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Chemistry
1
CCGT Operations Principles
COURSE OBJECTIVES
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CCGT Operations Principles
What is an Element ?
What is an Atom ?
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CCGT Operations Principles
What is a Compound ?
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 ?
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CCGT Operations Principles
Impurities of Water ?
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CCGT Operations Principles
What is a Molecule ?
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
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CCGT Operations Principles
SCALING
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CCGT Operations Principles
SCALING
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CCGT Operations Principles
Permanent Hardness
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CCGT Operations Principles
Scale Formation
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:
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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
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
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
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CCGT Operations Principles
Demineralisation pH Values
pH 1 ish
Mixed
Cation De- Anion
Gasser Bed
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CCGT Operations Principles
Demineralisation Silica
Silica Silica
8 ppm 8 ppm
Mixed
Cation De- Anion
Gasser Bed
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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.
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CCGT Operations Principles
Osmosis
Semi-permiable Membrane
Dilute
solution
Concentrated
solution
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CCGT Operations Principles
Osmosis
Less
dilute
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
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CCGT Operations Principles
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
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CCGT Operations Principles
Boiler Water Chemistry
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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
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
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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
100
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
2HCl + Fe = FeCl2 + H2
C + 2H2 = CH4
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CCGT Operations Principles
Corrosion
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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
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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
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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
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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
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?
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
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CCGT Operations Principles
Instrumentation
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CCGT Operations Principles
Instrumentation
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CCGT Operations Principles
Instrumentation
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CCGT Operations Principles
Instrumentation
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CCGT Operations Principles
Instrumentation
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CCGT Operations Principles
Chlorination of Cooling Water
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CCGT Operations Principles
Chlorination of Cooling Water