Water Chemistry Aspects of

Supercritical Thermal Power

Plants

Dr. S. Satpati
NPTI(ER)
Durgapur
WHAT IS “Supercritical Boilers”
“Supercritical” is a thermodynamic
expression
describing the state of a substance where
there
is no clear distinction between the liquid and
the gaseous phase (i.e. they are a
homogenous fluid).
In addition, there is no surface tension in a
supercritical fluid, as there is no liquid/gas
phase boundary.
Liquid-vapour critical point
Critical point contd………
The commonly known phases solid, liquid and
vapour are separated by phase boundaries, i.e.
pressure-temperature combinations where two
phases can coexist.
At the triple point, all three phases can coexist.
However, the liquid-vapour boundary terminates
in an endpoint at some critical
temperature Tc and critical pressure Pc. This is
the critical point.
Water reaches this state at a pressure around 220 Kg
Bar ( 225.56 Kg / cm2) and Temperature = 374.15 C.
Change in Properties of water at critical point
 Inthe vicinity of the critical point, the physical properties of the liquid
and the vapor change dramatically, with both phases becoming ever
more similar.
 For instance, liquid water under normal conditions is
◦ nearly incompressible,
◦ has a low thermal expansion coefficient,
◦ has a high dielectric constant, and
◦ is an excellent solvent for electrolytes.
 Nearthe critical point, all these properties change into the exact
opposite: water becomes
◦ compressible,
◦ expandable,
◦ a poor dielectric,
◦ a bad solvent for electrolytes, and
◦ prefers to mix with nonpolar gases and organic molecules.
 At the critical point, only one phase exists. The heat of vaporization is
zero
Introduction

 A boiler is a device for generating steam, which consists of two

principal parts:
◦ the furnace, which provides heat, usually by burning a fuel,
◦ and the boiler proper, a device in which the heat changes water into
steam.
The steam or hot fluid is then recirculated out of the boiler for use in
various processes in heating applications.
 Characteristics of boiler feed water
 Water has the highest specific heat than any other common
inorganic substance. Steam is capable of carrying large
quantities of heat. These unique properties of water make it
an ideal raw material for heating and power generating
processes.

 The amount of minerals dissolved in water varies from 30 g/l

in sea water to anything from 0.005 to 1500 mg/l in fresh water
supplies.

 Water impurities cause boiler problems.

 The purity requirements for any feed-water depend on how much
feed water is used as well as what the particular boiler design
(pressure, heat transfer rate, etc.) can tolerate.

 If the feed water does not meet these requirements it must be

pretreated to remove impurities.
 The three main reasons for water treatment are :

◦ Prevention of Corrosion in feed boiler, steam and

condensate systems.

◦ Elimination of Scale.

◦ Economic boiler operation without carryover.

Water Impurities
 The common impurities in raw water can be classified as follows:
◦ Dissolved solids - These are substances that will dissolve in water.
Eg. carbonates and sulphates of calcium and magnesium, which are
scale-forming when heated.
There are other dissolved solids, which are non-scale forming.

◦ Suspended solids - These are substances that exist in water as suspended

particles.
They are usually mineral, or organic in origin.
These substances are not generally a problem as they can be filtered out.

◦ Dissolved gases - Oxygen and carbon dioxide can be readily dissolved by

water.
These gases are aggressive instigators of corrosion.
Boiler system problems
 There
are three main problems caused in boilers due to
impurities in feed water. They are:

◦ Deposits,

◦ Corrosion, and

◦ Carryover
DEPOSITS
 Common feedwater contaminants that can form boiler deposits include
calcium, magnesium, iron, copper, aluminum, silica, and (to a lesser
extent) silt and oil. Most deposits can be classified as one of two types:
 scale that crystallized directly onto tube surfaces
 sludge deposits that precipitated elsewhere and were transported to the
metal surface by the flowing water
 The deposits typically found in boilers include:
◦ Calcium and Magnesium salts (Carbonates, Phosphates and Sulphates)
◦ Silica
◦ Iron

 A carbonate deposit is usually granular and sometimes of a very porous

nature.

 A sulphate deposit is much harder and more dense than a carbonate deposit
because the crystals are smaller and cement together tighter but is more
brittle.

 A high silica deposit is very hard, resembling porcelain. The crystal of silica
are extremely small, forming a very dense and impervious scale. This scale is
extremely brittle and very difficult to remove

 Iron deposits, due either to corrosion or iron contamination in the water, are
very dark coloured.
SLUDGE
 Sludge is the accumulation of solids that precipitate in the bulk boiler
water or enter the boiler as suspended solids.

 Sludge deposits can be hard, dense, and tenacious.

 When exposed to high heat levels (e.g., when a boiler is drained hot),
sludge deposits are often baked in place. Sludge deposits hardened in this
way can be as troublesome as scale.

 Once deposition starts, particles present in the circulating water can

become bound to the deposit
Implications of scale deposits
 If unchecked, deposition causes progressive lowering of the boiler
efficiency by heat retardation, acting as an insulator. Failure of boiler
tubes due to overheating of the metal
 deposits restrict boiler water circulation. They roughen the tube
surface and increase the drag coefficient in the boiler circuit
 Reduced circulation in a generating tube contributes to accelerated
deposition, overheating, and premature steam-water separation.
 Corrosion of the metal surface under the deposit
 Increased boiler cleaning expenses to remove the deposit
Retardation of heat transfer by Scale in Boilers
Corrosion
 Corrosion is the loss of metal as it oxidises back to the ore form, for
example iron reverts to iron oxide.
 corrosion can be
◦ uniform over the metal surface or
◦ localised, resulting in deep pits in the metal.
 Pitting corrosion caused mainly by dissolved oxygen is severe and can
result in premature replacement of boilertubes, feedwater lines and
condensate return lines.
Corrosion can be of various types:
 Galvanic corrosion
 Caustic/ alkaline Corrosion
 Hydrogen embrittlement
 Oxygen pitting
Simplified corrosion cell for iron in water
Problems created by corrosion are:
 productiondowntime and high costs for equipment
replacement.
 Increased fuel costs due to deposition of corrosion products
inside boiler tubes
 underdeposit corrosion
Carryover

 The third major problem related to boiler operations is carryover from the
boiler into the steam system.
 The steam produced from the boiler should always be as dry as possible
and contain minimal dissolved solids.
 Carryover may be a mechanical effect, such as boiler water spraying
around a broken baffle; it may be caused by the volatility of certain boiler
water salts, such as silica and sodium compounds; or it may be caused by
foaming.
 Boiler water carryover results in poor quality steam and is caused through
two problem areas:
 Foaming: Bubbles form on the boiler water surface and leave
with the steam. Foaming is caused by high TDS, high
suspended solids and contaminants such as oils,
greases, fats and certain organics.
Oil, in particular, can cause major problems due to the saponification process
where it reacts with caustic in the boiler water to form soaps.
 Priming: This is a more severe form of carryover where a sudden
surge of boiler water is drawn into the steam line.
Priming can be caused by operating the boiler above its rating,
sudden changes in steam demand and finally by
operating the water level in the boiler too high.
Calcium carbonate scaling in condenser due to
poor pH control
Fouling reduces exchanger's heat transfer efficiency
Typical oxygen pitting of condensate line
Boiler and pre-boiler corrosion

Boiler system tube shows high pH gouging

Oxygen pitting of a boiler feedwater
pipe
Boiler system failure

Economizer tube severely damaged

by oxygen

N2H4 + O2 N2 + H2O
Physical de-aeration by De-aerator

Deposit accumulation restricted heat

transfer, leading to long-term
overheating

Reduce Flow Accelerated Corrosion

by Feed Water Treatment
Boiler system failure

Boiler tube shows effect of acid attack

Acidic condition generated on tube surface

beneath the deposits. Presence of chloride
was confirmed

Violent rupture caused by hydrogen

embrittlement
Boiler system failure

Liquid metal embrittlement of boiler tube caused

by copper deposits and high temperature (greater
than 1600 °F).

Steam blanketing caused metal wastage

on top of sloped tube
WATER FLOW DIAGRAM FOR A TYPICAL POWER
PLANT
 Boiler Water Treatment
 There are three basic means for keeping these major problems under
control.
◦ 1. External treatment: Treatment of water—makeup, condensate, or
both, before it enters the boiler, to reduce or eliminate chemicals
(such as hardness or silica), gases or solids.
◦ 2. Internal treatment: Treatment of the boiler feed water, boiler
water, steam,or condensate with corrective chemicals.
◦ 3. Blowdown: Control of the concentration of chemicals in the boiler
water by bleeding off a portion of the water from the boiler.
External water treatment
 The boiler treatment program aims at control of seven broad
classifications of impurities:
◦ suspended solids,
◦ hardness,
◦ alkalinity,
◦ silica,
◦ Total dissolved solids(TDS),
◦ organic matter, and
◦ gases.
DEMINERALIZATION
TECHNIQUES
DISTILATION

ELECTRODIALYSIS

REVERSE OSMOSIS

ION EXCHANGE
 A TYPICAL REVERSE OSMOSIS
PLANT
LOW
PARTICULAT HIGH
PRESSURE
E FILTERS PRESSURE
RAW WATER PUMPS
PUMPS

RO plant

Stage-1
7 modules

PRODUCT
WATER Stage-2
4 modules

Stage-3
2 modules

STORAGE PRODUCT DEGASSING

WATER TOWER
PUMPS

CONCETRATE
TO WASTE
 REVERSE OSMOSIS
Osmosis occurs when two solutions of different
concentrations are separated from one another by a
membrane which is permeable to solvent but
impermeable to solute. Solvents flows from dilute to the
concentrated solution, until, at equilibrium, the chemical
potential of the solvent is equal on both sides of the
membrane.
 REVERSE OSMOSIS CONTI...
A pressure at which just prevent the solvent flow is
called Osmotic pressure. If the pressure greater than the
osmotic pressure is applied to the concentrated solution,
the solvent can be forced through the membrane leaving
the dissolved substances behind. This method of
purifying water is
termed reverse osmosis.
RO Membrane:
Reverse Osmosis Fundamentals:

FEED WATER: Main flow of impure water to be treated;

PRODUCT WATER: Portion of feed water which passes through membrane as permeate
REJECT WATER: Portion of feed water which did not pass through membrane; carries
impurities to drain
MODULE: Combination of spiral round membrane element &
pressure vessel
Spiral Wound Membrane:

• RO membrane is a method of fine filtration but much smaller

• Membrane consists of tiny pores which are approximately 0.0005
microns in size
• THEREFORE reverse osmosis membranes are capable of rejecting
contaminants as small as 0.0001 to 0.00001 microns
RO Membranes:

• Membrane is the work-horse of an reverse osmosis system

• When choosing an RO system you must do so wisely – taking into
account water quality is very important
• Two main types of membranes:
CTA membrane: Cellulose acetate/triacetate blend
• Provides lowest cost per gallon of water
• Resists chlorine but has a lower flow rate limit in applications of high
water consumption
TFC membrane: Thin film/thin layer composite
• Can handle high flow, has a high rejection rate & can handle high
water consumption
• Cannot handle chlorine concentrations; water must be carbon pre-
filtered
 A TYPICAL REVERSE OSMOSIS
PLANT
LOW
PARTICULAT HIGH
PRESSURE
E FILTERS PRESSURE
RAW WATER PUMPS
PUMPS

RO plant

Stage-1
7 modules

PRODUCT
WATER Stage-2
4 modules

Stage-3
2 modules

STORAGE PRODUCT DEGASSING

WATER TOWER
PUMPS

CONCETRATE
TO WASTE
 A TYPICAL REVERSE OSMOSIS
PLANT
LOW
PARTICULAT HIGH
PRESSURE
E FILTERS PRESSURE
RAW WATER PUMPS
PUMPS

RO plant

Stage-1
7 modules

PRODUCT
WATER Stage-2
4 modules

Stage-3
2 modules

STORAGE PRODUCT DEGASSING

WATER TOWER
PUMPS

CONCETRATE
TO WASTE
 A TYPICAL REVERSE OSMOSIS
PLANT
LOW
PARTICULAT HIGH
PRESSURE
E FILTERS PRESSURE
RAW WATER PUMPS
PUMPS

RO plant

Stage-1
7 modules

PRODUCT
WATER Stage-2
4 modules

Stage-3
2 modules

STORAGE PRODUCT DEGASSING

WATER TOWER
PUMPS

CONCETRATE
TO WASTE
 DEMINERALIZATION BY
ION- EXCHANGE PROCESS

Ion exchange is the reversible interchange of ions between a

solid (ion exchange material) and a liquid in which there is no
permanent change in the structure of the solid. Ion exchange is
used in water treatment and also provides a method of
separation for many processes involving other liquids. It has
special utility in chemical synthesis, medical research, food
processing, mining, agriculture, and a variety of other areas.
The utility of ion exchange rests with the ability to use and reuse
the ion exchange material.
DEMINERALISATION STREAM
ACTIVATED CARBON FILTER
(ACF)
Acts on principle of adsorption which is a
surface active phenomenon .

It removes residual turbidity (<2 NTU) of

water to its 1/10 level.

It removes organic molecules to control

color and odor.

It removes free residual chlorine present in ACTIVATED

filtered water(0.5 ppm Nil) CARBON
 TYPES OF RESIN
SAC: Strong Acid Cation
WAC: Weak Acid Cation
SBA: Strong Base Anion
CH3
WBA: Weak Base Anion
|

(R)
R-SO3H R-CH2-NH+ OH
|
Sulphonic Acid CH3
Tertiary Ammonium
(SAC)
(WBA) CH3
R-CH2CHCH3 |
| R-CH2-N-CH3 OH
COOH |
CH3
Carboxylic Acid Quarternary Ammonium
(WAC) (SBA)
VESSEL DESIGN
WEAK ACID CATION (WAC)

Weak acid cation exchange resins derive

R-CH2CHCH3 their exchange activity from a carboxylic
| group (-COOH). When operated in the
COOH
hydrogen form, WAC resins remove cations
that are associated with alkalinity,
producing carbonic acid as shown:
STRONG ACID CATION (SAC)

SAC resins can neutralize strong bases and convert neutral salts into
their corresponding acids.
SAC resins derive their functionality from sulfonic acid groups
(HSO3¯). When used in demineralization, SAC resins remove nearly all
raw water cations, replacing them with hydrogen ions, as shown below:
 DEGASIFIER DESIGN
In water demineralization, a degasifier, or degasser, is often used to
remove dissolved carbon dioxide after cation exchange. The most
common degassers are of the so-called forced draft or atmospheric
type.
 WEAK BASE ANION EXCHANGER

Weak base resin functionality originates in primary (R-NH 2),

secondary (R-NHR'), or tertiary (R-NR'2) amine groups. WBA
resins readily re-move sulfuric, nitric, and hydrochloric acids, as
represented by the following reaction:
 STRONG BASE ANION EXCHANGER
SBA resins derive their functionality from quaternary
ammonium functional groups. When in the hydroxide form,
SBA resins remove all commonly encountered anions as shown
below:

As with the cation resins, these reactions are reversible,

allowing for the regeneration of the resin with a strong alkali,
such as caustic soda, to return the resin to the hydroxide
form.
 MIXED BED EXCHANGERS

A mixed bed exchanger has both cation and anion

resin mixed together in a single vessel. As water
flows through the resin bed, the ion exchange
process is repeated many times, "polishing" the
water to a very high purity.

Due to increasing boiler operating pressures and

the manufacture of products requiring
contaminant-free water, there is a growing need
for higher water quality than cation-anion
demineralizer can produce.
INTERNAL TREATMENT
The purpose of an internal treatment is to

 react with any feed-water hardness and prevent it from

precipitating on the boiler metal as scale;
 condition any suspended matter such as hardness sludge or
iron oxide in the boiler and make it non-adherent to the
boiler metal;
 provide anti-foam protection to allow a reasonable
concentration of dissolved and suspended solids in the
boiler water without foam carry-over;
 eliminate oxygen from the water and provide enough
alkalinity to prevent boiler corrosion.
CHEMICAL TREATMENT CHEMICALS
 Chemical Treatment: corrosion and scale inhibitors which contains
the following components, in the form of separate chemicals:

 1 hydrazine as an oxygen scavenger.

 2 Phosphate or EDTA as a scale inhibitor.
 3 Ammonia and Morpholine as an alkalinity builder.
 4 Antifoaming agents and sludge conditioners
Boiler Water pH Control
 The pH of the water in the C,FW,B system is controlled via
chemical additions downstream of the CEP discharge.
 On-line pH measurements are made in this area, prior to
the LP feedheaters.
 Thus-boiler water pH is controlled by maintaining the
feedwater at the correct pH.
 Although the value of the desired operating pH for the
C,FW,B system depends on the materials used in the
vessels and piping, it is always alkaline.
 Chelant Programs
 A chelate is a molecule similar to an ion exchanger; it is low in molecular
weight and soluble in water.
 The sodium salts of ethylene diamine tetraacetic acid (EDTA) and
nitrilotriacetic acid (NTA) are the chelating agents most commonly used
for internal boiler treatment.
 These chelate (form complex ions with) calcium and magnesium.
 Because the resulting complex is soluble, this treatment is advantageous
in minimizing blowdown.
 The higher cost compared to phosphate usually limits the use of chelates
to feed waters having low hardness.
 There is the risk that breakdown of the organic molecule at higher
temperatures could create a potential problem of control that could result
in corrosion.
 The addition of polymers as scale control agents increases the
effectiveness of chelate programs.
 It also reduces the corrosion potential by reducing the chelant dosage
below theoretical requirements, so that there is no chelant residual in the
boiler water.
 Chelates can react with oxygen under boiler water conditions, which can
increase the cost of a chelate program substantially.
 Overfeed of chelates and concentration mechanisms in the boiler can lead
to severe localized corrosion and subsequent unit failure.
 Oxygen Removal
 Dissolved oxygen is removed from the condensate by the deaerator
(DA) which contains sprays and cascade trays over which the hot
water tumbles.
◦ The combination of heat and large surface area imparted to the
water provides very efficient stripping of dissolved gases Oxygen is
reduced to < 10 µg/kg(ppb) and nitrogen is also removed.
◦ This efficient stripping action reduces the consumption of
hydrazine.
 The final stage of dissolved oxygen removal is by the injection of
hydrazine (N2H4), between the deaerator and the deaerator storage
tank, to chemically
 The specification for hydrazine depends on the materials
used in the system:
 - Ferrous/Copper: 10 - 30 µg/kg
 - Ferrous: 10 - 60 µg/kg
 These hydrazine levels are selected, as noted above, to
control the dissolved O2 concentration in the boiler
feedwater at <5 µg/kg.
Major Concerns with initial Super Critical
Technology water – STEAM OXIDATION

The formation of steam oxide scale in

stainless steel tubing is an important issue
to be taken into account in the design for
high steam temperatures.
 The steam oxide scale formation rate
increases with operating temperature, and
as a result the potential for exfoliation of
oxide scales can become very high.
 WATER TREATMENT IN
SUPERCRITICAL BOILERS- EXTERNAL
Depending on the source of water
1. Clarification
2. Filtration
3. Demineralization
4. DM With RO
Make up water quality at DM Outlet
Conductivity of > 0. 1 ms/cm
Silica - <10 ppb
 FEED WATER TREATMENT

Type - A: AVT(R) ;using Ammonia and a

Reducing Agent (such as Hydrazine)

Type – B: AVT (O); Similar to Type – A minus

reducing agent

Type – C : (OT); Oxygenated Treatment using

only ammonia and oxygen
OXYGEN TREATMENT FOR SUPER
CRITICAL POWER PLANTS
 Supercritical boilers do not have a steam
drum. Therefore, extremely high levels of purity is
required for feed water
 Poor feed water can result into carry over

of impurities which will result in turbine

blade deposits
 Oxygen Treatment improves the quality of

water by reducing the flow assisted corrosion

 Oxygen is injected in the range of 30-150 ppb for
once through units and 30-50 ppb for drum units, with
the pH in the range of 8.5-9.5 for once through units
 OT AN ALTERNATIVE
 PROVIDES LONG TERM PROTECTION OF PRE
BOILER SYSTEM BY FORMING HAMETITE
LAYER.
 CPU OPERATING PERIOD WILL BE MORE DUE TO
LOW CONDENSATE AMMONIA CONTENT
 IRON TRANSPORT WILL BE REDUCED BY 90%
 LESS GENERATION OF SLUDGE
 REDUCTION IN CHEMICAL CLEANING
FREQUENCY
 REDUCTION IN OUTAGE TIME AND FASTER
START UP
SCHEMATIC OF OXIDE GROWTH AND MORPHOLOGY
UNDER 0XIDISING AVT AND OT

2 Fe3O4 + 0.5 02 = 3 Fe2O3

ADVANTAGES OF OXYGENATED
TREATMENT
Oxygen treatment minimizes flow
assisted corrosion by the production of
more stable iron oxide Hematite layers .
Oxygen gas is dosed at deaerator and
Condensate polishing unit outlet through
gas
cylinders in a controlled manner.
FEED WATER QUALITY PARAMETER FOR SC BOILERS
Thank You