WELCOME

Flow of the Presentation

Stages in Boiler Water Treatment

Filtration and Clarification
Pre-Treatment
Types Of Boiler / Problems Faced
Boiler water treatment Low Pressure
High Pressure
Amine Technology
Boiler Precautions

Impurities in Water
Impurities Present

SurfaceWater

Borewell Water

SeaWater

Recycled Effluent

Suspended Solids

High

Low

Low

High

Dissolved Solids

Low

High

Very high

Variable

Organics

High

Low

High

High

STAGES IN BOILER WATER

TREATMENT
Pre-treatment:

Removal of suspended
dissolved impurities
De-aeration: Removal of gases,
especially dissolved oxygen
Internal Treatment: Boiler water
conditioning

Clarification & Filtration

Removes
Reduces
ALUM

suspended impurities.

organics to certain extent.

/ PAC
POLYELECTROLYTE

Raw Water
Treatemnt
Turbine / Process
De-Areator
Pre-Treatment
Scheme

Boiler

Economiser

De-Areator

Boiler Water Treatment

High Pressure Boilers
DM / RO-MB FEED
PROBLEMS
CORROSION
02/C02/ Caustic Emb
H2 Damage /Chelant
STEAM PURITY
Carryover
Colloidal Silica
Wet Steam
DEPOSITION
Sludge- B.Dn Problem
Phosphate Hide-out

Low Pressure Boilers

NON-DM FEED

Raw Water
Softned Water
DE-Alakalised Water
DM

PROBLEMS
SCALING
Hardness/TDS/P04
Carbonates/Fe
CORROSION
pH/02/C02
CARRYOVER
Water Hammer/ ALK

TREATMENT BASIS
Maintaining

Boiler water quality

Pre-Treatment and Blow-down
Proper treatment
Oxygen

Scavenging
Corrosion Inhibition
Scale Inhibition/ Sludge Conditioning
Carry Over reduction
Return Line Treatment

Scaling

Solutions

Carbonate Cycle
Phosphate Cycle
Sludge Conditioners
Chelates

Importance of Blow-Down

Importance of Blow-Down
NAME

FORMULA

COMMON CAUSES

Hydroxyapatite

Ca10(OH)2PO4)6

Insufficient sludge conditioner

Insufficient blow down

Calcium Silicate

CaSiO3

Low alkalinity
Inadequate blow down

Gypsum

CaSO4

Low phosphate high calcium and

Sulphate.
Inadequate blow down

Serpentine

3MgO.2SiO2.2H2O

Low alkalinity
Inadequate blow down

Magnesium

Mg3(PO4)2.Mg(OH)2)

Inadequate blow down

High phosphate

Hydroxyphosphate

Thermal Conductivity [ x 10 3 ]
CaCO3 : 2.2
Ca3(PO4)2 : 8.6
CaSO4 : 3.1

% B.Dn = Feed water Salts [ Fws] x 100

Boiler Water Salts Limit Fws

Scaling
Thermal Conductivity [ x 10 3 ]

Fe2O3 Ferric Oxide

Magnetite Fe304
SiO2 (Quartz)
Serpentine 3Mg0.2Si02.2H20

1.4
6.9
3.6
2.4

Energy Loss: % Fuel extra Consumed for same

steam out put: due to Deposits
Scale ThicknessNormal
[ Inches ] High Iron Iron + Silica
[1/64]
1
1.6
3.5
[1/32]
2
3.1
7
[3/64]
3
4.7
[1/16]
3.9
6.2

Solutions
Phosphate based Treatment
& Polymers

SCALE INHIBITORS
Sludge

Conditioning

Crystal Modifier with Dispersants

They

avoid formation of fine crystalline

sludge
particles which ct as bubble nuclei /
stabilizers

SCALE INHIBITORS
Chelation

SCALE INHIBITORS
Precipitation

PO4 cycles

CO-ORDINATED PHOSPHATE TREATMENT

SCALE INHIBITORS
Precipitation

PO4 cycles

DSP

TSP
DSP TSP

Na: P04

2.2

2:1

Solution Na: P04

3:1

TSP-NaOH
2.8

Congurent Point

3
2
0

Solid Na: P04

1.5

2.5

Corrosion

Mechanism of Corrosion
Anodic : Area over which metal is oxidised is Anode.
Fe + OH- = Fe (OH)2 + 2eCathodic: Area over which the oxidant material is reduced
is called Cathode. 2 e - + 02 + H20 = 20H _

Ions flow through the solution ( water ) and Electrons

flow through the metal.

CORROSION
Deaerator pressure psig

Temperature oF

212

205

197

188

178

164

148

133

218

212

204

195

186

175

162

149

227

221

215

208

200

191

180

189

237

227

220

215

208

200

190

181

239

235

230

224

218

204

196

Max. O2
content
ppm

0.7

1.4

2.2

2.9

4.3

5.0

3.6

CORROSION
Primarily caused by Dissolved oxygen
and dissolved carbon-di-oxide.
High temp & Pressure means even trace
quantities of oxygen are highly corrosive
Oxygen pitting

General Thinning due to H2CO3

Caustic Gouging
High Conc of Na0H during Film Boiling
Next Stage is Caustic Embrittlement

CAUSTIC EMBRITTLEMENT
Fe3O4 + 4NaOH = 2 NaFeO2 + Na2FeO2 + H2O
(Sodium ferroate)
Fe + NaOH = Na2FeO2(Sodium Ferrite) + H2

Porous magnetite films, deposits, cracks allow

localised build up of OH in that cause damage.

Hydrogen Damage
Almost

all
The
hydrogen damage is
associated
with
Caustic Gauging

Chelant Corrosion
the
Flow

Smooth & Along

Direction of

Dosage of chelants
if Non-Stiochiometric
Fe304 + Fe + 8H + 4 Chelant = 4 Fe(II)Chelant
+ 4 H20
Conc. Chelants can also attack magnetite layer:

Carbonic Acid Attack Control

Carbon dioxide is present both in free &
combined form
CO2 + H2O <---> H2CO3-

Controlled by using : Amine

Technology:
Neutralising Amines

Solutions
Oxygen Scavengers
Carbon-dioxide scavengers
Proper Treatment chemicals

OXYGEN SCAVENGERS
Tannins
- Tannin chemisorb

Oxygen Molecules

- Tannin also is an excellent

Iron Dispersant
- Tannin forms Tannate Film
Excellent Corrosion Inhibition
- Tannins improve the
performances of Antifoam

OXYGEN SCAVENGERS
Sulphites

/bisulphites
Hydrazine10.0
Tannins 8.0

N2H4 + 02

N2

Na2S03 + 02

+ 2H20
Na2S04

Hydrazine

Catalysed Hydrazine

D.O.
ppm

6.0

4.0

2.0

Sulphite
Catalysed Sulphite

10

Contact Time In Minutes

20

OXYGEN SCAVENGERS

Hydrazine

6Fe203 + N2H4 = N2 + 2H20 + 4 Fe304

10.0
Hydrazine
8.0
Catalysed Hydrazine
6.0

D.O. 4.0
ppm

DEHA

Catalysed DEHA

2.0
10

Contact Time In Minutes

C2H5)2 NOH + 9O2 8 CH3 COOH + 2N2 + 6H2O

Its Bye Products too scavange Oxygen

20

Carry over

Priming / Foaming
Priming : Mechanical reasons
- Faulty steam
separators
Load fluctuation
- Water level fluctuation
Sudden steam demand
Foaming
Carry over :
- Chemical reasons

Solutions
Antifoam for Carryover problems

CARRY OVER
Cut

Down by Proper Feed water quality.

No oils/ Grease.
Use Anti Foam /Tannins etc for LP
boilers.

Silica

Silica Volatilisation
Max Pr
[ psi ]

Silica
Steam

500

0.02

1000

0.06

1500

0.3

2000

1.4

2500

3000

25

BW-Silica:50ppm

Silica Volatilisation
Max Pr Max-BW
[ psi ]

Silica

Effect :pH on Silicic Acid

Volatility.

500

40

pH

Silica ppm Steam/

Sio2 in H20 as %

600

35

750

30

12

0.55

900

20

11

0.77

1000

10

10

1.02

1500

1.25

2000

1.48

1.73

AMINE TECHNOLOGY

Drawbacks of Conventional
Technology
CHEMICALS

TSP
Hydrazine
CHA
Sulphite
Polymer Based
Caustic

DRAWBACKS

Addition of TDS
Carcinogenic, High
initiation temperature
Volatile, High DR
TDS addition, requires
catalyst
Unstable
Caustic alkalinity,
foaming, TDS addition

Amine Technology

D.R = Concentration of Amine in Liquid phase

Concentration of Amine in vapour
phase.

High D.R= High volatility - Protects Cold End

Low D.R. = Low Volatility
- Protects Hot End
NEUTRALIZING
CHEMICAL
DISTRIBUTION
AMINE

FORMULA

RATIO

Ammonia

NH3

1 : 7 10

Cyclohexylamine

C6 H13N

1 : 2.6

Morpholine

C4H9NO

1 : 0.48

Aminomethyl
propanol

(CH3)2.C(NH2).CH2OH

1 : 0.30

Diethylamino ethanol

(C2H5) 2.NCHCH2OH

1 : 1.45

Diethylhydroxylamine

(C2H5) 2.NOH

1 : 1.26

Return Line Treatment

Pretreatment A Must
De-alkalisation / De-Mineralisation + Deaeration

Oxygen Scavenging (Volatile) - D.E.H.A

Use of Volatile Neutralising Amines to keep
BFW & condensate pH > 8.5
Filming Amines

*Softening Will not remove alkalinity &

should be avoided

Filming Amine / DEHA

N
N
N

Triangular

AMINE FILM
R
R
R

Square

WATER
METAL
SURFACE
LEGEND
R
N
MOLECULE
N+
R-

1A0

5A0

= AMINE
= AMINO GROUP
= ALKYL GROUP

Oxygen
12A0
Carbon Dioxide
14A0

DEHA

V/s

FILMING
AMINE

+ A.V.T.
+ L.P. DOSING
+ DEHA+ AMINE BLEND
RECOMMENDED

+ A.V.T.
+ L.P. DOSING
+ SINGLE
FORMULATION

+ SCAVENGES
OXYGEN

DOES NOT
SCAVENGES
OXYGEN

+ ENSURES pH OF
CONDENSATE = 8.4
approx.
+ THERMALLY STABLE
+ LOW DOSAGE
REQUIRED

+ ENSURES pH OF
CONDENSATE = 8.4
approx.
+ THERMALLY STABLE
HIGHER DOSAGE
REQUIRED

D.E.H.A.
D.O.,ppm

10.0

8.0

LD50 value (rats, oral):

2190 mg/kg, for DEHA
59 mg/Kg for Hydrazine

6.0
Catalysed Hydrazine

4.0
2.0

Catalysed DEHA
Catalysed Sulphite
1.0

Time Minutes

2.0

3.0

(C2H5)2 NOH + 9O2 8 CH3 COOH + 2N2 + 6H2O

Its Bye Products too scavange Oxygen

TOTAL SOLUTION
GOOD PRE-TREATMENT SCHEME
WITH AMINE TREATMENT

D.E.H.A.

NEUTRALISING AMINES

DISPERSING AMINES

PH BUFFERING AMINES

Phosphate as Contigency

BOILER PRECAUTIONS

Boiler Boil out

Alkaline

Boil out.
Removes Mill scales, Greese, oil, rust
etc..
Prevents on line operational problems
of the boiler.
Prevents Film Boiling and Hot Spots.

Boiler Preservation
Dry

Preservation:
For very long periods e.g 6 and
more months.Metal Loss is High.
Wet Preservation:
For Short periods e.g Below 6
months.Metal Loss is low.

THANK YOU