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WATER CHEMISTRY CONTROL

IN HRSG

WATER SOURCES TO HRSG


BFW
MAKE UP WATER
DIFFERENCE

TYPES OF IMPURITES
Impurity
Soluble Gases

H2S

Resulting in

Got rid by

Corrosion of boiler tubes

Aeration, deaeration and


chemical treatment

Sludge and scale carryover

Clarification, filtration and


chemical treatment

O2
CO
Suspended
solids

Dissolved
colloidal solids

Sediment and
turbidity
Organic matter

Carryover, foaming and


corrosion

Oil and grease

Foaming, deposition

Coagulation, filtration

Hardness Ca
& Mg

Scaling, inhibits HT, boiler tube


burn thru

Softening and internal treatment

Na, Alkalinity,
Na2CO3,

Foaming, corrosion,
embrittlement

Ion exchange, deionization

Sulphates

Hard scales if Ca present

Deionization

Chlorides

Priming, foaming

Deionization

Fe, Mn

Rusting, resistence to HT

Aeration, filtration, ion exchange

Silica

Scaling

Deionization, lime-soda process

Best HRSG Water Treatment


Control
External Treatment

Internal Treatment

External methods of
conditioning

Clarification
Filtration
Ion exchange
Membrane separation

Clarification

Removes all types of solids & large particles sediments, oil,


natural org. matter, colour etc.
Consists of 4 steps screening, coagulation-flocculation,
sedimentation, fine filtration.
Screening protects downstream units from large, easily separable
objects.
Three types:
Fine screening (spacing < 10 mm)
Medium screening (spacing 10 40 mm)
Coarse screening (spacing > 40 mm)
Coagulation-flocculation removes suspended solids & colloidal
particles.

Clarification (contd.)
Important factors velocity gradient, time, pH
Flotation to separate particles having density lesser
than water.
Three types:
Natural
Aided
Induced
Induced flotation facilitated through bubbling of air; 2
types
Dissolved air flotation (DAF) (bubbles of 40 70 m)
Mechanical flotation (bubbles of 0.2 2 mm)

Filtration
Separates undissolved solids from water by means of a
filter - porous substance, membrane or permeable fabric.
Three types of filtration:
Micro filtration (pore size 0.1 10 m)
Ultra filtration (pore size 1-100nm)
Nano filtration (pore size < 1 nm)
Micro filtration removes bacteria; used for biological
wastewater treatment, effluent treatment, separation of
oil-water emulsions.
Ultra filtration - separation of suspended solids, colloids,
bacteria, virus.

Filtration (contd.)
2 ultra filtration module configurations:
Pressurized system or pressure-vessel configuration
Immersed system
Nano filtration water softening, decolouring, micropollutant removal (org. matter, heavy metals, pesticides).
Ultra & nano filtration pressure driven processes.
Pre-treatment protects filtration membranes;
microfiltration pre-filter for ultra filtration and so on.

Ion Exchange

Resins - acidic/basic radicals with ions fixed on them; exchanged


with ions present in water.
Theoretically removes 100 % of salts; does not remove organics,
virus or bacteria.
2 types of resins gel type (microporous) and macroporous or
loosely cross-linked type.
3 systems of resin beds:
Strong acid cation + Strong base anion
Strong acid cation + weak base anion + Strong base anion

Mixed-bed Deionization
Ion exchange plant softens water, removes heavy metals,
produces demineralized water.

Reverse Osmosis (RO)


By applying pressure greater than osmotic pressure, water flows from
the higher concentration solution to lower one.
Mostly used for desalination; also for waste water treatment.
Applied pressure depends on the type and salinity of water.
Working pressure:
< 15 bar for tap water (< 1500 ppm)
15 25 bar for brackish water (< 8000 ppm)
50 75 bar for sea water (35000 45000 ppm)
RO plant preceded by pretreatment to avoid membrane fouling by
sediments, bacteria, metal oxides & chlorine.
RO permeate water more acidic than the feed water due to dissolved
CO2. Common post-treatment are pH neutralization and
remineralization.

Electrodionization
Combines membrane separation and ionexchange to provide high efficiency
demineralization process.
Electric potential transports & segregates charged
aqueous species.
Electric current continuously regenerates resin; no
need for periodical regeneration.
Deionization chamber - ion exchange resin,
packed between cationic & anionic exchange
membranes.

Electrodionization
Advantages
continuous operation
eliminates use of chemicals for regeneration
low power consumption

Disadvantages
Not used for water with hardness > 1
requires purification pretreatment
Pre-removal of CO2

INTERNAL TREATMENT OF
HRSG

Internal Treatment methods


Internal treatment can constitute the
unique treatment when boilers operate at
low or moderate pressure, when large
amounts of condensed steam are used for
feed water, or when good quality raw
water is available.

PURPOSE OF INTERNAL
TREATMENT
1) react with any feed-water hardness and
prevent it from precipitating on the boiler metal
as scale;
2) condition any suspended matter such as
hardness sludge or iron oxide in the boiler and
make it non-adherent to the boiler metal;
3) provide anti-foam protection to allow a
reasonable concentration of dissolved and
suspended solids in the boiler water without
foam carry-over;
4) eliminate oxygen from the water and provide
enough alkalinity to prevent boiler corrosion.

CHEMICALS USED FOR


INTERNAL TREATMENT

PHOSPHATE (TSP, NALCO 7208)


CHELATES
POLYMERS
All above chemicals condition the calcium and
magnesium.
Chelates and polymers forms water soluble
complexes.
Phosphates precipitates the hardness
Sludge conditioners are also used to precipitate
hardness

MECHANISM OF PHOSPHATE
TREATMENT FOR HARDNESS
At boiler operating temperatures
calcium bicarbonate in the feed water breaks down to
form calcium carbonate. Since it is relatively insoluble, it
precipitates. Internal treatment with phosphates
transforms calcium bicarbonate to calcium phosphate
and sodium carbonate
Sodium carbonate in the water partially breaks down to
sodium hydroxide and carbon dioxide.. In the presence
of hydroxide alkalinity, magnesium bicarbonate
precipitates as magnesium hydroxide or reacts with silica
to form magnesium silicate.
These minerals are precipitated from solution in form of
sludge, which must be conditioned to prevent its sticking
to the boiler metal. The conditioned sludge is then
removed from the boiler by blowdown.

MECHANISM OF CHELATES AND


POLYMERS FOR HARDNESS
When chelate is used for internal treatment, it
reacts with calcium and magnesium salts to form
soluble complexes. These complexes are in the
form of dissolved solids and are removed by
blow down.
Dispersant polymers used in conjunction with
chelate produces reaction products, which are
better conditioned. They do not precipitate and
are more easily removed by blow down.

INTERNAL TREAMENTS FOR


SULFATES
The boiler temperature makes the calcium and
magnesium sulfates in the feed water insoluble.
With phosphates used as internal treatment,
calcium reacts with the phosphate producing
hydroxyapatite, which is much easier to
condition than calcium sulfate. With chelates or
polymer used as internal treatment, calcium and
magnesium react with these materials producing
soluble complexes that are easily removed by
blowdown.

INTERNAL TREATMENT FOR


SILICA
If silica is present in the feedwater, it tends to
precipitate directly as scale at hot spots on the
boiler metal and or combines with calcium
forming a hard calcium silicate scale. In the
internal treatment for silica, the boiler water
alkalinity has to be kept high enough to hold the
silica in solution. Magnesium, present in most
waters, precipitates some of the silica as sludge.
Special organic materials or synthetic polymers
are used to condition magnesium silicate from
adhering to the boiler metal.

INTERNAL TREATMENT FOR


SLUDGE CONDITIONING

Starches effective on high silica feedwater


and where oil contamination is a problem
Lignins effective on phosphate type sludge
Tannins fairly effective on high hardness
feedwater
Synthetic polymers Highly effective sludge
conditioners for all types of sludges
Note: For low pressure boilers Only.

INTERNAL TREATMENT
CHEMCIAL DOSAGE

TSP or NALCO 7208


LP DRUMS: 5-15 PPM
HP DRUMS: 1- 5 PPM
Na: Po4

TESTS FOR TREATMENT


CONTROL

pH
Conductivity
Phosphate
Silica
Iron
Na:Po4
Chlorides
Sulfates

ROLE OF BLOW DOWN


Blowdown is the discharge of boiler water
containing concentrated suspended and
dissolved feed water solids. As the blowdown
water is replaced with lower solids feed water,
the boiler water is diluted. With proper regulation
of blowdown, the amount of solids in the boiler
water can be controlled. The amount of
blowdown needed depends on how much feed
water impurities a given boiler can tolerate.

BLOW DOWN EXAMPLE


If a particular boiler can tolerate 500 ppm
maximum dissolved solids, and the feed water
contains 50 ppm, it can be concentrated only
about 10 times. This means that for every 100
pounds of water fed to the boiler about 10
pounds of boiler water must be blown down to
keep the dissolved solids from exceeding 500
ppm. Total dissolved solids is not the only
limiting factor in determining blowdown, other
considerations include suspended solids,
alkalinity, silica and iron.

CORROSION CONTROL IN
CONDENSATE SYSTEM
Corrosion in steam condensate system is
caused by carbon dioxide and oxygen
carried into the system by steam.
Dissolved carbon dioxide in condensed
steam forms corrosive carbonic acid. If
oxygen is present with carbon dioxide, the
corrosion rate is much higher, and is likely
to produce localized pitting. Ammonia, in
combination with oxygen, attacks copper
alloys.

PREVENTION OF CONDENSATE
CORROSION
Condensate treatment is done by use of
volatile amines, ammonia to neutralize
carbon dioxide or volatile filming inhibitors
to form a barrier between the metal and
the corrosive condensate
Nalco 72310, Nalco 352, Ammonia 25%

REMOVAL OF NON
CONDENSIBLE GASES BY
DEAERATION

WHAT IS IT

REMOVING OXYGEN

REMOVING OXYGEN

REMOVING OXYGEN

REMOVING OXYGEN

CORROSION PROCESS

PITTING

GENERAL SKECTH

DA PROBLEMS

MONITORING

OXYGEN SCAVANGING BY
CHEMICALS

HYDRAZINE
ELIMINOX

Corrosion Control contd.


Control: downtime and storage
Oxygen in-leakage and pH lowering
Dry storage: long downtime, month or more
Completely dried
Applied dessicants like quicklime, silica gel,
activated alumina

Wet storage: short downtime


Cleaning, inspection and filling with deaerated
feedwater
Addition of scavenger, heat addition

Deposits
Scaling/deposition from carryover
Carbonate/Phosphate control
Addition of certain amounts of carbonate/phosphate for ensuring
precipitate in the form of salts. Prevention of Sulphates
For removal of hardness, Ca and Mg
Precipitation in bulk instead of at walls, non-adherent

Organic supplements: fluid sludge formation (polymer


addition)
Bottom blowdown removes sludge

Chelant control
Combination of additives
Blowdown

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