WATER CHEMISTRY

IN
THERMAL POWER PLANT
(OVER VIEW)

Presented by:
Pradip Patel
ESSAR POWER GUJARAT LTD -
JAMNAGAR
1
Role of Chemistry in Power Plant


Water Chemistry is important

to
Achieve higher operation efficiency
Minimize corrosion and scale formation problem
To reduce plant down time.


High water quality standards are to be maintain particularly in
high pressure boiler and upcoming super critical boiler.
2
WATER

The purest available form is from water vapour in atmosphere , as
rain, snow or produced by melting of ice.

This water on reaching the ground absorbs different types of
gases from atmosphere like nitrogen, oxygen and to a lesser
extent carbon dioxide.

Other gasses like ammonia, oxides of nitrogen and sulphur etc.
also dissolves during rain depending upon the pollution level of
the atmosphere.

Apart from this, the surface water travels to various places and
catches organic matter, suspended solids etc.
3
SOURCES OF WATER

Rivers, Lakes and reservoirs (Surface drainage water)

Underground water (shallow well, deep well, springs)

Rain water

Sea water

Snow melting
4
MAIN IMPURITIES IN WATER

Non dissolved & Non Ionic :
Suspended (Macro size) Sand, dirt, silt. This contributes
turbidity to raw water.

Colloidal Micro size particles (1 to 100 nm)

Dissolved & Ionic :
Dissolved form Alkaline salts and neutral salts, organic matter,

Alkaline salts are mainly bicarbonates rarely carbonates and
hydrates of calcium, magnesium and sodium.

Neutral salts are sulphates, chlorides, nitrates of calcium,
magnesium and sodium.
5
TYPE OF WATER IN THERMAL POWER PLANT

Raw Water

Process water

Boiler water

Cooling water


6
WATER TREATMENT IN POWER PLANT

(1) External Treatment
(2) Internal Treatment

(1) External treatment
Pre Treatment
Post Treatment

Why Pre treatment Plant ?

Pretreatment is required for removing Floating Solids, Suspended
Solids and Colloids.




7

Pretreatment:

(1) Screening
(2) Storage of raw water
(3) Chlorination
(4) Coagulation & Flocculation
(5) Filtration


8
Water Flow Diagram
9



Water
Intake
Raw
Water
Reservoir
I
Raw
Water
Reservoir
II

Clarifier
Tank-I

Clarifier
tank-II

Thickener
/Settler

Thickener
/Settler


Filer
Water
Reserv
oir
Tank


DMF

DMF

Service Water Tank /
DM Feed Tank

Cooling Tower Make
Up
Blow
Down

DM
PLANT
DM
Water
For
Boiler

Coagulation & Flocculation

Ferric Alum:
(Alum, Ferric Chloride, PAC)
Fe
2
Al
2
(SO4)
3
.18H2O+ Ca(HCO
3
)
2
---
Fe(OH)
3
+3CaSO
4
+2Al(OH)
3
+6CO
2

Hydrated Lime:-
Ca(HCO3)
2
+Ca(OH)
2
------2CaCO
3
+2H
2
O
Mg(HCO
3
)
2
+2Ca(OH)
2
------Mg(OH)
2
+2CaCO
3
+2H
2
O
Mg(OH)
2
+Al(OH)
3
----- SLUDGE

Coagulation aid:-
Poly electrolytes
10
Why Post Treatment Plant?
Dissolved Solids present in water is removed by Post Treatment.
Like,
Cation:
Calcium, Magnesium, Sodium etc.
Anion:
Bi Carbonate, Carbonate, Sulphate, Chloride, Silica
(1) Calcium bicarbonate Ca(HCO3)2 Scale
(2) Calcium carbonate CaCO3 Scale
(3) Calcium chloride CaCl2 Scale
(4) Magnesium bicarbonate Mg(HCO3)2 Scale
(5) Magnesium carbonate MgCO3 Scale
(6) Magnesium chloride MgCl2 Scale

11

Different type Post treatment plant

(1) MED
(2) R.O
(3) DM Plant etc.

12
WBA SBA MB
DGT
WAC SAC
D M Plant

DMST
ACF
DEGASSER

Dissolved solids present in water are removed in DM plant by Ion
exchange process and resin are used for this Ion exchange
process.
Depending upon the amount of water to be treated and quality of
the filter water, different types of demineralization schemes are
made.

DM Water Specification

pH : 6.5 6.9
Cond. (S/cm) -: < 1.0
SiO2 -: < 0.02 ppm


14
Service & Regeneration

SERVICE:-
Ion Exchange process in Cation Resin.
R-H
+
+ CaCl2, MgSO4, NaCl --- R-Ca, Mg, Na + HCl, H2SO4, 2HCl
Ion Exchange process in Anion Resin.
R-OH
-
+HCl, H2SO4 ----- R-Cl,SO4 + H2O

REGENERATION:-
Exhausted Cation exchange resin R-Ca, R-Na, R-Mg is converted
back to its original form by passing HCl
R-Mg + 2 HCl---- 2 R-H + MgCl2
R-Na + HCl R-H + NaCl
Anion exchange resin is regenerated by treating with NaOH
R-Cl + NaOH ----- R-OH + NaCl

15
Boiler Water Parameter

17
Sample
Detail
pH Sp.
Cond.
SiO2 PO4 N2H4 CC TH Fe
(s/cm) (ppm) (ppm) (ppm) (s/cm) (ppm) (ppm)
F.W 8.8-9.2 < 5 <0.02 < 0.03 < 0.2 0 <0.01
5
B.D 9.0-9.7 <20 <0.20 < 2.0 - 0
M.S 8.6-9.2 < 5 <0.02 <0.2 0 < 0.01
C.S 8.6-9.2 < 5 <0.02 <0.3

0 < 0.01
INTERNAL WATER TREATMENT
(BOILER FEED WATER & BOILER WATER TREATMENT)

Why required boiler water treatment ?
Prevention from scale/deposition on heating surfaces.
Prevention from corrosion, contamination & metal pickup in feed,
boiler & steam system (dissolve O2,CO2 and condenser tube
leakage)
Maintain of high level purity of steam.
Corrosion:
Dissolve oxygen:-
Fe --- Fe
++
+2e

Electrons migrate to the cathode area through the metal and
react
O2 +2H2O + 4e
-
---4OH
Fe + 2OH --- Fe (OH)2 (ferrous hydroxide)



18

The ferrous hydroxide is further converted to red rust seen on
the iron surface.
4Fe(OH)2+O2+2H2O ---- 4Fe(OH)3
2 Fe(OH)3 ---- Fe2O3 (corrosion)+ 3H2O

Dissolve CO2 present in water/steam forms H2CO3 (Carbonic
Acid)
CO2 + H2O ----H2CO3
2Fe +2H2CO3 ---2FeCO3 + 2H2
2FeCO3 + 5H2O + O ----- 2Fe(OH)3 + 2H2CO3
As H2CO3 double in volume the process leading to further
corrosion. It can be stopped till H2CO3 is neutralized.

19
Volatile Treatment (De Oxygenation)
Hydrazine Hydrate:

(1) Oxygen Scavenger

O2 + N2H4 ---- 2H2O +N2
It also decomposes at high temperature producing ammonia &
increases pH.
3N2H4 ----- 4NH3 + N2

(2) Reducing agent to passivate metal

6Fe2O3 + N2H4 --- 4Fe3O4 +2H2O + N2
(magnetite layer)
4CuO + N2H4 ----- 2Cu2O +2H2O +N2
(Cuprous Oxide)
20
Ammonia:

CO2 convert in Carbonic Acid
Due to carbonic acid pH is decrease and create corrosion.
Dissolved carbon dioxide is neutralized by Ammonia Solution and
pH boost up.
Carbonic Acid neutralized by addition of ammonia
H2CO3 +2NH3 --- (NH4)2CO3+2H2O
21
Coordinated Phosphate- pH Method


Caustic alkalinity in boiler water can develop via the reaction:

Na2CO3 + H2O ~> 2 NaOH + CO2

Tri sodium phosphate and disodium hydrogen phosphate react
similarly:

Na3PO4 + 2 H2O ~> 2 NaOH + NaH2PO4

Na2HPO4 + H2O ~> NaOH + NaH2PO4

22
Phosphate concentration vs. pH curve


23
Phosphate and pH
8
9
10
11
0 10 20 30 40
~> mg/l PO4
pH
Na3PO4 + NaOH
Na3PO4 + Na2HPO4

Coordinate Phosphate treatment Program ( Conventional treatment)
using Tri sodium phosphate.
Advantages: Protection against caustic embrittlement , caustic gouging.
Sudden pH fluctuations.
Vital parameters : pH/Conductivity/Ortho Phosphate /Silica/
Iron/P&M alkalinity/ Chlorides

Significance of boiler water analysis:
pH control is important because:
Corrosion rate of metals used in boiler systems are sensitive to
variations in pH.
Low pH or insufficient alkalinity can result in corrosive acidic attack.
High pH or excess alkalinity can result in caustic gouging, caustic
embrittlement, cracking, forming ( carryover)


24
Speed of O2 scavenging is dependent on pH levels.
Silica carryover (as Silicic acid) with steam is dependent on pH levels.
Corrosion rate of carbon steel at feed water temperatures approaches
a minimum values in the pH range of 9.2-9.6.
Significance of Conductivity
forming, water carryover with steam results super heater failure
Increase in conductivity increases the corrosion rate initially and then
decreases the same.
Significance of Ortho phosphate
Sufficient amount of PO4 has to be maintained in boiler water to
protect boiler from scale formation. PO4 reacts with scale forming ions
and forms non adherent complexes which can be removed by giving
blow down.
Amount of PO4 to be maintained in boiler water to be determined
based on BFW quality

25
Significance of Silica:
Solubility of silica in steam increases with increase in temperature.
Hence, at higher boiler water silica concentrations, silica carryover as
silicic acid with steam increases, which in turn results in deposition on
turbine blades.( reduces turbine efficiency and further failures). To
avoid all above, lower silica concentration in boiler water suggested.
Significance of Iron : is a measure of corrosion rate in boiler.

Significance of P& M alkalinity: appropriate control on alkalinity
levels is required to avoid caustic corrosion . P & M alkalinity is being
measured in boiler to ensure absence of Free caustic alkalinity ( 2P-M
values </= 0 ensures absence of free OH concentration).
Significance of Chlorides: control of chlorides in boiler water is very
essential especially on presence hardness. Trace of amount of Ca, Mg
ions react with chlorides to calcium , Magnesium chlorides which in
turn forms hydrochloric acid. This will reduce the pH of boiler water to
greater extent.

26

The exact composition of the phosphate precipitate depends on
temperature and has been found to be in the range of 2.6-2.8 for
pressure ranging from 1500psig to 3000psig. Thus, an Na/PO4 ratio of
2.6:1 is considered safe for all drum type boilers.
pH/PO4 coordinates can be maintained in 2.6-2.8 Na:PO4 molar curve
by using lower molar ratio dozing solution.( lower molar ratio dosing
solution can be attained by mixing various propositions of TSP & DSP
mixtures)
Operating boilers with continuous blow down. This is to provide more
stability to boiler water system.( keep check on alkalinity build up as
well as unexpected acid ingress)
Caustic corrosion : 1. Caustic gouging
Caustic gouging: Continuous dilution of magnetite layer due to excess
free caustic concentration in boiler water.
27
Cooling Water Chemistry

To avoid scale formation
To control corrosion
To control micro biological growth
To control vacuum in condenser

Circulating water chemistry is maintained primarily to control

Corrosion
Inhibit scale formation
To minimize micro organism growth in condenser tube or in
cooling water system.

29
Types of cooling water system

Once through cooling system
Open recirculation cooling system
Closed cycle cooling water system

Cooling water treatment:

Softening plant for make up as soft water with chlorination
Chemical treatment for scale inhibition and corrosion control
Acid dosing
Micro organism growth control by Chlorination
30

Chlorination:

This is the most practiced technique for cooling water treatment
in power plants. Chlorine is a powerful oxidizing agent and react
with nitrogenous part of microbial substances to form
chloramines.

Cl2 + H2O HOCl + H + Cl
HOCl H + OCl
NH3 + HOCl NH2Cl + H2O (Monochloramine)
NH2Cl + HOCl NHCl2 + H2O (Dichloramine)

31
Water Requirement at Different COC
32
COC
EVAPORATION
LOSS
DRIFT
LOSS
BLOW DOWN
REQUIREMENT
TOTAL MAKEUP
REQUIREMENT
M
3
/HR M
3
/HR M
3
/HR M
3
/HR
2 2429 50 2429 4907
3 2429 50 1214 3693
4 2429 50 810 3289
5 2429 50 607 3086
6 2429 50 486 2965
10 2429 50 270 2749