Boiler Water

Treatment

Training
Handouts .
AGD 1
Boiler Water System
pre-treatment Feed
s s
Tank s

Feed pump
Condensate s Receiver

s
Water
Column
Boiler Plant Process s Sample point
s
s
Continuous Blowdown
Benefits Of Using Steam
 High Heat Content.
 Gives up heat at constant
temperature.
 Produced from water which is cheap
and readily available.
 It is clean, odourless and tasteless.
 Can be used to generate power.
 Can be easily distributed and
controlled.
3
 Types 0f Boilers

 Coil type
 Smoke tube
 Water tube
 Spreader stroker

4
 Major Problems

 Scaling
 corrosion
 Priming / Foaming
 Silica carryover
 Caustic embrittlement / cracking

5
Problems Caused
By Impurities
 Water
Impurities Problems

 Dissolved Gases O2/CO2  Corrosion

 Hardness  Scaling
 Ca/Mg salts
 Carbonates
 Phosphates
 Silicates

 High TDS, SS, Alkalinity  Foaming/Priming

and Organic Matter
 High OH- Alkalinity  Caustic
embrittlement/
Grooving
7
 EFFECT OF SCALING,
CORROSION, CARRY-OVER ON
BOILER SYSTEM
 Reduction in heat transfer
 Severe elevation of metal/tube temperature
 Promotes under deposit corrosion - pitting
 Loss of construction material
 Failure of boiler tubes
 Water losses
 Increased maintenance cost
 Unplanned shut downs
 Ultimately, increased operational costs and loss of
productivity.
8
 Internal Boiler
Pretreatment
Treatment Heat

Condensate return line treatment

1.0 System: Feed
Problems Causes Treatment
Deposits Thermal decomposition and Deposit
precipitation of Alkaline Controllers
hardness

Precipitation of non-alkaline
hardness , by carbonate ,
alkali or orthophosphate
added for deposit control

Elevation of temperature

Corrosion Dissolved Oxygen Oxygen

Scavengers
Low pH Neutralising
Amines
10
 2.0 System : Boiler Drum
Problems Causes Treatment
Deposits Precipitation of Deposit Controller
Hardness

Silica Keep below the limits

recommended for the
particular boiler pressures

Control pH>9.4

Metal Oxides Disperants

Corrosion Oxygen and Low Feed Treatment before

pH Entering boiler
11
2.0 System: BoilerDrum
Problems Causes Treatment

Foaming High Dissolved and Antifoams

Suspended sollids
Contamination in feed
water eg. Oil, Organics ,
Sugars etc.
Priming Mechanical faults, Poor No chemical
Operation eg. Too high a treatment
water level, High loads,
Sudden steam demand

12
3.0: System:Steam /
Condensate
Problems Causes Treatment
Deposits Carry over from Antifoam
drum
Limit SiO2 control
Silica Volatalisation pH>9.4 in the drum water

Corrosion Oxygen ingress Volatile oxygen scavenger

Low pH Volatile neutralising amines in

boiler

13
Boiler Water Treatment
No Scale: Heat transfer surfaces
. free from Scale, sludge,
. & deposits
No corrosion: Surfaces covered
. by film of magnetite
Pure steam:Elimination of
. carryover
Safe Operation: Prevention of
. sludge in the water
. level & blow down control
Deposit Formation
Deposit Formation

 Caused by hardness salts ppting,-

Reduced solubility with increased temp.&
increased conc. due to steam formation
 Scale: occurs at the point of steam
. generation
sludge: occurs in bulk water & deposit on
. metal surfaces
 Lowers thermal conductivity
 Reduces boiler efficiency
 Increases fuel consumption
16
Deposits - Effects on Metal

 Furnace temp. over 2500 deg F

 Metal deforms at 900 deg F
 Water temp 338 deg F (100 psig)
. 546 deg F (1000 psig)
 Deposits form insulating barrier,
tolerence depends on nature & heat
tranfer of deposite

17
 Thermal Conductivities
( BTU .ft / ft2.hr.deg F )

 CaCO3 1.10
 Ca3(PO4)2 2.20
 CaSO4 0.90
 Fe2O3 0.35
 SiO2 (Quartz) 0.97
 Carbon steel 30.0
 Copper 218
18
 Scale Deposition
Potential
Tonnes/Year Entering Boiler
4
3.5
3.0 10 ppm hardness
Tonnes
2.5
2.0 5 ppm hardness
1.5
1.0 2ppm hardness
0.5
Steam Production kg/hr
10,000 20,000 30,000 40,000 19
SCALE / DEPOSIT CONTROL
 Deposit Control
 Correct Pre-Treatment of Feed Water
 Hardness Precipitation.
 ppted as CO3-2 or PO4-3 in presence of alkali.
 Add sludge conditioners-polymers.
 Metal Oxides
 Dispersed with phosphonate + polymer.
 Silica
 Mainly present as Silicic acid H2SiO3
 Decomposes above pH 9.4 into ions
 Treatment
 pH>9.4
 Keep below limits specified
21
 pH and PO4 Concentration
10.8
Above curve
10.6
Free caustic present
10.4
10.2 Below curve
10.0
pH all alkalinity in the form of phosphate
9.8
9.6
9.4
9.2 PO4- conc in ppm
10 20 30 40 50 60 70 80 90
22
CORROSION CONTROL
 Corrosion
 Presence of Oxygen, causing ferric
oxide rust ,Fe2O3
 Fe +2H2O ---> Fe(OH)2 + H2
 Under favourable conditions oxide
reduces to magnetite,Fe3O4,a very thin
protective adherent film/layer
3Fe(OH)2 ---> Fe3O4 + 2H2O + H2
 Magnetite film is most stable between
pH 10.5 - 11.5
24
 Corrosion Control

 Removal of oxygen
*Mechanical Deaeration
*Scavenging by chemicals

 Neutralising carbon dioxide

25
Mechanical Deaeration
 Steam or Vacuum is used

 Design to remove gases depends on:

- Solubility of gases
- Partial pressures
- Operating temperatures

 Technique employed :
- To reduce partial pressure
- Continuously extract evolved gases
26
Vacuum Deaerator
 Oxygen Scavenger
Reactions
 Hydrazine
N2H4 + O2----------> N2 + 2H2O
 Sulphite
2Na2SO3 + O2 ---------->2Na2SO4

 Diethylhydroxylamine (DEHA)
C2H5
NOH + [O] --> 2CH3COOH + 2N 2 + H2O
C 2H5
28
 Sulphite
Limitations:
 Adds to boiler water TDS

 Reaction slower at low temp

 At max temp/press (5400F /950 psig)

Na2SO 4 + H2O---> NaOH + H2SO3
H2SO3-------> H2O + SO2

 It can undergo auto-oxidation/reduction

4Na2SO3------>3Na2SO4 + Na2S

 Both SO2 and Na2S are corrosive

29
 Hydrazine
 Any Excess Hydrazine breaks down to give
Ammonia
3N2H4 ------> 4NH3 + N2

 Small amounts < 0.5 ppm useful to neutralise

CO2

 Metal Passivator
6Fe2O3 + N2H4 -----> 4Fe3O4 + 2H2O + N2

 Non-Volatile -----> Not available in return line

 Carcinogenic
30
Di-Ethyl-Hydroxyl-Amine
DEHA
 Non-Toxic
LD50 values---> 2190 mg/kg
(RATS, ORAL)
-------> 59 mg/kg for N2H4
 Volatile : Available in return condensate line
 Does not impart any solids to Boiler Drum Water
 1.24 ppm DEHA  1 ppm O2
 Forms stronger magnetite film

31
Reaction Rates Of Oxygen
Scavengers At 700F And pH 8.5
10.0
Hydrazine
8.0
Catalysed Hydrazine
D.O. 6.0 DEHA
ppm
4.0 Sulphite
Catalysed DEHA
2.0 Catalysed Sulphite

10 20
Contact Time In Minutes
Reaction rates of oxygen
scavengers at 700F& pH 11
10.0

8.0
D.O.,ppm Catalysed Hydrazine
6.0

4.0

Catalysed DEHA
2.0
Catalysed Sulphite

1.0 Time Minutes 2.0 3.0

 Ammonia Generated By
DEHA and Hydrazine
1.0

0.8
ppm NH3 Hydrazine
Generated
0.6
per ppm
Product 0.4

0.2
DEHA

100 200 300 400 500

Temperature (0F)
 Ability Of Catalysed Hydrazine to reduce
ferric iron to ferrous

10.0 Catalysed Hydrazine

Iron8.0
reduced
from ferric
6.0
to ferrous
Uncatalysed Hydrazine
4.0-

2.0 Catalysed Sodium Sulphite

0.1 0.2 0.3 0.4 0.5 0.6

Hydrazine Concn in Feed Water (ppm)
 Tannins

 Vegetable Tannins--Absorb O2 in
alkaline Condition
 Tannins form metal complexes & act as
corrosion inhibitors
 Decompose at high temp. Used in low
press. boilers
 useful at low temp. ,for protecting
feedline
36
 Carbon dioxide
Corrosion
 Carbon dioxide is present both in free &
combined form
 CO2 + H2O <---> H2CO3 ( H2O.CO2 )
. - +
H2CO3 <--->HCO3 + H (pK=4.2 )
. -2 +
HCO3 <---> CO3 + H (pK=8.3)
 Free CO2 is zero above pH 8.3 ,BFW is
therefore neutralised to pH 8.5 ~ 9.0 37
 Carbon Dioxide
Corrosion
CO2 is released on heating in the drum
_ _2
 2HCO3 + Heat ----> CO3 + H2O +CO2
_2 _
 CO3 + H2O + Heat ----> OH + CO2

 Fe + 2H2CO3 ----> Fe[HCO3]2 + H2

Soluble
 Fe(HCO3)2 Can Precipitate as FeO, Fe3O4,
FeCO3 in presence of O2 in codensate line

38
Return Lines Corrosion
 When steam condenses O2 & CO2
dissolve and produce dil.carbonic acid
containing O2
 This codensate will corrode return
system
 O2 causes pitting, while CO2 will
channel out as grooving
 Corrosion products will deposit in traps
& strainers, and may block narrow-bore
returns 39
Return Line Corrosion
Protection
 Pretreatment - 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
40
 Volatile Oxygen
Scavenging (V.O.S)
DiEthylHydroxylAmine (D.E.H.A)
 Volatile hence passed into steam
(Distribution ratio 1.26).
 Removes Oxygen directly from the
condensate
 Reduces corrosion and also promotes
formation of an adherent magnetite film
which gives additional corrosion
protection.
41
 Volatile Oxygen
Scavenger (V.O.A)

 Some pH elevation may be attributed to

DEHA

 As a RLT DEHA should be dosed in

combination with neutralising Amines.

42
 Neutralising Amines

 Steam volatile Alkaline materials which

prevent corrosion caused by carbon
dioxide

 Amine reacts with carbonic acid to form

Amine Carbonates or Bicarbonates and
fix CO2. Elevation of pH to above 8.5
minimises the corrosion rate
43
 Neutralising Amines
 Distribution ratio
Concentration of Amine in vapour phase
Concentration of Amine in liquid phase.

 High D.R= High volatility - Protects Cold End

Low D.R. = Low Volatility - Protects Hot End

 Single Neutralising Amines can be used but, more

often blend of amines with differing Distribution
Ratios is employed to maximise system protection.
Neutralising Amines are also used in combination
with V.O.S and with Filming Amines.
44
 Neutralising Amines
Amine Distribution Protects
Ratio
CycloHexylAmine 2.60 “COLD END”

D.E.A.E 1.45 General

Morpholine 0.48 “HOT END”

A.M.P. 0.30 “HOT END”

45
 Filming Amines
 Filming amines contain a cationic amine
group & a long hydrocarbon chain
(hydrophobic)
 Form an impervious, Non-Wettable film on
metal surfaces by attracting amine groups
 Steam condenses as a film & insulates
heat transfer surfaces.
 With filming amines the hydrophobic film
promotes condensation as droplets &
increases heat transfer ( Very useful on a
paper drying roller )
46
 Primary Amines

 Primary Amines form films which

completely cover metal surface giving
excellent corrosion protection
( Octadecylamine - 0.5 ~ 2.0 ppm )
 Insoluble - applied as an emulsion
 Incompatible with other products -
Separate Dosing system required.

47
 Secondary Amines

 Secondary Amines form less efficient

films. Should be used in conjunction
with neutralising Amines (e.g. Blended
products)

 Compatible with other products - can

use same Dosing system

48
 Filming Amines

 Filming Amines dosed to maintain Film

Integrity
 Over Dosing can cause Blockages
 Dosing must be carefully controlled
especially when applied to a previously
corroded system
 Should be introduced on a gradual
basis.
49
 Silica Carryover
 Silica is present as silicic acid, Si(OH)4
 It dissociates in alkaline condition :
. _ _
Si(OH)4 + OH ---> H2SiO3 + H2O
 Volatile silicic acid gets converted to
soluble silicate ion above pH 9.5
 As pressure increases ( B.P.Temp .
Increases) Silica becomes more
volatile,Silica content is therefore kept
within limits as per boiler pressure 50
 Silica in Boiler Water -
Relationship with Pressure
2.8

2.4 Maximum Silica Content in Boiler Water to

2.0 keep silica < 0.02 ppm in steam

1.6

1.2
Silica , ppm Boiler water pH > 10.3
0.8

0.4
Boiler water pH<9.0
0.0 Press.,psig
1300 1500 1700 1900 2100 2300 2500
Caustic Embrittlement

Under following conditions steel is

subjected to intercrystalline cracking :
 Boiler must be subject to high stress
 Boiler water must contain free NaOH

 Rivetted flanges & rolled-in tube ends

are more prone

52
 Inhibition Of
Cracking
 For HP & MP boilers - use zero caustic /
co-ordinated phosphate treatment
(normally stress relieved tubes are
used)
 for LP boilers following chemicals may
be used:
*NaNO3 - keep NaNO3 / T.Alk as
CaCO3 ratio above 0.4
*Na2SO4 - keep Na2SO4 / NaOH ratio
above 2.5 53
 Priming

 Ejection of boiler water into the steam

take-off
 Reasons:
*Too high drum water level
*Operating boiler below design pressure
*Operating at higher design capacity
 Controlled by strictly adhering to
operating conditions
54
 Foaming
 Pure water does not foam & steam
bubbles are large & burst quickly
 Following causes foaming by altering
surface tension- reduce bubble size:
*High suspended solids
*High alkalinity
*High dissolved solids
*Contamination of oils &other surfactant
 0.1 - 0.5 ppm antifom(certain organic
compounds) cause bubbles to coalse 55
Recommended Water Characterstics For Water
Tube Boilers
BS 2486 : 1978
Pressure at boiler outlet 20 40 60 80 100 120 >130
(Bar)/PSIG 300 600 900 1200 1500 1800

Boiler Feed Water At Economiser inlet

TH mg/l as O2 max 10 2 0.5 ND ND ND ND

PH 8.5-9.5 8.5-9.5 8.5-9.5 8.5-9.5 8.5-9.5 8.5-9.5 8.5-9.5
Oxygen Mg/l as O2 max 0.05 0.02 0.01 0.01 0.005 0.005 0.005
Total solids , Alkalinity silica ** ** ** ** ** ** **
Oil ND ND ND ND ND ND ND
Organic Matter - - - - - - -
Fe + Cu +Ni Mg/l as Max. 0.02 0.02 0.01 0.01 0.01

Boiler Water

Na phosphate mg/l as Na2PO4 50-100 30-70 29-50 10-40 5-20 3-10 !

OH Alk. Mg/l as CaCO3 , Min. 300 150 60 30 10 5 2
Total Alk. Mg/l as CaCO3 , Max 700 500 300 200 100 40 10
Silica , mg/l as SiO2 , Max < 0.4 of Caustic 20 10 ! ! !
Alkalinity
Na Sulphite mg/l as Na2SO3 30-50 20-40 15-30 10-20 - - -
Or
Hydrazine mg/l as N2H4 0.1-1.0 0.1-0.5 0.05-0.3 0.05-0.1 ! ! !
Susp solids mg/l Max 200 50 - - - - -
TDS mg/l max. 3000 2000 1200 700 350 100 15
Chloride mg/l as Cl- . Max - - - - 10 5 !

56
 Shell Boiler Operating Parameters
Type of boiler Lancashire Verticak Fire Tube Economic/Vertical Wt. Modern Packaged
Cornish
Boiler pr 350
Bar PSIG 150 150 150

Feed water
----------------
pH ---- ------- ------ 8.5-9.5

Tot Hardness Max, 200 100 40 2

Fe,Ni,Co,Max --- ---- ---- 0.2

Oxygen ----- ----- ------ -------

Oil Nil Nil Nil Nil

Boiler water
------------------
Caustic alk. Min. 200 250 250 350

Tot. alk. Max. ------------------------------------ -----------------------25% of TDS----------------------- -----------------

Phosphate asPO4 ------------------------------------ ------------30 - 60------ ------------------------------------- -------------------

Sulphite Na2SO4 50-100 50-100 50-100 30-70

Or
Hydrazine N2H4 --- ------ 0.1-1.0 0.1-1.0

Suspended solids max 2000 1000 1000 100

TDS max 8000 5000 5000/3500 3500

All reserves are as ppm. Hardness and alkalinity reserves are expressesd as CaCO3. The operating caustic alkalinity is 57
assumed to be half the maximum total alkalinity
Boiler Water Treatment
Programming
Calculations

58
 Survey Data
 Raw water analysis
 Pretreatment
 Feed water analysis
 Feed water Temperature
 Steam output and input pressure
 water consumption
 Condensate Return
 Steam Applications
59
Calculation steps
!. Determine Feed water quality
2. Determine oxygen scavenger dose
3 . calculate the maximum permissible boiler
conc.
4. calculate Alkalinity demand
5. calculate phosphate requirement
6. calculate sludge conditioner dosage
7. calculate return line treatment requirement
8. Determine blow down rate
9. convert product dosage ppm to weight
10. calculate cost of programme 60
 Determine Feed Water
quality
{ }
 Condensate Return% = 1 - Feed water Cl x 100
. Makeup Cl

 % Raw water usage = 100- Condensate

. Return %

 Feed water Quality= Make-up Quality x

. % Make-up water used

 (Assuming No Contamination of condensate
61
has occurred)
 Determine Oxygen
Scavenger Dose
 Sulphite Requirement
 [ Feed water O2(ppm) X 8 ]
+Sulphite Reserve/C

 Hydrazine Requirement
 [Feed water O2(ppm) X 1 ]
+Hydrazine Reserve/C

62
 Feedwater Temp
0C Temp. 0Dissolved
F oxygen
D.O.ppm
 100 212  0
 95 203  0.8
 90 194  1.6
 85 185  2.2
 80 176  2.9
 75 167  3.4
 70 158  3.9
 65 149  4.3
 60 140  4.7
 55 131  5.2
 50 122  5.6
 45 113  6.1
 40 104  6.6
 35 95  7.1
 30 86  7.5
 25 77  8.1 63
 20 68  8.8
 Determine Maximum Permissible
Boiler Concentrations

 C Max TDS = ________TDS MAX LIMIT_________

TDS FEED + SULPHITE DOSED

 C Max ALKALINITY = ALKALINITY MAXIMUM

TOTAL ALK. FEED - A

A is the Bisulphite allowance . Some Indion products are Bisulphite

based, check product application guidelines for allowance.

 C Max SILICA = MAX ALLOWABLE BOILER SILICA

ACTUAL SILICA IN FEED

64
 Alkalinity Demand

 Alkalinity Demand =
{(FWAlk - FW TH - Bisulphite Allowance) x Cmax}-
Alk Res
 Alkalinity reserve is normally taken as 850
ppm for low pressure boilers
 If demand is negative then no extra alkali is
required
 Dose 0.8 ppm Sodium Hydroxide per 1 ppm
of Alkalinity demand

65
 Determination of Phosphate
Requirement

 Assuming a product is 100%

phosphate as PO4 then dosage is given
by

 0.63 ppm product per 1 ppm CaH +

30/C max

66
 Checking Sludge
conditioner dosage
 Boiler Sludge Conditioner Dose =
Sludge Conditioner Conc ( 200ppm)
COC X Product Factor

 Typical Sludge conditioner levels are

minimum 200 ppm for normal operations and
minimum 300 ppm for on-line cleans

67
 Calculate Return Line
treatment requirement

 Dose of RLT Products is based on

maintaining condensate pH  8.5

 This in turn depends on CO2

generated in the boiler drum.

68
 Determination Of
Blowdown
 %Blowdown = 100 X S
. T-S
Calculated as %of Evaporation rate
 % Blowdown = 100 .
. C max
Calculated as % of Feed water
 Feedwater rate.
S - Feedwater TDS
T - Boiler water Maximum TDS
69
Conversion of dose rates to kg
product per day

 Say, Water Usage (Evaporation + Blow Down) = F

Tons/Day

 Say, product dose = X ppm

 Then, Product Required (Kg/Day) = F x X

1000

70
Water
Losses

71
Water Losses From Steam
System

 Evaporation Of steam
 Loss of Condensate
 steam Boiler leaks
 Blowdown

72
 Uncontrolled water
Losses

 Steam boilers
 Waste water
 Waste fuel
 Waste chemical
 Lead to poor control of inhibitor reserves
Lead to over running of pretreatment plant,
Fuel, increased chemical consumption

73