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Boiler Water

Chemistry

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CCGT Operations Principles
COURSE OBJECTIVES

Gain an appreciation of Chemistry


Help you to understand what is going on
within the boiler
Help you solve problems.
The course will NOT make you an expert

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CCGT Operations Principles
What is an Element ?

A Naturally Occurring Substance That Can


Exist On Its Own

What is an Atom ?

The Smallest Part of an Element Which Can


Exist Without Changing The Substance

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CCGT Operations Principles
What is a Compound ?

Two or More Elements Chemically Bonded


Together to Form a Single Substance

What is a Mixture ?
A Number of Substances Mixed Together, Which
Can Be Easily Separated. They Have No
Chemical Bond

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CCGT Operations Principles
Why Treat Water For Our Boiler ?

Water Contains Impurities That Can Damage The


Boiler Structure

What Causes The Problems ?

Scale Forms on Hot Surfaces Causing Both


Overheating & Material Degradation
Other Substances Form Acids Which
Corrode The Boiler
Oxygen in Water Causes Rust Formation

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CCGT Operations Principles
Impurities of Water ?

The Amount of Impurities Contained in Water,


Depends Upon Where The Water Came From

How Big is The Impurity Problem ?


Sea Water 50 000 S/cm
Industrial River 1 500 S/cm
Bore Hole 800 S/cm
London Town Water 450 S/cm
Manchester Town Water 40 S/cm

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CCGT Operations Principles
What is a Molecule ?

The Smallest Part of Any Compound Which


Can Exist Alone, Without Changing The
Substance

What is a Reaction ?
A Total Re-arranging of the Chemical
Structure of Two or More Substances
Brought Together Under The Right
Conditions

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CCGT Operations Principles
Does The Type of Boiler Make Any Difference ?
Higher Boiler Pressures & Saturation Temperatures Cause
certain chemicals & Impurities to Hide-Out - They seem to
disappear
They Concentrate in Less Turbulent areas of the Boiler Water
Path or form weak bonds with other substances
Pressure Range (bar) Dissolved Solids (mg/kg)

Up to 20 3000
21 to 40 2500
41 to 60 1000
61 to 80 200
81 to 100 50
101 to 120 20
Over 121 10
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CCGT Operations Principles
Temporary Hardness

Calcium Carbonate = CaCO3


Calcium Bicarbonate = Ca(HCO3)2
Magnesium Carbonate = MgCO3
Magnesium Bicarbonate = Mg(HCO3)2

Temporary Hardness Forms 80% of all


Hardness and can be Removed by Boiling

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CCGT Operations Principles
SCALING

When water containing Temporary


hardness is boiled, calcium
bicarbonate and magnesium
bicarbonate decompose to give
calcium carbonate and magnesium
carbonate.

Ca(HCO3)2 becomes CaCO3 + CO2 + H20


Mg(HCO3)2 becomes MgCO3 + CO2 + H20

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CCGT Operations Principles
SCALING

Calcium Carbonate CaCO3


and
Magnesium Carbonate MgCO3

These compounds are less soluble than


the bicarbonates, so they precipitate
out forming SCALE

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CCGT Operations Principles
Permanent Hardness

Calcium Sulphate = CaSO4


Calcium Chloride = CaCl2
Magnesium Sulphate = MgSO4
Magnesium Chloride = MgCl2
Magnesium Nitrate = Mg(NO3)2
20 % of all Contamination
Removed Chemically
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CCGT Operations Principles
Permanent Hardness Salts
Permanent Hardness salts do not
decompose on boiling.
All salts are soluble in water, but not to the
same extent, for example at 25oC:
Calcium carbonate 0.0153g/l
Calcium bicarbonate 0.091g/l
Magnesium carbonate 0.169g/l
Sodium chloride 362.0g/l

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CCGT Operations Principles
Scale Formation

As water heats up and steam is given off,


its volume decreases and therefore
some of the salt comes out of solution.

The least soluble salts come out first.

This is SCALING

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CCGT Operations Principles
Example of Scaling
A boiler evaporates 1000 tonnes of water per hour.
Make up is added to the system at a rate of 2% i.e.
0.02x1000 = 20 tonnes per hour
Due to a fault in the demin plant the boilers are fed
with make up water of conductivity ~150 S/cm,
i.e. containing 100 ppm (mg/l) of dissolved solids.
If we assume all the salts scaled out in the boiler,
the rate of scale deposition on heat exchangers
is:

20 x 1000 x 100 mg/h = 2 kg/hr or 48 kg/day

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CCGT Operations Principles
Filtration

Filtration Removes
Suspended Solids
Mediums :
Sand or Gravel
Floc (Pulverised Paper)
Paper Cartridge
Carbon (Organic)

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CCGT Operations Principles
Clarification
Clarification means
passing the raw water
through a solution of
Soda Ash
Removes Large amounts
of Temporary Hardness
Salts
Often Used As Pre-
Treatment in Very Hard
Water Areas

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CCGT Operations Principles
De - Ionisation

What Do We Mean By ionisation ?


Any Compound is Composed of Positive (+) ions
and Negative (-) ions; in Order to Remain
Electrically Neutral

A Simple Compound Looks Like This

Take Carbon Dioxide (CO2), if ionised it Becomes

C + + & OO
- -
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CCGT Operations Principles
Ion Exchange

Cation
Exchanges
Positive
Ions

Ca(HCO3)2
Mg (HCO3)2
Become
H2CO3
Weak Acid

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CCGT Operations Principles
Ion Exchange
Cation
Exchanges
Positive
Ions

CaCl2 MgSO4
Become HCl
and H2SO4

Strong Acids

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CCGT Operations Principles
Degassing
The bicarbonate anion CO2
is removed as
Carbin Dioxide
before the anion
exchange unit.
If there was no de- H2CO3
gassing, a very
large amount of De-
anion capacity Gasser

would be required. Air

2H2O
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CCGT Operations Principles
Ion Exchange
Anion
Exchanges
Negative
Ions
HCl and
H2SO4
Become
HOH + HOH
2H2O

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CCGT Operations Principles
Demineralisation Conductivity
A bit less than
3000
3000 s/cm
s/cm

Mixed
Cation De- Anion
Gasser Bed

600 2.5 0.06


s/cm s/cm s/cm

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CCGT Operations Principles
Demineralisation pH Values

pH 1 ish

Mixed
Cation De- Anion
Gasser Bed

pH 7 ish pH 7 ish pH 7 ish

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CCGT Operations Principles
Demineralisation Silica

Silica Silica
8 ppm 8 ppm

Mixed
Cation De- Anion
Gasser Bed

Silica Silica Silica


8 ppm 0.5 ppm 0.02 ppm

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CCGT Operations Principles
Organic Phosphates
Organic Phosphates in Raw Water or
Returned Condensate Cause Problems Within
The Demineralisation Process
Many Demin Units are Fitted With Organic
Traps
Build-up of Organic Phosphates Reduce
Anion Resin Efficiency
Back-washing With Salt Water & Caustic
Solution Removes These Phosphates and
Restores The Resin to About 98% Efficiency
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CCGT Operations Principles
Regeneration Period
Each ion Exchange Stream Should Produce About 250 m3
of Demineralised Water Between Regenerations
Ion Exchange Resins Are Polystyrene in Origin
Each Regeneration Slightly Depletes Resins Ability to
Exchange ions
Water Temperature >50 C Damage Resin Structure
Resin Traps Not 100% Efficient, Some Resin Lost
Resin is Changed or Topped Up About Every 3 Years

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CCGT Operations Principles
Reverse Osmosis
Osmosis is a natural phenomenon whereby water passes
from a weaker solution to a stronger one through a
Semi-permeable Membrane.
Reverse osmosis, as the name implies forces water from a
stronger solution to a weaker one.

Reverse osmosis is not suitable for all raw water sources


and can be expensive to operate due to the large, high
pressure pumps that are required, and the quantity of
waste water produced

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CCGT Operations Principles
Osmosis
Semi-permiable Membrane

Dilute
solution
Concentrated
solution

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CCGT Operations Principles
Osmosis

SOME TIME LATER!

Less
dilute
solution

Less concentrated solution

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CCGT Operations Principles
Reverse osmosis
Pressure

Concentrated
solution

Dilute solution

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CCGT Operations Principles
Reverse osmosis

Pressure
More
concentrated
solution

More dilute solution

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Reverse osmosis
The pressure applied to the concentrated solution forces
water through the membrane
In a commercial system, this water is collected and the
more concentrated solution (raw water) is rejected.
A typical RO plant consists of
Pre-treatment, including filtration, acid dosing &
chlorination equipment to prevent scaling and fouling
HP Pumps - 20 to 40 bar
Banks of membranes
Degasser.

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CCGT Operations Principles
Reverse osmosis
Reverse osmosis Membranes are made of plastic of about
100 microns thickness and 0.0001 microns porosity.
Commonly used materials are cellulose acetate and
polyamide.
Membranes are usually spiral wound or hollow fibre.
Spiral wound - the membrane is rolled on supporting
material like a swiss roll.
Hollow fibre - fine capillaries arranged in a U-shaped
bundle.

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CCGT Operations Principles
Reverse osmosis
Reverse osmosis Membranes have a working
life of 1-5 years depending on the nature of
the raw water.
Deterioration is caused by:
physical stress
chemical degradation
aging
fouling

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CCGT Operations Principles
Boiler Water Chemistry

CaCO3 & Ca(HCO3)2


MgCO3 & Mg(HCO3)2
Carbonates & Bicarbonates in dissolved solids
cause scale deposits inside heat exchange surfaces
Increase Boiler Water Conductivity & are
Removed by Blowdown

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CCGT Operations Principles
Boiler Water Chemistry

CaSO4 & CaCl2


MgSO4 & MgCl2
Sulphates & Chlorides In Boiler Water Form
Acids Which Corrode The Boiler Surfaces
Away

Counteracted by Dosing & pH Control

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CCGT Operations Principles
Corrosion

2Fe2O3 = Rust X
In High Temperature, Low Dissolved O2 Water,
Becomes
3Fe3O4 = Magnetite 9
Which Protects the Steel Fabric Of The Boiler
Erosion - corrosion; occurs in areas of high liquid flow.
The protective layer is eroded by the liquid and further
corrosion takes place attempting to re-form it.

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CCGT Operations Principles
Dissolved Oxygen
Most of the
dissolved oxygen
in feedwater is
removed by the
deaerator
e.g - down from 8
ppm to about 10
parts per billion
(ppb or g/litre)

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CCGT Operations Principles
Boiler Water Chemistry
Hydrazine
N2H4 + H2O + O2
Becomes

N2 + 2H2O
Nitrogen + Water
Hydrazine is usually dosed at a level that is twice that
of the dissolved oxygen content.
This gives a margin of safety in case air ingress
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occurs. CCGT Operations Principles
Boiler Water Chemistry
Ammonia
2NH3 + H2O + CO2
Becomes

(NH4 )2CO3
Ammonium Carbonate
At higher temperatures Hydrazine may decompose
3N2H4 4NH3 + N2
The ammonia produced assists in pH control

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CCGT Operations Principles
Using Ammonia

Advantages: Disadvantages:
Less aggressive than solid Does not protect against
alkalis acid chloride attack
Volatile, therefore affords Needs to be dosed
corrosion protection of continuously
steam circuits Not as effective at
Does not hideout - protecting against erosion
chemical control easier corrosion
Does not contribute to Risk of corrosion of
after column conductivity copper alloy components

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CCGT Operations Principles
Boiler Water Chemistry

TriSodiumPhosphate (Hides Out)

Na3PO4 + H2O
Becomes

Na2HPO4 + NaOH
DiSodiumPhosphate + Caustic Soda (Caustic Reserve)

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CCGT Operations Principles
Boiler Water Chemistry

Magnesium chloride
MgCl2 + H2O
Becomes

2HCl + MgO
Hydrochloric Acid + Magnesium Oxide
When magnesium chloride from CW System reaches boiler
temperature and pressure, it hydrolyses (reacts with

water) to produce hydrochloric acid

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CCGT Operations Principles
Boiler Water Chemistry
Strong
Acids &
pH
Controlled between
Alkalis will
corrode
Their
100
8.9 to 9.3
Environment
Corrosion Rate
Graph
Shows
Corrosion
Rate of Mild
Steel in 0
Acids/Alkalis 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH of solution

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CCGT Operations Principles
Corrosion
The curve shows that corrosion is most rapid in
acid solution
Localised acid formation can occur due to the
ingress of chloride following condenser leaks
Localised acid corrosion is rapid and causes
thick wall failures
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Corrosion Rate

0
1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH of solution 46
CCGT Operations Principles
Corrosion

Hydrochloric acid attacks iron and produces iron


chloride and hydrogen gas, which then reacts
with the carbon atoms in the steel to produce
methane.

2HCl + Fe = FeCl2 + H2
C + 2H2 = CH4

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CCGT Operations Principles
Corrosion

The methane (CH4) molecules are much larger


than carbon atoms and as they try to force
their way into the crystal structure of the steel,
the steel cracks and the tube bursts open.
This is called hydrogen damage and is the
worst type of on-load corrosion, having been
known to put out the fire in conventional
boilers.

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CCGT Operations Principles
Corrosion
General acid attack gives rise to excessive production of
iron oxide and therefore loss of tube metal.
The thicker than normal oxide layer can exacerbate the
phenomenon of Hide-Out and, if caustic soda is
used in the boiler, the likelihood of caustic attack.
The curve shows that at high pH (alkaline) mild steel
also corrodes rapidly.
This can happen if caustic soda is used, and if
phosphate hide out occurs 100

Corrosion Rate
0
1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH of solution
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CCGT Operations Principles
Corrosion

Caustic corrosion is a relatively slow process


and occurs in localised sites of high heat flux.
The boiler tube thins down until the pressure of
the boiler water causes a pinhole leak.
This type of on-load corrosion is often called
caustic gouging.

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CCGT Operations Principles
Boiler Water Chemistry

Silica as SiO2
Becomes Volatile Under High Pressure & Temperature

10% Reactive
Is Carried Over in Steam

Leaves Brown Glass-Like Deposits on Cooler


Pipework; Pressure Vessels; Turbine Blades etc.
Very Difficult to Remove

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CCGT Operations Principles
Action For Serious Contamination
Inform The Chemist
Isolate Stator Water Header Tank
Check WTP Output Quality
Shut LP Feed to D/A
Reduce Load & Dump Condensate
Isolate Superheater Spray-water System
Open Boiler Blow-downs
Check Chloride Concentration in Boiler Water
Chlorides 0.2 to 2.0 ppm, Inject Caustic to 3.0ppm
Only Few Hours Permissible above this level
Chlorides 2.0 to 5.0 ppm, Inject Caustic to 5.0ppm
Commence Shut-Down
Inject Caustic
Blow Down & Flush Boiler
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CCGT Operations Principles
Some Important Terminology

After column conductivity - is a


measurement of the conductivity of water
which has passed through a column of
cation exchange resin.
The cation resin amplifies the level of
undesirable impurities but removes
conductivity due to ammonia.

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CCGT Operations Principles
After column conductivity
CONDENSATE
Condensate Containing a Ko CONTAIING A
TRACE OF
Trace of Sodium Chloride SODIUM
CHLORIDE
NaCl = Na+ & Cl-
Na+ exchanges with H+
CATION
(from resin) RESIN

HCl is formed and the H+

Conductivity rises

Ko

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CCGT Operations Principles
After column conductivity

CONDENSATE
Ko CONTAIING
Condensate Containing a AMMONIA

Trace of Ammonia
NH4OH = NH4+ & OH-
NH4+ exchanges with H+ CATION
RESIN
(from resin)
H+
HOH is formed.
Conductivity falls

Ko

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CCGT Operations Principles
WHAT IS HAPPENING?

Conductivity of Condensate Trend

Ko before
column
10

Ko after
column
0.3

CONDENSER LEAK!!! 56
CCGT Operations Principles
WHAT IS HAPPENING?

Conductivity of Condensate

Ko before
column 10

Ko after
column 0.3

COLUMN EXHAUSTING!! 57
CCGT Operations Principles
Instrumentation

pH meters need their electrodes carefully


stored when not in use so they will be
ready for action.
pH meters require regular buffering
pH readings rarely shoot off scale in one
direction or another - usually the trend
shows slowly.

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CCGT Operations Principles
Instrumentation

Sodium meters need their electrodes


carefully stored when not in use so they
will be ready for immediate use.
Readings rarely shoot off scale in one
direction or another - usually the trend
shows slowly.

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CCGT Operations Principles
Instrumentation

Oxygen meters (membrane type) should


run relatively trouble-free
High oxygen levels deplete electrolyte
more quickly
Readings sometimes noisy

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CCGT Operations Principles
Instrumentation

Silica meters do not give instantaneous


readings - they are a chemistry set in a
box and the result you get is normally of a
sample that was taken 15 - 20 minutes
earlier
Reagents (solutions) must not be allowed
to run out

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CCGT Operations Principles
Instrumentation

Hydrazine meters do not give


instantaneous readings - the result you
get is normally of a sample that was
taken 10 minutes earlier
Reagents (solutions) must not be
allowed to run out

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CCGT Operations Principles
Instrumentation

common Instrumentation faults

Loss of sample flow


Sample flow too fast
Sample too hot
Reagents run out
Poor calibration

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CCGT Operations Principles
Chlorination of Cooling Water

Biological matter such as algae grows


very rapidly in the warmth of the
condenser
The addition of sodium hypochlorite
minimises the growth of biological
matter in condensers.
The free chlorine arising from sodium
hypochlorite is corrosive, so materials
of construction are carefully chosen

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CCGT Operations Principles
Chlorination of Cooling Water

Chlorine demand of water is the


amount of chlorine required to kill
contaminants.
The amount of hypochlorite dosed must
be slightly more than the chlorine
demand
Algae, biological slime and certain
nitrogen compounds all exert a chlorine
demand.
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CCGT Operations Principles
Other Cooling Water Treatment
sulphuric acid dosing
Objective is to produce water that is
neither CORROSIVE nor SCALING
Add acid to make water less alkaline
but definitely not acidic
Acid is dosed at cooling towers
Cooling water in the circuit must have a
Ryzner Index between 6 and 7
(equivalent to a pH of about 7.8)
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CCGT Operations Principles