of ammonia
more severely as follows :
2 Cu2O + O2 4 CuO
CuO + 4 NH4OH Cu (NH3)4 (OH)2 + 3 H2O
(insoluble) ( soluble )
The corrosion product is transported more easily in a soluble
form into the boiler
The copper-ammonia complex decomposes inside the boiler at
elevated temperatures ( > 140oC )
The liberated free copper gets deposited on the heat
transfer surfaces
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Pre boiler corrosion salient features


Most-affected locations --- Economisers & feedwater heaters
High levels of oxygen can be expected in feed water more
during start-ups and low-load operations
Pitting severe during idle periods -- free entry of oxygen ---
moisture can be collected in bends , sags , etc leading to
enhanced corrosion
Appearance : perforations or pits on the tubewalls through
localized corrosion
if severe , during very high levels of dissolved oxygen ,
crater like sites develop having red,rusty appearance
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Boiler water guidelines


Drum Pr. 61-125 126-165 166-205 166-205
Kg / sq.cm
Treatment phosphate phosphate phosphate AVT
Type
pH at 250C 9.1-10.1 9.1-9.8 9.1-9.6 >8.5

Silica, ppm , max 7.0 0.9 0.9 0.2 0.10 0.10

PO4 residual , ppm 5 - 20 5 - 10 2-6 ---

TDS , ppm , max 100 50 15 ---

Cond. S / cm , max 200 100 30 ---

Cond. ( H+ ), S/cm, --- --- --- 0.2


max
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Boiler water treatment


Trisodium phosphate provides the needed alkalinity in
boiler systems as follows :
o Na3PO4 + H2O === NaOH + Na2HPO4
Absorption of contaminants :
o 10Ca2+ + 6PO43-- + 2OH-- 3Ca3(PO4).Ca(OH)2
calcium hydroxyapetite
o 3 Mg2+ + 2SiO32- + 2OH-- + H2O
3MgO.2SiO2.2H2O
serpentine
Calcium hydroxyapetite and serpentine exist as soft sludges
and much easier to remove ; typically settle in the drum
and removed by blowdown
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Boiler water guidelines
Operating SiO2 , ppm , SiO2 , ppm,max Chloride Sulphate
pressure (0.01 ppm steam ) (0.02 ppm steam) Cl, ppm, max SO4 , ppm,max
90 1.3 2.6 2.8 3.0
105 0.8 1.6 2.6 2.6
120 0.55 1.1 2.4 2.4
135 0.4 0.8 2.0 2.2
145 0.27 0.54 1.8 1.9
160 0.2 0.4 1.5 1.7
175 0.14 --- 0.9 1.6
190 0.1 --- 0.4 1.5
pH Vs PO4 & NaOH

11.5

11

10.5

pH 10

9.5

8.5
0 5 10 15 20 25 30 35 40

ppm PO4 N aOH


EFFECT OF PO4 / NaOH on pH

10.6
10.4
10.2
10
9.8
pH
9.6
9.4
9.2
9
8.8
0 2 4 6 8 10 12
ppm
PO4 NaOH
Operation of Drum-type Boilers 165 to 180 kg/cm2
Hotwell Operational Control limits Boiler water control
conditions limitations
Total solids none TDS < 25 ppm normal
(recommended) pH 9.1 9.8
< 0.05 ppm PO4 5 10 ppm
Total solids Volatile treatment TDS < 25 ppm If on volatile
(acceptable) not suitable ; pH 9.1 9.8 treatment , change
< 0.25 ppm Back to guideline PO4 5 10 ppm to PO4 treatment
values soon

Total solids Limited operations; TDS < 50 ppm chemical injection


(abnormal) Inspection and pH 9.1 10.1 to maintain excess
0.25 1.0 ppm repair of condenser PO4 5 20 ppm PO4 & pH conditions
boiler water control for [ 0.25 1.0 ppm (abnormal) ] condition :
If pH < 8.0 & Total solids < 50 ppm do not operate the unit
increase blowdown to limit TDS concentration
avoid use of desuperheating spraywater by (a) reducing load
and (b) permitting reheater temperature to fall - contd
Operation of Drum-type Boilers 165 to 180 kg/cm2
Hotwell Operational Control limits Boiler water
conditions limitations control
Total solids

Excessive Emergency TDS < 50 ppm Same as for


> 1.0 ppm operation : pH 9.1 10.1 abnormal hotwell
immediately PO4 5 20 ppm conditions of
reduce load 0.25 to 1 ppm
plus
orderly shut-
down of the unit
if hotwell prepare for
concentration wet lay-up of the
cannot be unit
reduced below condenser
1ppm repair
Cation conductivity
salient features
enhances sensitivity to mineral salt concentration
when sample passes through cation exchanger
NH4OH + H+ Resin NH4 + resin + H2O
NaCl + H+ Resin Na+ resin + HCl
Effect of ammonia nullified
Effect of contaminant minerals increased to
nearly 3 times and
sensitivity of measurement increased and
trace amounts of contaminants identified
Number of online analyzers
Parameter Phosphate treatment Volatile treatment
Max min max min
Chloride 3 0 3 0
Conductivity/cation 4 4 5 5
Conductivity / 1 1 1 1
degassed cation
Dissolved oxygen 3 2 3 2
Silica 5 2 5 2
Sodium 7 5 7 5
pH 2 2 2 2
Ammonia 2 0 1 0
Gold
Natural Process

Controlled for Useful


Applications

Formation of ore is natural


process

Separation of pure metal is man


made by using energy sources /
Smelting Hematite Ore
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Corrosion of boiler steel

Factors responsible for corrosion

pH

Dissolved oxygen
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Corrosion cell reactions

2 Fe 2 Fe2+ + 4 e
O2 + 2 H2O + 4 e 4 OH
-------------------------------------------
2 Fe + O2 + 2 H2O 2 Fe(OH)2

Fe (OH)2 , ferrous hydroxide , converts to


rust Fe2O3 . xH2O
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An Electrochemical reaction

water
OH--
O2 Fe2+
Electron flow

ww
Tube
Fe

ANODE REACTION CATHODE REACTION

Fe0 === Fe2+ + 2 e-- O2 + H2O + 2 e-- == 2 OH--


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Corrosion of steel vs boiler water pH

Corrosion 8.5 11.0


rate
safe range

4 6 8 10 12 14

acidic alkaline
pH
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Corrective actions
Control of dissolved oxygen and ammonia in feed water
Effects of pre-boiler corrosion severe during start-ups when
chemical control is difficult
Proper care and attention during condenser leakage
Condensate purification plants : to minimize soluble and
insoluble materials
Alternate materials : Titanium , stainless steel
Air-inleakage control : Expansion joints between turbine and
condenser ; turbine seals, diaphragms ; condensate pump seals
Dearator performance
Steam temperature and pressure and quantity
Tray alignment etc
Monitoring of dissolved oxygen . On-line
CAUSTIC DAMAGE
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Caustic corrosion
Irregular thinning of waterwall tube due to the corrosive
action of sufficiently concentrated NaOH
Under porous deposits , NaOH builds up from safe
level to corrosive level
Corrosion occurs by concentrations at the local tube wall
& not by concentrations existing in the bulk boiler water
Concentrated NaOH first attacks the protective magnetite
Fe3O4 + 4 NaOH === 2 NaFeO2 + Na2FeO2 + 2H2O
Further attack of NaOH on boiler metal
Fe + 2 NaOH === Na2FeO2 + H2
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Corrective actions

control of boiler water chemistry ( PO4 programmes )


control of water-side deposition
Periodic ( usually yearly basis ) assessment of tube
cleanliness & chemical cleaning to be carried out , if
needed based on deposit analysis
minimizing ingress of deposit forming materials ( pre-boiler
corrosion and condenser leakage )
Wall thinning , if severe , tubes to be replaced
HYDROGEN DAMAGE
HYDROGEN DAMAGE
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Hydrogen damage
Hydrogen damage occurs in boilers operated with low pH
water chemistry
by aggressive anions like chlorides
concentration of acidic species under deposits
During periods like condenser leakage , specially in sea
cooled power plants , lots of acidic species are introduced
MgCl2 + 2 H2O Mg(OH)2 + 2 HCl
Atomic hydrogen , so formed , can diffuse into steel and react
with iron carbide in steel
Fe3C + 4 H 3 Fe + CH4
Methane , being a bigger molecule, can not diffuse easily
Grain boundaries affected ; internal structure of the tube
damaged , making it brittle
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Corrective actions
Restoration water chemistry

condenser leakage

Removal of unit from service , if pH


falls below 8

Inadvertent release of water treatment


regeneration chemicals
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FLOW ACCELARATED CORROSION

Decay of protective oxide with the combined effect of

pH

Dissolved Oxygen
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Deposition
Even a relatively thin deposit layer significantly reduce heat
transfer . Leading to overheating of the tubes

In cases of severe deposition, overheating may occur very


rapidly resulting in catastrophic tube failure

deposits are also the precursor to under deposit corrosion


water enters a porous deposit through some opening
and boils off through other channels , leaving the solids
behind
the concentrated species may be an alkali (eg.NaOH) or
an acidic species ( eg, Chlorides during condenser leak)
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UNDER DEPOSIT CORROSION

Water wall tube Water wall tube


without deposit with deposit
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UNDER DEPOSIT CORROSION

Na3PO4 + H2O
NaOH + Na2HPO4
Boiler water with
Na3PO4 , Na2HPO4 , NaOH
enter through the pores
of the deposit and water
only comes out as steam
leaving the solids to
concentrate

WATER WALL TUBE FACING


THE FURNACE ( HOT ) SIDE
HEAT
Case study --- contaminated condensate
Boiler parameters : 80 MW unit ; 90 kg / cm2 ; PO4 treatment
Problem : ~ 0.75 ppm of TDS in condensate detected
Situation : chemists request to stop the unit denied ; load demand
high ; unit ran for about 15 days
Action : blowdown increased
pH and PO4 controlled in boiler water
monitoring frequency increased
Consequence :
After about 2 months , water wall tubes started failing
frequently
unit stopped on numerous occasions
Remedy :
tubes replaced at a cost of US $ 2,000,000 /-
Case study --- organics
Boiler parameters : 50 tph unit ; 40 kg / cm2 ; amine treatment
boilers generating steam for phenol production ; 80% condensate return
Problem : frequent failure of super heater tubes
Situation : deposits found in SH tubes having iron oxide and silica
Reason :
boiler water indicated organics
observed value : 20 to 200 ppm
recommended value : 0.5 ppm
Consequence :
foaming inside boiler drum resulting in carryover

Remedy :
Upgrade analytical system to detect organics in feed
water , and boiler water
organics to be removed condensate polisher
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Lay-up and offline corrosion


More corrosion can occur during an outage than any
other time
This is due air intrusion and subsequent corrosion by
oxygen
Lay up guidelines : boiler filled with water containing
200 ppm hydrazine and ammonia to pH 10
Nitrogen blanket ( 0.5 kg/sq.cm) to the drum and superheater
through the vent lines
The boiler lay up solution should be circulated periodically
to avoid stagnant zones, analyzed and replenished if needed
Before the boiler is started up , the lay up chemicals need
to be removed
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Steam Chemistry

Steam purity affected by carryover --- the process by which


solids are transported to steam

Carryover influenced by
solids become more soluble at high pressures
some like silica carry over as vapour
drum level , drum design (internals) , foaming

contaminants can also enter via attemperator systems ;


greatly exacerbated during upset conditions such as a
condenser leak
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CRITICAL FACTORS IN WATER CHEMISTRY


Recommended guidelines in entire water steam cycle
to be followed always !
Special care to be taken in controlling and monitoring
dissolved oxygen , silica , & cation conductivity
Critical periods of water chemistry
Start ups Condenser leakage lay- up
Periodic chemical cleaning --- a routine maintenance step to
keep heat exchanger tubes clean
Management support :
on-line and laboratory measurement facilities
updating chemical technology knowledge base
REFERENCE

Power Plant Water Chemistry -- a practical


guide by Brad Buecker ( Pennwell )
Betz Handbook of Industrial Water Conditioning
BetzDearborn, Inc., ( Pennsylvania )
Drew Principles of Industrial Water Treatment
Cantafio. A. R., ed., ( New Jersey)
The Nalco Guide to Boiler Failure Analysis
by Herro,H.M and R.D.Port ( McGraw-Hill )
Fundamentals of Steam Generation Chemistry
by Brad Buecker ( Pennwell )
THANK YOU
DEMINERALIZATION / DIONIZATION
PROCESS BY ION EXCHANGE

Resin fouling decreases the efficiency


Slippage of exchanged ionic species will lead to
contaminant ingress into the boiler
Exhaustion of resin has to be carefully monitored
to avoid contamination by Na , Silica.
Removes 95 % -
98 % dissolved
solids having high
MW
Removes organics
Removes cationic
and anionic
contaminants
Gases are not
removed
CHEMICAL TREATMENT PROGRAMS
CHARACTERISTICS

program favourable unfavourable

All volatile deposition of salts can be Feed water contamination may


eliminated ; high purity exceed inhibiting ability of
steam under ideal feed volatile feed , leading to boiler
water conditions ; no carry corrosion ; marginal acid
over of solids neutralization ; no protection
during mild hardness ingress

oxygenated Low corrosion rates of Can tolerate very low


ferritic steels and conden- concentration of impurities ; no
treatment ser tubes ; better oxide corrosion protection in case of
coating , hence frequency upset ; copper alloys should not
of chemical cleaning be used in the system ; requires
increased excellent purity feed water ;
precise chemical control required