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BOILER WATER

CHEMISTRY

Boiler Types
1 Coil
2 Fire Tube
3 Water Tube

Waste recovery
Heat Recovery Steam Generators
CPP
CCPP
IPP

Boiler Coil type


1 Capacity < 1000 kg/hr
2 Pressure <15 kg/cm2
3 Usage
< Textile, Processing,
Rice mills,
1 Water Quality
1
2
3
4
5
6

Feed
pH
Cond
TH
SO3
D.O.

Soft water,
7.5 8.5
<100
<5 ppm
30-60 ppm
< 10 ppb

Boiler Fire Tube


1 Capacity < 10 TPH
2 Pressure <20 kg/cm2
3 Usage
Process Industry, Oil Mills.
Pharmaceutical etc
1 Water Quality

Feed
pH
Cond
TH
SO3
D.O.

Soft water /DM water


7.0 8.0
<10
ND
30-60 ppm
< 10 ppb

Boiler Water Tube


1 Capacity > 5 TPH
2 Pressure > 20 kg/cm2
3 Usage
Chemicals & Process
Industry, Oil Extraction Mills, Power
Plant, Sugar Industry, etc
4 Plant Accessories

Air Pre-heater
Economiser
De-aerator
Super Heater
Spray attemperators
DM Plant

Boiler - Water Tube


1 Water Quality - Feed Water DM water

pH
Conductivity
TH
Feed Temp
D.O.
Silica
Cl
Fe+ Cu

6.8 7.2
<0.2 cms/cm2
ND
>100 0C
< 10 ppb
<20 ppb
ND
<20 ppb

Goals of Boiler Operations


Produce steam for the lowest
possible overall cost
Minimize Water Use / Wastage
Minimize Chemical Use / Wastage
Minimize Operating and
Maintenance Costs

Our goal is to provide value


when we address customer
needs.

Resourcefulness
Quality
Performance
Cost-Effectiveness

Objectives of Boiler Water


Treatment
Prevent Scaling and Deposits
Prevent Corrosion Failure and
Damage to System Equipment
Avoid Carryover of water & solids
into the Steam

Boiler
Pre-Treatment
Turbines
Process
Process
Process
Low pressure Blowdown flash
tank
steam

Flash
tank
Condensate
Receiver

PROBLEMS ASSOCIATED
WITH WATER

Corrosion of Boiler or piping - almost


always due to oxygen

Basic ingredient in respirationAlso, a


great menace to many situations !!!

Scale - usually due to hardness,


sometimes silica
Corrosion of steam / Condensate piping
or equipment

The success of every boiler water


treatment program relies on a primary
mechanical means for reducing the
potential and deposition, followed by a
secondary chemical means

Treatment of Boiler
Systems
Is a science
Uncontrolled factors or variables
are few
Mechanical procedures can solve
many problems
Keys are Energy Efficiency &
Equipment Reliability

MAXIMUM RELIABILITY
is Provided by
CONTROL OF OXYGEN
CORROSION

Oxygen Corrosion Control


Remove as much oxygen as
possible by mechanical methods
higher temperature water / feed water
de-aeration

Polish with chemical scavenger

Types of Deaerator

Spray Type
Tray Type
Heat
Heat

Heat
Heat

Heat
Heat

Steam

SPRAY TYPE

TRAY TYPE

Chemical Removal of Oxygen


O2 + X Scavenger = XO salt
O2 + 2SO3- = 2SO4=
O2 + N2H4 =

N2 + H20

O2 + (N2H3)2CO = N2 +H20

BOILER WATER TREATMENT


OXYGEN SCAVENGERS
SCALE AND SLUDGE CONTROL
DISPERSANTS
ANTIFOAM
CONDENSATE LINE CORROSION
INHIBITORS

OXYGEN SCAVENGERS

Sulphite, (Catalyzed & USDA Approved)


Hydrazine,(Catalysed)
Carbohydrazide
Other non-sulfite, non-hydrazine compounds,
Tannin - Lignin

SLUDGE CONTROL
PHOSPHATES
Precipitation of scale forming salts
PHOSPHONATES
Prevent deposition of precipitated salts
DISPERSANTS
Dispersion of sludge for easy removal through blow down

DISPERSANTS & ANTIFOAM

Dispersants based on Polyacrylates, Polymethacrylates & Polymaleates

Specific for high suspended solids

Stable at high temp.

CONDENSATE LINE
CORROSION INHIBITOR
CYCLOHEXYL AMINE
DIETHYL AMINO ETHANOL
MORPHOLINE

WHY TO SCAVANGE OXYGEN

MAIN WATER RELATED


PROBLEMS
Corrosion of Boiler or steam,
condensate lines- almost always
due to OXYGEN
Scale usually due to hardness,
sometimes silica
Corrosion of steam / condensate
piping or equipment

Scale Deposit Formation


Heat and Pressure cause natural
reactions
Calcium & Magnesium react, form
scales, inverse solubility.
Excess Silica can cause hard scale
Cu, Fe, galvanic corrosion
Iron oxides, corrosion product
increases deposits

Thermal conductivities of various scales and other


materials
M a t e r ia ls

A n a lc ite

T h e r m a l c o n d u c t iv it y
( B T U /f t 2 h r . o F in )

8 .8

C a lc iu m p h o s p h a te

25

C a lc iu m s u lfa te

16

M a g n e s iu m p h o s p h a te

15

M a g n e tic ir o n o x id e

20

S ilic a te s c a le ( p o r o u s )
B o ile r s te e l
F ir e b r ic k
In s u la tin g b r ic k

0 .6
310
7
0 .7

Methods for Boiler Deposit


Control
Remove as much scale potential as
possible mechanically
Maximize solubility (Silica +
Hardness)
Change reactions to not form scale
Condition sludge to not stick, be
removed via blowdown

HIGHEST ENERGY EFFICIENCY


is Provided by
MINIMUM BLOWDOWN
&
MAXIMUM DEPOSIT
PREVENTION

Internal BWT Treatment


History
Alkaline Phosphate Treatment
Introduced in 1920S
Widely Used Today
Precipitates Calcium,
Magnesium and Silica As
Sludge Rather Than Scales

Alkaline Phosphate
Treatment
Calcium Hardness Forms Calcium
Hydroxyapatite

(3 Ca3(PO4)2 . Ca(OH)2)
Magnesium Hardness Forms Serpentine

(2 MgSiO3 . Mg(OH)2 . H2O)


These Non-Adherent Sludge Are Removed
Through Bottom Blowdown
Silica controlled as Serpentine or via
Hydrate Alkalinity & Maximum
Concentration Control

PHOSPHATE TREATMENT
Program Operation
Phosphate Residual: 30-50 ppm PO4 in the
Boiler
Hydrate Alkalinity: 100-600 ppm as CaCO3 in
the Boiler
Co-Ordinated Phosphate 4 -10 ppm PO4 in HP
Boiler
Co-Ordinated Phosphate treatment - 4 to + 0
ppm Hydrate Alkalinity (2p-m)

AWC PRODUCTS
OXYGEN SCAVENGERS
AWC A-410: Liquid catalyzed oxygen scavenger for low
and medium pressure boilers (up to 900 psig).

AWC A-413: Powdered catalyzed oxygen scavenger for


low and medium pressure boilers (up to 900 psig).

AWC A-415: Powdered oxygen scavenger for high


pressure boilers (900 - 1500 psig).

AWC A-417: Liquid oxygen scavenger for very high


pressure boilers (> 2500 psig).

AWC PRODUCTS
PHOSPHATE TREATMENTS AND SCALE
CONTROL
AWC A-430: Powdered polyphosphate blend.
AWC A-434: Liquid polymer based sludge conditioner
and metal oxide dispersant.

AWC A-451: Liquid polyphosphate / polymer blend for


optimal scale control.

AWC PRODUCTS
CORROSION INHIBITORS FOR STEAM
CONDENSATE
AWC A-480: Blend of neutralizing amines for long and
short steam distribution lines.

AWC A-485: Blend of neutralizing amines for short


steam distribution lines, such as turbines and steam hot
water heaters.

AWC PRODUCTS
MULTI-FUNCTIONAL BLENDS
AWC A-460: Polyphosphate/sludge conditioner/scale
inhibitor/oxygen scavenger.

AWC A-465: Polyphosphate/sludge conditioner/scale


inhibitor/oxygen scavenger/neutralizing amines.

Organic Adjuncts
Iron Sequestering Agents
Sludge Conditioners
Synthetic Polymers

Synthetic Polymers
Long Chain of Repeating
Monomer Units, Typically of
Anionic Charge
Distort Scale Crystal Structure
Inhibit Scale Growth
Disperse Scale Particles

Combination Treatment
Approaches
Incorporate Proprietary Blends of
Sequestrates, Dispersants (Natural and
Synthetic), Reducing Agents, Etc. to
Minimize Deposition
Blends Can Be Customized to Address
Feed water Quality, System Pressure,
Testing Requirements, Governmental
Regulations

Internal Boiler Treatment


Selection Methodology
Feed water quality
Feed system constraints
Boiler pressure
Steam uses
Performance, Chemistry
Testing needs
Quantity requirements , Costs
FDA needs

Summary
Operating conditions dictate
treatment programs
All program options have
advantages and disadvantages
Pretreatment equipment and
processes cannot be ignored
Proper control is necessary

After Boiler
Treatment

After Boiler Section


Super heaters
Turbines
Process equipment
Steam-handling equipment
Condensate lines

Condensate Corrosion
Acidic attack due to acid gases
Carbon Dioxide naturally forms
in boiler
Carries over in steam, enters
condensate & forms carbonic
acid

After Boiler Corrosion


Low pH attack caused by CO2
H2O + CO2 = H2CO3
Fe + H2CO3 = FeCO3 + H2
Oxygen attack
Fe + O2 + H2O = Fe(OH)2
Fe(OH)2 + Heat = Fe2O3

Possible Causes of Low pH


Presence and/or formation of carbon
dioxide (CO2)
Breakdown of bicarbonate and carbonate
alkalinity in the boiler
Free CO2 in raw water (e.g. well water) / air
leakage
Internal treatment chemicals (e.g. soda ash)
Decomposition of some organic compounds

Breakdown of sulfite above 900 psig to


SO2 and H2S

Results in
Thinning of metal
Threaded pipe
Grooving
Equipment and piping failure in the
steam and Condensate system
Metallic oxides returned to boiler
Corrosion caused leaks

Grooving and Thinning

CO2 Attack

Thinning below
water line

Oxygen and Carbonic Acid Attack

Effects of Corrosion on Plant


Efficiency
Iron-bound deposits in boilers
Destruction of capital equipment
Repair and labour costs
Steam leaks, wastage
Unscheduled outages
Lost or damaged production

Treatment Options
Neutralizing amines

React with CO2 to neutralize acid attack


Several specific amines can be used to tailor
the protection to a specific system
Filming amines

Form impermeable barrier to liquid


Blended amine
Blended amine and metal passivator programs

Conditions Affecting Selection


of Chemicals
Complexity of after boiler section
Operating pressures of de-aerators
Percent boiler blow down
Metallurgy of system
Direct steam usage
FDA regulations

Neutralizing
Amines

Neutralizing Amines
Ammonia
Cyclohexylamine
Morpholine
Diethylaminoethanol (DEAE)
Methoxypropylamine (MOPA)
Ethylene diamine
Diethyl Tetra amine
Amino methyl butanol
Monoethanolamine (MEA)
Aminomethylpropanol (AMP)

Corrosion Inhibitors
Neutralizing amine blend
Provides control of
condensate low pH
corrosion

Reaction Mechanism
Neutralizing amines
combine with carbonic acid
to raise the condensate pH
OC4H9N + H2CO3 OC4H9NH2CO3

N
H

Advantages of
Neutralizing Amines
Easy to feed
Blends provide good distribution
Wont slough off iron oxide
Dont release ammoniacal N2
Wont degrade
Recycled

Control

Condensate pH 8.5 to 9.5


Copper MOC, pH 8.8 - 9.2
Iron Monitoring, <10 ppb
Copper monitoring <10 ppb

Film-Forming Amines
Octadecylamine
CH3- (CH2)16 - CH2- N - (CH3)2
Ethoxylated Soya Amine
Ethoxylated Fatty Amines

CH3 - (CH2)16 - CH2- N+ - (OC2H5)3

MECHANISM
CONDENSATE

METAL
H
H

CH3
+
N - CH3

CH3

Advantages
Theoretically the least
expensive
Prevents O2 attack
Prevents CO2 attack

Limitations
Poor control over recycling
No meaningful chemical test
Wont film over deposits
Wont film over pits
Sloughs off iron oxide
Degrades
Susceptible to contamination
Difficult to feed

Solutions are More Than Just


Chemicals
Mechanical efficiency of boiler system
Steam trap efficiency
Proper pretreatment equipment, process
and chemistry to optimize the entire
system
Monitoring and control issues
Handling and disposal safety

BWT PRODUCTS PHILOSOPHY


- Broad range of deposit control
programs
Best fit approach for individual
customer needs
Able to provide the Total System
Management programs needed

Steam to
De-aeration
T/HR

DE-AERATOR

BFW STORAGE
TANK

POLISHED
D.M.WATER

STEAM DRUM

ECONOMISER

MUD DRUM
CONDENSATE

Amines

Oxy-Scav
Scale In

Schematic Of Chemical Dosing

Drum Operating
Pressure Kg/cm2

0 - 20

21 - 40

Dissolved O2 ppm
< 0.007 < 0.007
TDS
2500
1500
pH
9.0-10.5 9.8-10.5
OH -Alk
250
150
M-Alkalinity
500
300
Total Hardness
0.1
0.1
Phosphate (PO4)
30-70
30-50
Silica
--Oxygen Scavenger (SO3) 30-60
20- 50
(Organic Base) 0.3-1.0 0.1 -.2
Chlorides
--Iron, Fe
<1
<0.3
WATER SAMPLES TO ANALYZED.

61 - 80
< 0.007
200
9.50-10.0
10-20
20
NIL
10-20
<5
N/R
0.05-0.1
<8
<0.05

100 -120
< 0.007
50
9.2-9.8
5
10
NIL
4 -10
<1.0
--0.03-.05
<4
ND

BFW, B/D, S.H. STEAM, TURBINE


CONDENSATE, PROCESS
CONDENSATE

MONITORING

THANK YOU