Topics

Water Chemistry- Major Impurities & Significance

Need for internal treatment.
Various internal treatment programs.
Water treatment from seawater to Boiler feed water
Fundamental of deaeration, its internal chemical
treatment and its significance.
Case study on past disturbance and its analysis or
phenomena substantiated with photographs
Water treatment philosophy in CPP boilers
WATER CHEMISTRY
 SOURCE
RAIN
SURFACE
UNDERGROUND
SEA
IMPURITIES
SUSPENDED / DISSOLVED
INORGANIC
ORGANIC
GASEOUS
 Inorganic
Silt / Mud
Salts, Na, Ca, Mg - Cl, SO4, HCO3, OH, H+
Organic
Slime / Humic Acids
Alcohol, Aldehydes, Acid
Gases
O2, N2, CO2
Ammonia , H2S
 WATER ANALYSIS
Turbidity NTU : Suspended, Colloidal
Matter
pH ( 0 - 14) : Acidity, Alkalinity
TDS (ppm) : Total dissolved solids
TSS (ppm) : Total suspended solids
Conductivity (ms/cm) : Dissolved solids
Total (M) Alkalinity (ppm) : OH, CO3, HCO3
P - Alkalinity (ppm) : CO3, OH
OH - Alkalinity (ppm) : OH
Chlorides (ppm) : Chlorides
Sulphates (ppm) : Sulphates
Silica (ppm) : Silicate
BOD (ppm) : Organics
COD (ppm) : Organics
 WATERSIDE PROBLEMS IN BOILERS
SCALING
INADEQUATE MAKE UP WATER QUALITY
( SCALE FORMING IONS)
REACTIONS Ca ++,Mg ++,CO3--,HCO3 --,SiO3--
Ca +2 HCO3 CaCO3 + H2O + CO2
Ca + SO4 Ca SO4
Ca + SiO3 Ca SiO3
Mg + SiO3 MgSiO3
Ca & Mg COMPOUNDS HAVE INVERSE OVER HEATING OF TUBES
SOLUBILITY - INSOLUBLE AT ELEVATED REDUCTION OF HEAT
TEMPERATURES. TRANSFER
CALLS FOR SHUT DOWN
RESTRICTION OF WATER -
CIRCULATION

CONTAMINATED CONDENSATE LEAKAGE

OF TURBINE CONDENSORS/ PROCESS
LEAKS
 WATERSIDE PROBLEMS IN BOILERS
CORROSION
LOW pH
LOW ALKALINITY METAL LOSS,PITTING
DISSOLVED OXYGEN LOSS OF PROTECTECTIVE OXIDE FILM
(DESIRED PROTECTECTIVE FILM IN BOILER
IS MAGNETIC IRON OXIDE, Fe3O4. OXYGEN
DESTRUCTS THE PROTECTIVE OXIDE FILM)
4Fe3O4 + O2 6 Fe 2O3

CONDENSATE CORROSION
CARBONDIOXIDE
BICARBONATES + HEAT CO2
CO2 + H2O H2CO3 ( CARBONIC ACID)
Fe + H2CO3 Fe (CO3)2

CAUSTIC CORROSION / EMBRITTLEMENT

HIGH CAUSTIC Fe3O4 + 4NaOH = 2 NaFeO2 + Na2FeO2 + H2O
ALKALINITY (Sodium ferroate)
Fe + NaOH = Na2FeO2(Sodium Ferrite) + H2
 WATERSIDE PROBLEMS IN BOILERS
CARRY OVER

OCCURS WHEN MOISTURE & ENTRAINED SOLIDS PASS OVER WITH STEAM .
MECHANICAL
HIGH WATER LEVEL
INCOMPLETE SEPARATION OF STEAM & WATER
HIGH STEAMING RATE
BOILER DESIGN AFTER BOILER DEPOSITS
UNEVEN FIRE DISTRIBUTION
LOAD FLUCTUATIONS PLUGGED VALVES AND
TRAPS

CHEMICAL DEPOSITION ON TURBINE

HIGH TDS (TOTAL DISSOLVED SOLIDS) BLADES
HIGH ALKALINITY
LEAKAGE OF OIL / ORGANICS
 Internal Treatment - Need

To maintain the BFW/BW & Steam quality

as per standard specified norms.
Malfunctioning of the equipment
(Softener/DM/Deaeration).
To take care of upsets in water quality
- Unexpected ingress resulting in pH
fluctuations , Oil Contamination etc.
Internal Treatment - Various
Methods
Phosphate - Hydroxide

Coordinated Phosphate control

Polyphosphate-Polymer Based
Chelant program
All organic treatment- filming
Amine based.
SCALE CONTROL
 Phosphate - Hydroxide Method

In this method Trisodium Phosphate & Caustic are used to

maintain pH 10.5 - 11.2 . Calcium Precipitate as Calcium
Hydroxyappatite - Non adherent sludge - which is drained
during the blowdown.

Magnesium reacts with caustic to form magnesium Hydroxide

Mg(OH)2

10 Ca ++ + 6 PO4 -- + 2 OH - Ca10(OH)2(PO4)6

0r

( 3 Ca3(PO4)2.Ca(OH)2)
Calcium Hydroxyapatite
 Polyphosphate - based

Polyphosphates are long chain phosphates which form fairly

soluble complexes with scale forming salts. The dispersing
action of polyphosphate further helps in keeping the boiler
internals clean.

This program is commonly used as formulations. The selection

of polymer to be added in formulation is important.
Polyphosphates

O O

NaOP O P ONa

O O
Na Na
X
 Chelant - based

The chelant reacts with the hardness ions ( Calcium & Magne
sium) , Iron and form soluble complexes which can be
discharged during the blowdown.

EDTA & NTA are common chelants used in chelant based

programs

-OOC - CH2 CH2COO-

N CH2 CH2 N

-OOC - CH2 CH2COO-

Co-ordinate Phosphate
Treatment Programme
Na3PO4 + H2O Na2HPO4 + NaOH
Na2HPO4 + H2O NaH2PO4 + NaOH

TSP to DSP DSP to MSP

pH % complete pH % complete
9 100 5 100
10 100 6 94
7 61
11 95
8 14
12 67
13 17 9 1

14 2 10 0
 Caustic
TSP

DSP

MSP
Blowdown

VECTOR CONTROL DIAGRAM

 Sea water to BFW
Sea water filtration : To remove all suspended solids from Sea Water.
Passing through ion trap : To remove heavy metals and Copper from
sea water higher corrosive to aluminum tubes ( galvanic corrosion)
Desalination plant with 4 * 500TPH capacity.
Multiple effect distillation process ( MEDP) To separate fresh water
( 5-7us/cm) from sea water by MED. Heat source for MED is LP / LLP
steam from the refinery. Analysis : pH/Conductivity/Iron/ TOC/Silica
Mixed bed treatment to Desal water- For replacing cations by H+ and
anions by OH-( 0.05-0.08us/cm & pH :6.7-7.0,Silica)
Deaeration: To remove Dissolved gases from the Boiler feed water
( presence oxygen (pitting corrosion))
Chemical treatment : Oxygen scavenger , pH booster ( for protecting
condensate system as well as BFW system).
 RELIANCE PETROLEUM LIMITED
UTILITY COMPLEX

SIMPLIFIED FLOW DIAGRAM: DESALINATION PLANT

EJECTOR
SYSTEM

VAPOUR VAPOUR VAPOUR VAPOUR

1 2 11
CONDENSER

FEED
SEAWATER

STEAM

STEAM
CONDENSATE

BRINE
OUTFALL
PRODUCT
DM Plant
Total capacity 1340 Cu.M/hr ( 4 beds)
Following reactions take place during ion exchange process.
Conductivity of fresh water is being reduced from 5-7us/cm to 0.05-
0.08us/cm
Bed regeneration is being done using Sulfuric acid and sodium
hydroxide.
Vital parameters : pH / conductivity / Silica
Online pH/Conductivity and Silica analyzers available to maintain
quality of Mixed bed water
Strong base Cation:
Ca++ HCO3- Ca ++ HCO3
Mg++ CO3-- Mg++ CO3
+
RSO3-H+ + Na+ Cl- RSO3- Na+ + H Cl-
K+ SO4- K+ SO4--
Fe++ NO3- Fe++ NO3-
Al+++ Al+++
Strong base Anion:

HCO3- Cl-
RN+(CH3)3OH-- + H+ Cl- + CO2 + SiO2 + Na + SO4
NO3- NO3-

NO3-
RN+(CH3)3 Cl- + H2O + Alkaline solutions like NaOH , Na2CO3, NaHCO3
HCO3-
HSiO3-
SO4
 Deaeration
Deaeration is required to remove all dissolved gases from
Boiler feed water . Especially Dissolved Oxygen and Carbon
dioxide.
Deaeration of boiler feed water done by following principles :
The solubility of any gas in a liquid is directly proportional to
the partial pressure of gas at liquid surface.- Hendrys Law of
dilute solutions.
The solubility of gas in liquid decreases with increasing liquid
temperature.
Efficiency of removal is increased when the liquid and gas are
thoroughly mixed.
 Expected Dissolved oxygen in exit of deaerator is <7ppb. To
further reduce the O2 content in BFW, suitable Oxygen
scavenger is used.
Types of Oxygen Scavenger :
1. Sodium Sulfite : Used Low Pressure boilers.
Higher contribution to TDS in boiler
Produces SO2& H2S..Corrosive to condensate system
2. Hydrazine hydrate: Normally used in high pressure boiler
( >1000 psig)
N2H4+O2 2H2O +N2
Decomposition products Ammonia and nitrogen.
Decomposition at around 400F and rapid >600F
Added advantage : Good passivating agent
N2H4 +6Fe2O3 4Fe3O4+N2+2H2O
Disadvantages : Slow reaction time( at lower temperature)
ammonia formation, effects of copper bearing alloys and
handling problems.
 Oxygen Scavengers & pH Boosters

Hydrazine Hydrate & Sodium Sulfite based oxygen

scavengers
most commonly used.
Other Oxygen scavengers

DEHA, Carbohydrazide, Hydroquininone etc.

pH boosters
Ammonia, Morpholine, MCHA are used.

Chemical DR at 600 PSIG

Morpholene 1.3:1
MCHA 6.6:1
Ammona 4.2:1
Vital parameters : pH, Dissolved oxygen, Residual hydrazine
hydrate
Reaction rate of Hydrazine hydrate with O2 is high at higher pH
values ( 9-9.5) and higher BFW pH to be maintained.

Existence of residual N2H4 ensures absence of dissolved oxygen

Neutralization reaction with Carbonic acid.

R-NH3+ + OH- + H2CO3 R-NH3+ + HCO3- + H2O

 pH boosting & steam condensate system
protection:
Higher pH of BFW is required to facilitate the hydrazine
reaction with Oxygen. Being alkaline in nature, amines
maintain pH throughout BFW system and Economizer to
protect system from corrosion.( acid corrosion)
pH boosting is done with amine blend. Maxtreat-3305 ( 60%
Morpholene & 40% MCHA).
Amine blend is used to protect steam condensate system due
to its better distribution coefficient ( 50:50). This blend is
required as steam is being used in various pressure levels
Amine Blend chosen based on following criteria
Distribution coefficient ( steam-water)
Thermal stability
Basicity
 Boiler water treatment
Coordinate Phosphate treatment Program ( Conventional treatment) using Trisodium phosphate.
Advantages: Protection against caustic embrittlement , caustic gouging. Sudden pH fluctuations.
Vital parameters : pH/Conductivity/Ortho Phosphate /Silica/ Iron/P&M alkalinity/ Chlorides
Significance of boiler water analysis:
pH control is important because:
Corrosion rate of metals used in boiler systems are sensitive to variations in pH.
Low pH or insufficient alkalinity can result in corrosive acidic attack.
High pH or excess alkalinity can result in caustic gouging, caustic embrittlement, cracking, forming
( carryover)
 Speed of O2 scavenging is dependent on pH levels.
Silica carryover (as Silicic acid )with steam is dependent on
pH levels
Corrosion rate of carbon steel at feed water temperatures
approaches a minimum values in the pH range of 9.2-9.6.
Significance of Conductivity
forming, water carryover with steam results super heater
failure
Increase in conductivity increases the corrosion rate initially
and then decreases the same.
Significance of Ortho phosphate.
Sufficient amount of PO4 has to be maintained in boiler water
to protect boiler from scale formation. PO4 reacts with scale
forming ions and forms non adherent complexes which can be
removed by giving blowdown.
Amount of PO4 to be maintained in boiler water to be
determined based on BFW quality
Significance of Silica: Solubility of silica in steam increases with
increase in temperature. Hence, at higher boiler water silica
concentrations, silica carryover as silicic acid with steam increases,
which in turn results in deposition on turbine blades.( reduces
turbine efficiency and further failures). To avoid all above, lower
silica concentration in boiler water suggested.
Significance of Iron : is a measure of corrosion rate in boiler.
Significance of P& M alkalinity: appropriate control on alkalinity
levels is required to avoid caustic corrosion . P & M alkalinity is
being measured in boiler to ensure absence of Free caustic
alkalinity ( 2P-M values </= 0 ensures absence of free OH
concentration).
Significance of Chlorides: control of chlorides in boiler water is
very essential especially on presence hardness. Trace of amount of
Ca, Mg ions react with chlorides to calcium , Magnesium chlorides
which in turn forms hydrochloric acid. This will reduce the pH of
boiler water to greater extent ( as low as 4.3).
Vital parameters in Steam :
pH/Conductivity/ Silica/Sodium/Chlorides:
Sufficient pH values in steam condensate is to be maintained to protect
condensate system.
Silica content must be <0.02ppm in steam to avoid deposition over
turbine.( pls find attached graphs)
Deposition formation guide ( Courtesy : Drew s Water chemistry book)

Deposition Formation Guide

Solids in steam Super heater

ppm Turbine Deposition deposition
<0.01 NO NO
0.01-0.1 Possible NO
0.1-1.0 Yes Possible

>1.0 Yes Yes

Case study:
Super heater failure in 522-V01 steam generator:
System details : 45Kg/cm2 Steam generator, natural circulation
boiler with steam drum & process gas boiler. Normal steam
generation rate is 125-130TPH.
Treatment :
Hydrazine hydrate as oxygen scavenger (added in CPP).
Amine blend for pH boosting( added in CPP).
TSP (30-40ppm as PO4) for protecting the system from scale
formation . As per Coordinate Phosphate treatment Program.
(added in steam drum through HP dosing system)
Incident occurrence : 15th of Jan-2003.
Type of failure : fish mouth burst / Thin lipped burst
Root cause : Phosphate deposition in super heater / over
heating / Caustic corrosion/ under deposit corrosion
 On 29thy Aug-02.Sudden plant trip due to process problem.
Rapid fluctuations in steam drum level observed during start
up.
PO4 values of boiler water has got increased from 30ppm to
1500ppm during plant trip with conductivity rise of above
5000us/cm
pH values of boiler water has got increased from 9.8 to 11.2
during plant trip.
Increase in PO4 values in boiler water is due to sudden drop in
plant load.
PO4 in form of TSP+DSP mixture got deposited at high heat
flux zones of PGB( process gas boiler). Due to heat flux
variations, PO4 deposited got re-dissolved in boiler water and
resulted in higher alkalinity , PO4 and pH levels.
 Higher Alkalinity values in boiler water created forming/ carryover
in steam drum. As a result of carry over , PO4 in boiler water
carried over with steam and got deposited in super heater section.
PO4 deposition in Super heater resulted in localized Over heating
of tubes. Caustic available in PO4 resulted in caustic corrosion and
under deposit corrosion. Combination of all above three
phenomena resulted in Violent burst of super heater tubes
Recommendations to avoid recurrence of incident:
Operating boiler with minimum required PO4 concentration in
boiler water with reduce the PO4 deposition intensity.
Operating boiler with as minimum as possible steam drum level to
provide more vapor space for steam water disengagement.
Suitable demisters/cyclone separators to be provided to reduce
intensity of carryover.
Follow an IBD schedule to remove accumulated sludge from
PGB /Steam drum.
Various specification for BFW, Boiler water, Steam
DRUM OPERATING PRESSURE (psig)

0-300 301- 451- 601-750 751-900 901- 1001- 1501- OTSG

450 600 1000 1500 2000

STEAM

TDS max 0.2- 0.2- 0.2- 0.1-0.5 0.1-0.5 0.1-0.5 0.1 0.1 0.05
(ppm) 1.0 1.0 1.0

BOILER WATER

TDS max 700- 600- 500- 200- 150-750 125-625 100 50 0.05
(ppm) 3500 3000 2500 1000
350 300 250 200 150 100 Not Not n/a
ALK max specified specifie
(ppm) d
TSS Max 15 10 8 3 2 1 1 n/a n/a
(ppm)

Conducti 1100- 900- 800- 300- 200- 200- 150 80 0.15-.25

vity max 5400 4600 3800 1500 1200 1000
(mho/c
m)

Silica 150 90 40 30 20 8 2 1 0.02

max
(ppm
SiO2)
FEEDWATER (CONDENSATE & MAKEUP, AFTER DEAERATOR)
0-300 301-450 451-600 601-750 751-900 901-1000 1001- 1501- OTSG
1500 200
0
Dissolved 0.007 0.007 0.007 0.007 0.007 0.007 0.007 0.007 Not
Oxyg sensit
en ive
(ppm
O2)
Total Iron 0.1 0.05 0.03 0.025 0.02 0.02 0.01 0.01 0.01
(ppm
Fe)
Total 0.05 0.025 0.02 0.02 0.015 0.01 0.01 0.01 0.002
Copp
er
(ppm
Cu)
Total 0.3 0.3 0.2 0.2 0.1 0.05 None None None
Hard dete dete detec
ness cted cted ted
(ppm
CaC
O3)
8.3- 8.3-10.0 8.3-10.0 8.3-10.0 8.3-10.0 8.8-9.6 8.8-9.6 8.8-9.6
10
pH @ 25 .0
C
Nonvolatil 1 1 0.5 0.5 0.5 0.2 0.2 0.2 None
e detec
TOC ted
(ppm
C)
Oily 1 1 0.5 0.5 0.5 0.2 0.2 0.2
Matt
er
(ppm
)
 IS
ASME: Specs;
specification 45kg/c
Sl.No Parameter , 45kg/cm2 m2 NDS specs,
1 Dissolved Oxygen in ppb <7ppb <5ppb <20ppb
2 Total Iron in ppb <25ppb <30ppb
Fe+Cu =
3 Total Copper in ppb <20ppb <10ppb <5ppb
4 Total Hardness in ppb <200ppb nil <10ppb
5 pH 7.5-10 8.5-9.5 >9.0
6 Conductivity in us/cm NS <0.3 <0.2
7 KMnO4 NS NS <3ppm
8 Oil NS NS <1
9 Silic acid ( SiO2) NS <20ppb <20ppb

NS = Not specified

Conductivity to be measured after passing through Cation column

 Reliance specification

CPP Feed Water CBD sample

Specs
Sr.NO Parameters Unit Limit Parameters Unit

1 pH NA 8.6-9.2 pH NA 8.9-10
Conductivity @ 25 micro-
2 Deg .C s/cm 9 max Ortho PO4 ppm 4.0-10.0
Above micro-
3 Residual N2 H4 ppm traces conductivity s/cm 100max

4 SiO2 ppm 0.05 max. SiO2 ppm 2max

5 TDS ppm 6.03 max TDS ppm 67Max

Total Iron as
6 Total Iron as Fe ppm To report Fe ppm To report

Chlorides ppm 5max

Optional P-alkalinity ppm To report

1 Oil Content ppm 0.2 max M-alkalinity ppm To report

2 TOC ppm 4 max 2P-M < or = 0

3 Total Copper as Cu ppm 0.01 max

4 Dissolved Oxygen ppb 20 max

5 Chlorides ppm 0.1 max

 Boiler water treatment in CPP
Treatment : Hydrazine hydrate as oxygen scavenger
Amine blend for pH boosting
HRSG systems : DSP (4-10 ppm as PO4) for protecting the system from scale
formation . As per Coordinate Phosphate treatment program.( being added in
steam drum through HP dosing system)
Auxiliary boilers : DSP +TSP mixture of 2.3-2.5 Na to PO4 ratio(4-10 ppm as
PO4) for protecting the system from scale formation . As per Coordinate
Phosphate treatment program.( being added in steam drum through HP dosing
system)
Suggested regime for pH/PO4 coordinates in vector control diagram is 2.6-2.8
Na:PO4 curves. As a result of concentrating effect at tube surface, it appears to
be that a combination of TSP and DSP precipitates form. If Na to PO4 ratio in
water phase is greater then that of precipitate, the result is an excess of NaOH in
supernatant liquid. If water phase and precipitate have same ratio then, system
will act as chemically congruent. Further if ratio is congruent or lower in the
water phase in the solid phase, no free caustic available in boiler water.
 The exact composition of the phosphate precipitate depends on
temperature and has been found to be in the range of 2.6-2.8 for
pressure ranging from 1500psig to 3000psig. Thus, an Na/PO4
ratio of 2.6:1 is considered safe for all drum type boilers.
pH/PO4 coordinates can be maintained in 2.6-2.8 Na:PO4 molar
curve by using lower molar ratio dozing solution.( lower molar
ratio dosing solution can be attained by mixing various
propositions of TSP & DSP mixtures)
Operating boilers with continuous blowdown. This is to provide
more stability to boiler water system.( keep check on alkalinity
build up as well as unexpected acid ingress)
Caustic corrosion : 1. Caustic gouging ,2.Caustic embrittlement.
Caustic gouging: Continuous dilution of magnetite layer due to
excess free caustic concentration in boiler water.
Caustic embrittlement: is an inter-crystalline stress corrosion
cracking of boiler carbon steel caused by a corrosion reaction
along the grain boundaries within the metal. Caustic
embrittlement occurs when specific conditions are present :
tensile stress in the metal, high hydrate alkalinity (50,000ppm
for example) in contact with the stressed metal, and water with
embrittling characteristics.
Free Caustic Zone

Acid Zone