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Boiler Water

Treatment

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

Feed pump
Condensate Receiver
s

s
Water
Column
Plant Process Sample point
Boiler s
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
P r o b l e ms C a u s e d
By
I mp u r it ie s
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 Treatmen
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
De posit For mation
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 CONTRO
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 PO 4 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
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Corrosion Control

Removal of oxygen
*Mechanical Deaeration
*Scavenging by chemicals

Neutralising carbon dioxide

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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 70 0 F 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 70 0 F& 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 fer ric iron to fer rous

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 is37
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 50
Silica in Boiler Water -
Relationship with
2.8
Pressure
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
B oiler W ater T reatment
P rogramming C alculations

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

61
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
Dissolved oxygen
D.O.ppm
0
C Temp. F
0
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
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
69
T - Boiler water Maximum TDS
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