You are on page 1of 59

APEX CHEMICAL TECHNOLOGIES

PRESENTER

Mr. AFAN MIRAJ


(Bsc. Chemical Engineer)
HONDA ATLAS (PVT) LIMITED
(NESPAK)
PRE-TREATMENT OF WATER
 As the demand for clean water increase across the
industrial spectrum, including for power plant,
companies are searching for more efficient and cost
effective way to source and select water treatment
system.
 In considering the industrial system design, Three Items
have to be evaluated.
1. Pre-treatment equipment selection based on
the feed water quality.
2. Evaluating the industrial system demand for
which water is Pre-treated.
3. Complete understanding of water chemistry
control for cooling tower, Boiler, HRSG, Steam
Quality Demand etc.
FLOW SHEET DIAGRAM FOR
HRSG SYSTEM
INFORMATION REGARDING STEAM
QUALITY
• Deposits on the turbine balding Due to steam
contamination my bring about Thermodynamic and
mechanical disturbances.

• If chlorides are present there is additional possibility of


blade fracture under certain circumstances.

• Corrosion stress caused by aggressive deposits affects


alternating bending strength of the blade material
especially at the beginning of the wet steam region.
GUIDE VALUES FOR INLET STEAM
CONDENSATE
Issued by VGB (Large boiler users association) edition April 1972.

TESTING FOR UNIT GUIDE VALUE COOPERATION


Continuous Start up
Operation Operation
Conductivity at 25oC for CO2
ms/Cm <0.2 <0.5
free Water
Silica (Sio2) mg/L <0.02 <0.05
Total iron (Fe) mg/L <0.05 <0.05
Copper (CU) mg/L <0.01 <0.01
Sodium and Potassium mg/L <0.01 <0.02
Chlorides
mg/L <0.2
• The Guide values have to show a
downward tendency.

• When commissioning newly installed


plants, the values guaranteed for
continuous operation have to be
achieved with in two days.

• To avoid misunderstanding we would


point out that even full compliance with
the guidelines does not absolutely
guarantee safe deposits steam turbine.
COOLING TOWERS
COOLING TOWER SCHAMATIC
MAJOR CONCERNS

Corrosion
Scaling
Foreign Matter/Deposits
Biological Fouling
Corrosion
• Corrosion is an
electrochemical
process where metals
are converted to their
more stable form (i.e.
oxides)
• The process requires
an Anode, Cathode, and
an ionic conduction
path through an
electrolyte (i.e. water)
Corrosion Cell
Corrosion Mechanism
in Alkaline Environment
H
H Fe(OH)2
O H
H O Fe+3

H
H H
Fe+2 O
H O H H
O H
O Fe+3 Fe+2 O H
H Fe(OH)3
Fe+2 O H
O H Fe+2
H O O
Fe+2
Fe2O3
Fe+2
Anode e– Cathode
Cost of Corrosion
• Production loss
• Equipment damage and
replacement
• Increase in utility costs
• Increase in labor costs
• Increase in water treatment
costs
Scaling
• As little as 1/8 of scale can reduce the efficiency of a cooling
tower, heat exchanges by 40%
• Scale formation always causes higher energy consumption and
this applies all year round regardless of the load on system.
scale itself is not considered as a nutrient for a biological
growth, heavy scaling provides a breeding haven for micro-
organisms and can therefore add to the risk of biological
contaminations. The following reaction governs formation of
CaCO3.

Ca(HCO3)2  CaCO3 + CO2 + H2O


CaCO3 scaling is also governed by pH, Ca concentration,
alkalinity, temperature and TDS.
• In addition to the chemical factors already mentioned, there are
several mechanical factors affect the tendency for scaling,
including water velocity, design, operating conditions, and
surface material
Chart Heat Efficiency vs Scale Thickness

Scale Thickness 
Scale
Hard crystalline
deposits
Precipitation of
mineral salts
CaCO3, CaSO4,
SiO2
CaSiO3, MgSiO3,
etc.
Suspended Solids – Related Problems

• Fouling

Reduce heat exchanger efficiency due to


deposition
Increased power consumption
Nutrients provided for microbiological
growth
 Deposition
 Corrosion
Color imparted to products
Production Losses
Fouled Condenser Tubes
Treatment Approach
Zinc / Phosphate Programs
All Organic Programs
Silicates based Programs
Azoles
Synergistic blends
Corrosion Inhibitors (Zinc)

Cathodic inhibitor
Precipitates at a pH above 8.0
Forms zinc hydroxide – zinc
carbonate film
Operating LSI is from – 0.5 to + 0.5
Toxic to marine life
Banned in some locations
Film Formation (Zinc)
Ionic Migration
Reduction of Ions
and Oxygen
Dissolution of
Metal Ions (Fe²¯)

3Zn(OH)2 – 2ZnCO3

Electron Migration
Cathode Anode
Stabilized Phosphate Programs

Requires minimum calcium of 50


ppm
Requires pH control above 8.0
Operating LSIs up to 1.5
Effective phosphate deposit
control required
Phosphate discharge regulated in
some locations
Film Formation Polyphosphate
Ionic Migration
Reduction of Ions
and Oxygen
Dissolution of
Metal Ions (Fe²¯)

Calcium polyphosphate
Complex

Electron Migration
Cathode Anode
BIOLOGICAL FOULING
MICROBOILOGICALLY INFLUENCED
CORROSION (MIC)
EFFECTIVE SOLUTIONS FOR A COSTLY PROBLEM,
• It induces generalized or localized corrosion such as
pitting.
• Is a serious form of degradation of system materials
in several industries like:
• Power generation
• Oil refineries
• Chemical processing plants
• Nuclear industries
Micro Biological Fouling
THE HIGH COST OF (MIC)
Generating plants have been
forced to undertake material
replacement.
To make extensive repairs to
service water system at
enormous cost.
Effects reliability, safety and
maintenance cost.
Microbiological Control
Biocides
Generally classified as
Oxidizing Biocides
– Irreversibly oxidize protein groups of the cell,
resulting in loss of enzymes activity and rapid
death.

Non – Oxidizing Biocides


– Do not oxidize cell structure but inhibit
microorganisms by interfering with or disrupting
vital life processes.
Oxidizing Biocides

Example are Cl2 , Br2, ClO2,


Hypo, etc.
Properly applied can effectively
control the wide range of
microorganisms – bacteria,
slime, algae, fungi and
protozoa.
CHEMISTRY
 Cl2 + H2O  HOCl + HCl
 HOCl is very effective and economical general
purpose biocide.
 pH conditions (7 ~ 9) typically in cooling tower convert
HOCl to OCl¯.
 pH 7.5 ~ 8.0 is ideal for better biocidal activity.
 Studies indicate that OCl¯ is 100 times less effective
than HOCl.
 HOCl  H+ + OCl¯
 In practice FAC (Free Available Chlorine) of between
0.2 ~ 1.0 ppm continuous or 0.5 ~ 2.0 ppm on a
periodic sludge bases lead to good microbial control
in cooling tower.
OXYGEN REDUCTION POTENTIAL (ORP)

 ORP is a measure of the


“cleanliness” of water and
its ability to break down
contaminants.
ORP sensors works by
measuring dissolved
oxygen.
Generally, the higher the
ORP level, the more ability
the water has to destroy
microbes and carbon based
contaminants.
Non – Oxidizing Biocides
Oxidizing biocides are generally poor at
penetration and dispersing heavy,
anaerobic infestations.
Therefore a fundamental need existing
for non oxidizing biocides as a
supplement to oxidizing biocides.
Example are Isothiozolines,
Benzolkonium chloride, (Quaternary
ammonium chloride), Glutaraldehyde
etc.
Boiler Water Treatment
BOILER TREATMENT COST
Problems Area
• Overview
1. Scale
2. Corrosion
3. Condensate line corrosion
4. Carryover /Priming
Scale can lead to

Loss of Efficiency
Higher fuel consumption
Blockage
Tube Failure
In server cases, Explosions !
Scale on Boiler Tubes
Scale Causes
High temperature & pressures
Bare Metal Surfaces
Under – deposit corrosion
Oxygen & CO2
Low pH excursions
High pressure systems – caustic
embitterment
Condensate corrosion
 Condensate is an excellent source of feed water
 Condensate is typically of better quality then normal Make up
Water boiler water c/c and be increased and Blow Down can be
reduced
 It result in a reduction of heat loss through Blow Down, which
reduces the amount of heat (Fuel) required t maintain operation
pressures.
 As condensate what is hot, again less heat (Fuel) is required to
maintain operation pressures.
 Re-using condensate water if treated represents a valuable
investment that can be utilized over.
 Condensate water if not treaded/badly treated can become a
maintenance nightmares.
 Most common problems associated with condensate is corrosion
of the piping that returns it to the feed with system and ultimately
the boiler.
 Almost all problems associated with condensate is corrosion can
be trace to gasses Co2 and O2.
Carbon dioxide
 Alkalinity is the form of carbonate and bicarbonate ions under
pressure and high Temperate is below decompress as
 2HCO3CO3 + CO2 + H2O -----1
 CO3 + H2O2OH + CO2 -----2
 Reaction 1st achieves 100% Completion and reaction 2nd achieves
80% or more completion at pressure over 150psig.
 CO2 is carried along with the steam.
 After the steam has done its work and condenses CO2 will dissolve
in the condensate forming H2CO3.
 CO2 + H2O  H2CO3
 H2CO3 causes low pH based corrosion in condensate line.
 H2CO3 acid corrosion typically manifests its self as general thinning
of metal.
 H2CO3 acid corrosion result in high iron content in boiler feed water
resulting in boiler tube failure as iron precipitate out on to the boiler
tube.
 This deposition can cause galvanic as well as under deposit
corrosion, accelerating the corrosion rates to the point of failure.
CONDENSATE LINE TREATMENT
 It depends on a number of factors that include:
 Complexity, size and age of the system.
 The quantity and source of condensate and the raw
water characteristics.
 Generally two types of chemical are used for condensate
line treatment: neutralizing amines and filming amines.
 Neutralizing amine neutralize H2CO3 reducing the
potential for low pH.
 Common neutralizing amine include—Morpholine,
cyclohexylamine, diethylaminoithanol (DEAE).
 Filming amine function by laying down a monomolecular
film on metal surfaces providing protection against
H2CO3 acid attack.
 The two most common filming amines are octa-
decylamine (ODA) & ethoxylated soya amine (ESA)
Corroded condensate pipe
Priming
1. Priming Caused by:
 Rapid drop in boiler pressure
 Rapid increase in steam load
2. Both lead to:
 Increase in specific volume of steam
 Increase in steam velocity
Boiler water in “Sucked Out” of the boiler
Foaming

Normal Operation Slight foaming

Sever foaming Danger


Treatment Methods
External Methods:
Base Exchange Softening
Reverse Osmoses
De – Precipitation Softening (Lime –
Soda)
Alkalization
De – Mineralization
Treatment Methods
Internal Methods:

Phosphate (precipitation)
Oxygen Scavenger
Amines
Phosphate Program
3Ca++ + 2PO4– 3  Ca3(PO4)2↓
Phosphate reserves of 40 – 80 ppm as
PO4, must be maintained in boiler water,
equivalent to 70 – 100 ppm of Na3PO4.
Phosphate precipitate out in the boiler
water and is removed by blow down (not
continuous Blow down). Dispersant
(known as sludge conditioner) required
for Calcium Phosphate, which Otherwise
will form a sticky deposit.
Oxygen Scavengers
Sulphite
Na2SO3 + ½ O2  Na2SO4
Bisulphite
NaHSO3 + NaOH  Na2SO3 + H2O
Metabisulphite
Less Bisulphite are required than Sulphite,
per ppm of oxygen in the water (5.9 for
Metabisulphite, 6.5 for Bisulphite, and 7.88
for Sulphite.
Oxygen Scavengers
• Hydrazine
N2H4 + O2  N2 + H2O
as oxygen scavenger, dose rate
1:1
usually dose is excess; 1.5 – 2:1
normally use catalyzed hydrazine
for BWT feed water pH > 9.5
suitable for up to 2,500 psig
Passivates metal surface
Condensate Protection

Neutralizing Amines
Filming Amines
Combination & Blends
Objective of Boiler Water Treatment

Prevent Scaling and Fouling


Prevent Corrosion failure and damage
to system equipment
Avoid carryover of undesirable
material into the steam to ensure
steam quality & purity
Maintain a consistent and optimum
steaming rate
Close Loop System
Close Loop System
Treatment Methods
• Chemical
Corrosion Inhibitors
Biocides
• Non Chemical
Clean system to start with
Prevention of leaks
Good Housekeeping
Eliminate mixed metallurgy where possible
Chemical Treatment

Summary and Comparison

 Molybdate
 Nitrite
Molybdate
Works best with other inhibitors
Nitrite
Phosphate
Phosphonate
Azole copper inhibitor
Improves strength of oxide layer
Low toxicity
Expensive per kg. but cost effective
Nitrite
Similar mechanism to chromate –
promotes formation of protective
gamma iron oxide.
100% Anodic
Less toxic than chromate
Usually used as part of mixed inhibitor
Buffer
Copper Inhibitor
Aluminum Inhibitor
Closed System Biocide

Non oxidizing
Thermally stable
Non – corrosive
Compatible
Effective against anaerobic
bacteria
THANK YOU
FOR YOUR ATTENTION