Boiler Water Best Practises

Boiler Water
Internal Treatment
Technology
Why is Effective Internal Boiler
Water Treatment Necessary ?
Effective Internal Boiler Water
Treatment

Controls

• Deposition

• Corrosion

• Carryover

and
 Enhances System Reliability
and Efficiency

• Avoids unscheduled shutdowns

• Helps ensure uninterrupted production

• Reduces maintenance costs

• Reduces operating costs

What Operating Costs are
Associated with Boiler
Operation ?
 Boiler Operating Costs

• Fuel - Gas, Oil, Coal

• Water - Influent and Effluent

• Regenerants - Salt, Acid,

Caustic

• Water Treatment
 Boiler Operating Costs
• Fuel - Gas, Oil, Coal
• Water - Influent and Effluent
• Regenerants - Salt, Acid, Caustic

• Water Treatment
 Boiler Operating Costs
• Need to minimise all operating costs
Reducing boiler water blowdown gives
water, energy and chemical savings

• Need to maximise efficiency

Maintain clean heat transfer surfaces
Heat recovery systems
Effective Internal Boiler Water
Treatment

Controls
Deposition •
Boiler Water Deposit Control

• Hardness salts
• Calcium
• Magnesium

• Metal oxides
• Iron
• Copper
Comparison of Heat Transfer Surfaces
With and Without Deposits

Metal Metal Scale

Fireside Waterside Fireside Waterside

800°F
and
600°F above
500°F 500°F

Without deposits With deposits

 Energy Loss from Scale Deposits
(from Energy Conservation Programme Guide for Industry & Commerce)
8
e
al

ale
7 c
tS

Sc
n
nte ale

ica
c
6
Co eS
at

S il
n n
Energy Loss %

Iro rbo

n&
5
igh Ca
Iro H
c i um
4 Cal
al "
orm
3 "N

0
1 1 3 1 5 3
64 32 64 16 64 32
0.4 mm 0.8 mm 1.2 mm 1.6 mm 2.0 mm 2.4 mm

Scale Thickness, inches or mm

Long Term Overheating
Boiler Water Deposit Control

• Removal of impurities
• Pretreatment plant

• Chemical treatment
• Controlled blowdown
Effective Internal Boiler
Water Treatment

Controls
• Deposition

• Corrosion
Boiler Water Corrosion Control

• Oxygen pitting

• Caustic corrosion
• Embrittlement or gouging

• Acidic attack
Oxygen Corrosion - Pitting
Caustic Gouging
 Acid Corrosion

Acid Corrosion
Effective Internal Boiler
Water Treatment

Controls
• Deposition

• Corrosion

• Carryover
Control of Boiler Water Carryover

• Effective mechanical steam separation

• Proper control of boiler water chemistry
• Antifoam, as needed
• Avoid major contaminant ingress
• Proper boiler operating practices
 What Types of
Internal Boiler Water

Treatments are
Available ?
 Internal Treatment
Programmes

General Classifications
• Precipitating

• Solubilising

• Combination
 Internal Treatment
Programmes
• Phosphate/Polymer

• Phosphonate/Polymer

• Chelant/Polymer

• Phosphate/Chelant/Polymer

• All Polymer

• Coordinated pH/Phosphate/Polymer

• All Volatile Treatment (AVT)

Boiler Water Polymers

are Crucial to the

Success of any

Internal Treatment
Programme
How do Boiler Water Polymers
Function ?
 Boiler Water
Polymers
The mechanisms by which boiler
water polymers function are

• Complexation / Solubilisation

• Crystal modification

• Dispersion
Calcium phosphate,
magnesium silicate
crystals formed in
boiler water without
dispersant
Calcium phosphate,
magnesium silicate
crystals formed in
boiler water in the
presence of a
sulphonated polymer
Variables Affecting Polymer
Performance

• Functional group
• carboxylated (SCP/SCCP)
• sulfonated (SSP)
• phosphorylated (HTP)

• Polymer backbone

• Molecular weight
 Typical Polymer Structures
CH CH2 CH2 CH CH2 CH

C=O C=O C=O

O- OH NH2
X X

Polyacrylate Acrylate-Acrylamide Copolymer

CH3
CH2 CH CH CH
C CH2
C
= C =
O O
C=O O
SO3-
X Y
O-
X

Polymethacrylate Sulfonated Styrene-Maleic

Anhydride Copolymer
 Typical Polymer Structures
CH2 CH CH2 CH
O-

R P=O C=O CH2

O- O- H+ O [CH2 CH2 O]m H

n

Phosphonate
Polyethylene glycol allyl ether (PEGAE)

CH3 CH3
O O
=

C
=

-O
CH2
P C P O-
O=P OH
-O OH O-
O-
HEDP X
Poly (isopropenyl phosphonic acid)
PIPPA
 Polymer Performance
vs
Molecular Weight
Deposition

Polymer Molecular Weight

 Programme Selection
Considerations
• Boiler pressure, design

• Pre-treatment plant type

• Feedwater quality

• Hot well, deaerator type

• Steam turbine

• Control capabilities
 Chemical Factors

• Total Dissolved Solids (TDS)

• Alkalinity

• Silica

• Suspended Solids
 ASME Boiler Feedwater Quality
Guidelines for Modern Industrial
Water-Tube
Iron
Boilers
Copper Hardness
Drum Pressure •
(kg/cm²) • (ppm Fe) (ppm Cu) (ppm CaCO3)

0 - 21 • 0.10 0.05 0.30

22 - 31 • 0.05 0.025 0.30
32 - 42 • 0.03 0.02 0.20
43 - 52 • 0.025 0.02 0.20
53 - 63 • 0.015 0.10
0.02
64 - 70 • 0.05
0.02 0.015
71 - 105 •
0.01 0.01 0.0
 Internal Treatment
Programmes

• Phosphate/Polymer
 Phosphate/Polymer Treatment

• Reactions:

• Ca + PO4 + OH
Ca(OH)PO4
• Calcium Phosphate Hydroxide
Hydroxyapatite
•

• Mg + SiO3 + OH
Mg(OH)SiO3
• Magnesium Silica Hydroxide Serpentine
 Phosphate/Polymer Treatment

Characteristics
• Hardness controlled by precipitation
• Polymers used to control hardness
sludge and metal oxides
• Phosphate residual used for programme
control
• Hydroxide alkalinity required (pH : 10.5 -
12)
 Phosphate/Polymer
Treatment
Boiler Control Parameters
• Phosphate residual as PO4 depending on
hardness in the feedwater
• usually associated with boiler pressure
• and environmental legislation
• M alkalinity of 700 ppm as CaCO3 (25 % of
TDS)
• Polymer : min 360 ppm as SP8100
• Still the most used method for treating low
pressure boilers
 Phosphate/Polymer
Treatment
Advantages • Disadvantages

• Tolerates a wide range of • Is a precipitation

feedwater hardness programme (some
deposition is normal)
• Non corrosive treatment
• Higher blowdown rates
may be required
• Suitable for low to medium
pressure systems

• Easy operator control

Internal Treatment Programmes

• Phosphate/Polymer

• Phosphonate/Polymer
 Phosphonate/Polymer

Characteristics

• Organic phosphor donors combined

with three synergistic polymers
• Complexes hardness, iron and copper
ions in BFW
• Disperses/solubilises contaminants in
boiler minimising sludge formation
 Phosphonate/Polymer
a) Solubilising
Boiler Control Parameters
– 200 - 300 ppm in blowdown
– (BFW hardness + tot Fe) max 1 ppm for
300 ppm in boiler
– filtered tot. PO4 min 6 ppm in BD
– Other :
• conductivity
• SiO2
• M-alk
 Phosphonate/Polymer
b) Precipitating
Boiler Control Parameters

• Phosphate residual as PO4 depending on

hardness in the feedwater
• M alkalinity of 700 ppm as CaCO3 (25 % of
TDS)
 Internal Treatment
Programmes
• Phosphate/Polymer

• Phosphonate/Polymer

• Chelant/Polymer
 Chelant/Polymer
Treatment
• Common Chelating Agents

• EDTA

• NTA
 Chemical Structure of
EDTA

H H
- OOC - CH2 CH2 - COO -
N-C-C-N
- OOC - CH2 CH2 - COO -
H H
EDTA/Calcium Complex

CO
O CH2
CO CH2

O N
CH2
Ca
O N CH2

CO CH2 O CH2

CO
 Chelant/Polymer Treatment

Characteristics
• Are solubilising treatments
• Chelant complexes hardness and soluble iron /
copper
• Polymers used to enhance metal oxide control
• Must be fed to the feedwater line
 Chelant/Polymer Treatment
Advantages • Disadvantages

• Solubilising treatment • Requires intensive

operator control
• Effective on hardness and
soluble iron • Potentially corrosive if
misapplied
• Allow reduced blowdown

• Increased reliability and

efficiency

• Suitable for low to medium

pressure systems
 Internal Treatment
Programmes
• Phosphate/Polymer

• Phosphonate/Polymer

• Chelant/Polymer

• Phosphate/Chelant/Polymer
 Chelant/Phosphate/Polymer
Treatment
Characteristics
• Utilises EDTA chelant (partial chelation)
• Primarily a solubilising programme
• Phosphate provides back-up upset protection
• Residual phosphate test used as programme control
• Polymers used to control metal oxides and other
precipitates
 Chelant/Phosphate/Polymer
Advantages
Treatment
• Disadvantages
• Primarily a solubilising treatment
• Some precipitation is
• Effective on hardness and iron possible
• May allow reduced blowdown • Potentially corrosive
if misapplied
• Increased reliability and
efficiency

• Easy and accurate control test

• Tolerates a wide range of

feedwater hardness

• Suitable for low to medium

pressure systems
 Internal Treatment
Programmes
• Phosphate/Polymer

• Chelant/Polymer

• Phosphate/Chelant/Polymer

• All Polymer
 All Polymer Treatment
Characteristics
• Certain polymers can be effective
complexing agents
• Principle mechanism is complexation of
soluble impurities
• Secondary mechanism is dispersion of
particulates
• Fed to the boiler feedwater
Limitations of Polyacrylate Based
All Polymer Programmes

• Low tolerance to feedwater quality upsets

• Potential for calcium polyacrylate deposition
• Releases ammonia
• Economiser iron pick-up
• Precise testing for polymers is difficult
 Internal Treatment
Programmes
• Phosphate/Polymer

• Phosphonate/Polymer

• Chelant/Polymer

• Phosphate/Chelant/Polymer

• All Polymer/OptiSperse AP
 What is OptiSperse AP ?

• A new, revolutionary programme using

patented co-polymer technology

• A stand-alone all polymer / all organic boiler

internal treatment programme which
provides superior control over hardness and
iron deposition
 OptiSPerse AP Treatment vs.
Traditional All Polymer
• Traditional All Polymer • OptiSperse AP
Programme Programme
• Generates ammonia • No ammonia generated
• Forms calcium-polymer • No treatment related
deposits with BFW deposition
hardness excursions or
underfeed
• No steam purity
• Overfeed may cause problems
foaming
• Not corrosive to preboiler
• Corrosive to economiser circuit
surfaces
• May be fed ahead of
• Must be fed downstream of copper alloys in BFW
copper alloys
 Research Boiler Studies Under Fouling
Conditions
Test Conditions
900 psig (63 kg/cm2)
All-polymer Programme
Ca/Mg/Fe present

TRADITIONAL
ALL-POLYMER
DWD

OPTISPERSE AP

0 1 2 3 4 5
POLYMER/HARDNESS RATIO
 Research Boiler Studies
Under Potential Fouling Conditions
(Equal Polymer Actives)
Deposit Weight Density

300 psig (21 kg/cm2) 600 psig (42 kg/cm2) 900 psig (63 kg/cm2)

OPTISPERSE AP Traditional All-Polymer

 Internal Treatment
Programmes
• Phosphate/Polymer

• Phosphonate/Polymer

• Chelant/Polymer

• Phosphate/Chelant/Polymer

• All Polymer

• Coordinated
pH/Phosphate/Polymer
 Coordinated pH/Phosphate
Polymer Treatment
Characteristics
• Primarily for high purity/high pressure
systems
• Mainly a corrosion control programme
• Phosphate used to control pH and neutralise
excess caustic
• Polymers used to control deposition
 Corrosion of Mild Steel vs. pH

Relative Corrosive Attack

8.5 pH 12.7 pH

Safe Range
1 2 3 4 5 6 7 8 9 10 11 12 13 14
Caustic Concentration
Mechanism

Magnetite

NaOH

Steam Out

NaOH NaOH
NaOH

NaOH
Boiler Water in

Fe3O4 Porous
Deposit

NaOH
Prevention
magnetite
steam
escapes
porous
deposit
HPO42 - Na+
Na +

HPO42 -
Na+ Na+ HPO42 -
HPO42 -
Na+
HPO42 -
Boiler water in
 Minimising Caustic
Concentration and Corrosion
using Phosphate

NaOH + Na2HPO4 Na3PO4 + H2O

Caustic Disodium Trisodium Water

Soda Phosphate Phosphate
 Co-ordinated Congruent Phosphate/pH
Control Chart
10.8
10.6
"Free" Caustic O4
10.4 tio a/P
Region r Ra 2.8:
1N
Mola
10.2 O
a/P
4
1 N
10.0 3.0:
n dary
9.8 Bo u
O4
a/P
m 1N
i mu 2.7: "Captive"
9.6 Max r Ratio
Alkalinity
pH

ol a
9.4 O4 M Region
O4 Na /P
a/P 1
9.2 2.6:
1N 2.2:
nd ary
9.0 Bou
on trol

p h iu m
C

e
os od
at
8.8

Ph i-S
Vector

Caustic
Tr
Di-Sodium
Control
8.6 Diagram B lo
wd
own
M
o
Phosphate

Ph no-
os So
8.4 ph diu
at m
e

8.2
1 2 3 4 5 6 7 8 10 15 20 30 40 50 60
Ortho-phosphate, as PO4 mg/l
 Internal Treatment
Programmes
• Phosphate/Polymer

• Phosphonate/Polymer

• Chelant/Polymer

• Phosphate/Chelant/Polymer

• All Polymer

• Coordinated pH/Phosphate/Polymer OptiSperse

HTP
 Characteristics of HTP-2

• A unique new phosphorylated boiler polymer

• Particularly effective on iron

• Demonstrated clean-up ability

• Designed for high purity/high cycles systems

• Suitable for use up to 125 kg/cm²

 HTP-2 Polymer Structure

CH3

CH2 C

O=P OH

O-

X
Poly (isopropenyl phosphonic acid) . . . PIPPA
 Internal Treatment
Programmes
• Phosphate/Polymer - OptiSperse PO, OptiGuard MCP

• Phosphonate/Polymer - OptiSperse PQ

• Chelant/Polymer - OptiSperse CL

• Phosphate/Chelant/Polymer - OptiSperse CP

• All Polymer - OptiSperse AP, OptiGuard MCA

• Coordinated pH/Phosphate/Polymer - OptiSperse HTP

• All Volatile Treatment (AVT)