220354en - Water Chemistry Basic Level

Steam Turbines Water Chemistry
Basic Level
Training Lesson
ALSTOM (Switzerland) Ltd ABCD

Water Chemistry
ABCD Steam Turbines Basic Level
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Copyright by ALSTOM (Switzerland) Ltd 2005
This is a training lesson. It provides overall information about the specific system
only.
To understand the operation concept in detail the project specific documents as
defined in the document reference section have to be included together with this
lesson.
All mentioned / attached values and settings are for information only. Typical
values are used to clarify particular subjects. Settings furthermore are subject to
change site specifically during commissioning.
For actual values please refer to the final plant specific
Operation & Maintenance Documentation.
Power Plant Training Center

CSXA220354en_ Page 2
Water Chemistry
Table of Contents
Lesson Objectives................................................................................................................................ 6
Introduction to Water Chemistry ........................................................................................................... 7
General........................................................................................................................................... 7
Treatment, Purification...................................................................................................................... 8
Conditioning.................................................................................................................................... 9
Protective Layer on Steel in W/S Cycle ............................................................................................. 12
Supervision .................................................................................................................................... 14
Corrosion ......................................................................................................................................... 15
Types of Corrosion ......................................................................................................................... 16
Influence of Chloride...................................................................................................................... 22
Cathodic Protection ........................................................................................................................ 23
Galvanic Coupling ......................................................................................................................... 24
Deposits ........................................................................................................................................... 25
Introduction ................................................................................................................................... 25
Exceeding of the Solubility Product .................................................................................................. 25
Dosing & Sampling Points.................................................................................................................. 28
Chemical Dosing System ................................................................................................................... 29
General......................................................................................................................................... 29
Ammonia & Hydrazine Dosing........................................................................................................... 31
Phosphate Dosing ............................................................................................................................. 36
Sampling System............................................................................................................................... 40
Direct Conductivity ......................................................................................................................... 45
Acid-Conductivity ........................................................................................................................... 46
Measurement of the pH Value......................................................................................................... 48
Measurement of Oxygen ................................................................................................................ 50
Measurement of Silicate ................................................................................................................. 51
Closed Cooling Water ....................................................................................................................... 52
Introduction to Main Cooling Water Chemistry.................................................................................... 54
General......................................................................................................................................... 54
Types of Water Treatment ............................................................................................................... 55
Impact by Biology .......................................................................................................................... 56
Biocide Dosing............................................................................................................................... 58
Preservation ...................................................................................................................................... 60
Atmospheric Corrosion................................................................................................................... 60
Dry Preservation............................................................................................................................. 61
Wet Preservation ............................................................................................................................ 62
Components .................................................................................................................................. 62
Steam Turbine Protection ................................................................................................................ 63
Preservation Supervision ................................................................................................................. 63
Condenser Lay-up.......................................................................................................................... 64
General Supervision .......................................................................................................................... 65
Introduction ................................................................................................................................... 65
Conductivity Meter ......................................................................................................................... 66
pH Meter ....................................................................................................................................... 67
(Continued next page)

Water Chemistry
Table of Contents (continued)
Spectrophotometer......................................................................................................................... 68
Importance of Chemical Parameters ............................................................................................... 70
Trend-lines .................................................................................................................................... 72
Troubleshooting ............................................................................................................................. 73
Summary .......................................................................................................................................... 75
Annexs ............................................................................................................................................. 76
Annex 01: Units of Water Chemistry............................................................................................... 76
Annex 02: Conductivity of Pure Water ............................................................................................ 77
Annex 03: Types of Chemical Boiler Water Treatment ..................................................................... 78
Annex 04: Magnetite Solubility / Thickness of Protective Layer.......................................................... 79
Annex 05: Sacrificing Anodes ........................................................................................................ 80
Annex 06: Expansion Curves of Steam Turbines.............................................................................. 81
Annex 07: Description Ammonia/Hydrazine Dosing System............................................................. 82
Annex 08: Description Ammonia/Hydrazine Storage System............................................................ 84
Annex 09: Control Philosophy Ammonia/Hydrazine Dosing ............................................................ 86
Annex 10: Description Phosphate Dosing System ............................................................................ 88
Annex 11: Control Philosophy Phosphate Dosing ............................................................................ 90
Table of Figures
Figure 1: Causes of Infringement of Function on Turbines (Typical) ....................................................... 7

Figure 2: Oxides formed with Deoxygenated Treatment (Typical) ........................................................ 13
Figure 3: Oxides formed with Oxygenated Treatment (Typical)............................................................ 13
Figure 4: Influence on the Corrosion Process by Various Interactions (Typical)...................................... 15
Figure 5: Corrosion of Turbine Parts (Typical) .................................................................................... 17
Figure 6: pH-dependent Corrosion Speed (Typical) ............................................................................ 18
Figure 7: Corrosion Density Current (Typical)..................................................................................... 18
Figure 8: Velocity of Flow (Typical) .................................................................................................... 18
Figure 9: Influence of Acid (Typical)................................................................................................... 18
Figure 10: Localized Corrosion (Typical) ............................................................................................ 19
Figure 11: Contact Corrosion (Typical) .............................................................................................. 19
Figure 12: Crevice Corrosion (Typical)............................................................................................... 21
Figure 13: Crevice and Local Corrosion Potentials for Stainless Steel 304 L (DIN 1.4306) (Typical) ....... 22
Figure 14: Cathodic Protection (Typical) ............................................................................................ 24
Figure 15: Formation of Deposits: Bubbling (Typical) ......................................................................... 26
Figure 16: Formation of Deposits: Mechanism (Typical)...................................................................... 26
Figure 17: Deposits on the Steam Turbine (Typical) ............................................................................ 27
Figure 18: Dosing and Sampling Points (Typical)................................................................................ 28
Figure 19: Normal pH Scale (Typical)................................................................................................ 29
Figure 20: Rate of Corrosion as a Function of pH Value of Water (Typical) .......................................... 30
Figure 21: P&ID: Ammonia & Hydrazine Dosing (Typical)................................................................... 31

Water Chemistry
Table of Figures (continued)
Figure 22: Ammonia & Hydrazine Dosing System (Typical) ................................................................. 32

Figure 23: Ammonia & Hydrazine Dosing Local Control Panel (Typical) .............................................. 33
Figure 24: Ammonia & Hydrazine Dosing (Typical) ............................................................................ 34
Figure 25: Filling of the Ammonia Tank (Typical) ............................................................................... 35
Figure 26: Phosphate Dosing Pumps (Typical).................................................................................... 36
Figure 27: P&ID: Phosphate Dosing for Triple Pressure Stage Power Plant (Typical) .............................. 37
Figure 28: Relation of pH, Conductivity and Phosphate Concentration (Typical) ................................... 38
Figure 29: Phosphate mixing Basket with Agitator (Typical) ................................................................. 39
Figure 30: Sampling Conditioning Rack (Typical) ............................................................................... 40
Figure 31: Process Flow Sheet: Sampling System for Triple Pressure Stage Power Plant (Typical) ........... 41
Figure 32: Dosing and Sampling Points Example (Typical) .................................................................. 42
Figure 33: Water/Steam Cycle Sampling Rack (Typical) ...................................................................... 43
Figure 34: Flow Adjustment (Typical) ................................................................................................. 44
Figure 35: Measurement of direct Conductivity (Typical) ..................................................................... 45
Figure 36: Measurement of the Acid-Conductivity (Typical) ................................................................. 46
Figure 37: Regeneration Panel (Typical)............................................................................................. 47
Figure 38: pH Monitor (Typical) ........................................................................................................ 48
Figure 39: pH Sampling Probe (Typical) ............................................................................................ 49
Figure 40: Oxygen Monitor (Typical) ................................................................................................. 50
Figure 41: Silicate Monitor (Typical)................................................................................................... 51
Figure 42: Chemical Lock (Typical).................................................................................................... 52
Figure 43: Steel Corrosion in Humid Air (Typical) ............................................................................... 60
Figure 44: Dry Air Blower (Munters) (Typical) ..................................................................................... 61
Figure 45: Visual Inspection of Steam Turbine (Typical) ...................................................................... 63
Figure 46: Condenser Water Side (Typical) ........................................................................................ 64
Figure 47: Condenser Tube Sheet (Titanium) (Typical) ........................................................................ 64
Figure 48: Laboratory Conductivity Meter (Typical) ............................................................................. 66
Figure 49: Portable Conductivity Meter (Typical)................................................................................. 66
Figure 50: Laboratory pH Meter (Typical)........................................................................................... 67
Figure 51: Portable pH Meter (Typical) .............................................................................................. 67
Figure 52: Spectrophotometer (Typical) ............................................................................................. 68
Figure 53: Example of Phosphate Testing (Typical) ............................................................................. 69
Figure 54: Main Control Room (Typical) ............................................................................................ 72
Figure 55: Trend of different Chemical Parameters During Start-up (Typical) ....................................... 72
Figure 56: Magnetite Solubility (Typical) ............................................................................................ 79
Figure 57: Thickness of Protective Layer (Typical) ............................................................................... 79
Figure 58: Example of Efficiency Decrease (Typical)............................................................................ 80
Figure 59: Expansion Curves of Steam of 4 Different Turbines (Typical)............................................... 81

Water Chemistry
Lesson Objectives
Upon completion of this section, the trainee should be able to:
Recognize the dangers that could arise in the water/steam cycle of a power
plant due to water impurities.
Name the measures that should be undertaken in order to prevent damage of

the plant due to impure water.
Understand the function of the chemical dosing and sampling systems.
Understand the safety devices and handle them correctly.
Interpret the test readings.

Water Chemistry
Introduction to Water Chemistry

General
Salt: In the water/steam cycle of a power plant there are certain chemical reactions other
Deadly Disease than physical reactions that take place. Dissolved and undissolved salts in water can
cause corrosion and the formation of deposits on components. This not only affects
the function of the plant, but under the worst conditions can lead to irreparable
damage.
Reasons for
Damage
57 %
Deposition on blades
26 %
Localised corrosion
21 %
Formation
Formation
of cracks
0 20 40 60
CSXA403441.cdr
Figure 1: Causes of Infringement of Function on Turbines (Typical)
A study on turbines at US plants shows the main causes of infringed functioning:

57 % due to coating of deposits on the components.
26 % due to corrosion.
21 % due to cracks which arise from mechanically active forces (an aggressive
chemical environment stimulates crack formation).

Water Chemistry
General (continued)
Critical The following components and systems can be affected by corrosion and deposits:
Components
System Issues
Steam generating Corrosion in heat transfer zones by electrolyte
system containing deposits.
High temperatures and high pressure.
Compromises between material and design.
Turbine Corrosion by deposits and acids on the steam
expansion path.
High stress level.
Compromises between material and design.
Condensers Steam side:
Erosion corrosion/droplet impingement during
condensation.
Water side:
Corrosion under deposits. Plugging by biological
growth.
Pumps, pipes, Erosion and erosion corrosion.
joints/ceilings Mechanical wear and tear.
Cooling water system Scaling and biological deposits.
Tasks and The prevention of corrosion and deposits is the most important task of power plant
measures chemistry. Specific measures required for this task are:
Removal of salts (electrolytes) in the make up resp. feed water.
Conditioning of the water in the water/steam cycle
Monitoring/controlling of the water/steam cycle.
Treatment, Purification
Precondition Dissolved and undissolved salts in the water cause corrosion and the formation of
deposits on the components.
As the raw water for a power plant contains salts it cannot be used directly. It has to
be purified i.e. salts must be separated from the water through a dematerialize
plant.

Water Chemistry
Treatment, Purification (continued)
Removal of The concentrated contaminant resp. salt traces in the water/steam cycle are
Contaminants removed or at least reduced by the blow-down of the boiler.
from the Boiler
Make-up Water The make-up water parameters of the water/steam cycle can be checked through
Parameters various measuring parameters.
Parameter Unit Nominal Value

Spec. conductivity S cm-1 < 0.2
Sodium and Potassium g kg-1 < 10
Copper g kg-1 <3
Silicate as SiO2 g kg-1 < 20
Iron as Fe g kg-1 < 20
Source: HTDA 604862
Treatment Plant The most important components of the dematerialize plant are:
Water supply raw water.
Plant specific pretreatment (filters, flocculation, membrane systems, chemical
dosing).
Cation exchanger.
Degasser (for expelling of carbon dioxide).
Anion exchanger.
Mixed bed.
Conditioning
Anti-Corrosion It is not enough to simply remove salts as pure water itself cannot prevent corrosion
Dosing when no conditioning agent is applied. For this purpose ammonia and phosphate
are used in the water steam cycle. They prevent corrosion and provide a safety
measure in case the water/steam cycle is accidentally polluted.
The conditioning is implemented by special dosing systems:
Boiler water Phosphate dosing system
Steam/condensate Ammonia dosing system

Water Chemistry
Conditioning (continued)
Biological and To prevent the growth of biological life forms in the condenser and at the cooling
Anti-Scale water intake as well as to prevent hardness scaling in re-circulating cooling systems
Dosing (cooling tower), conditioning is again implemented by special dosing systems:
Condenser and cooling water intake Sodium Hypochlorite dosing system
Re-circulating cooling systems Sulfuric Acid dosing system
Feed water and The following table shows the typical specification for the feed water and boiler
Boiler Water water.
Specification
Feed Water
Parameter Unit Maximum Value
Conductivity after cation-exchanger S cm-1 < 0. 2
Spec. conductivity S cm-1 3-11
pH 9.0 ... 9.6
Copper g kg-1 <3
Oxygen g kg-1 <10
Silicate as SiO2 g kg-1 < 20
Iron as Fe g kg-1 < 20
Boiler Water
Parameter Unit Maximum Value
Spec. conductivity S cm-1 < 40
pH 9.1 ... 9.6
Silicate as SiO2 mg kg-1 1.6 *
Phosphate as PO4 mg kg-1 2 ... 6
* Depending on Pressure
Steam purity The ALSTOM steam purity specification is state of the art. It is nearly identical with
Specification the VGB guidelines and differs only in some details from the EPRI guidelines which
are somewhat more strict in some parameters.
On the following pages we add an excerpt from the Alstom Steam Purity
Requirements for Turbine Operation, HTGD 90 486 E.

Water Chemistry
Conditioning (continued)
Steam Turbine Requirements

for Turbine Operation
Table of Contents
Paragraph Title Page Code No. Mod.
V General description
V.1 Introduction V1
V.2 Steam purity requirements V1
V.2.1 Condensing turbines with superheated steam V1
Table: 1: Steam purity requirements V1
V.2.2 Condensing turbines with nuclear-generated saturated steam V1 P 0102 B
V.2.2.1 Boiling water reactors (BWR) V2
Table 2: Steam purity requirements, BWR plants V2
V.2.2.2 Pressurized water reactors (PWR) V2
Table 3: Steam purity requirements, PWR plants V2
V.2.3 Backpressure turbines V3 P 0202 B
V.2.4 Special cases V3
V.3 Deviations from the specifications V3
V.4 Supervision of the steam purity V3
V.4.1 Scope of application V3
V.2.4 Required minimum equipment V3 P 0302 D
V.4.3 General regulations V4
V.4.4 Plant-related chemical supervision system V4 P 0402 B
V.1 Introduction The specification is based on the guidelines of the
Impurities contained in the steam may cause deposits VGB (Vereinigung der Grosskraftwerkbetreiber) for
and corrosion in turbines, affecting adversely their the steam purity in continuous operation, issued 1980,
functioning. These problems can usually be avoided and on the experience gained by Brown Boveri. It is
when observing the recommendations listed below. applicable to fossil and nuclear fuelled plants.
The values stated are maximum values. The effective In addition to the requirements mentioned in table 1,
values should be kept lower whenever possible. Brown Boveri requires that the turbine is not exposed
to a liquid phase with a pH value below 5, neither
during operation nor standstill.
V.2 Steam purity requirements During start-up the values should have a declining
V.2.1 Condensing turbines with tendency; the values for continuous operation must be
superheated steam attained not later than 2 hours after start-up in case of
This specification is aimed at providing sufficient a warm start and 8 hours in case of a cold start.
protection of steam-exposed components against The steam purity requirements are identical for base
deposits and corrosion in areas with superheated load, peak load and industrial condensing turbines.
steam and against corrosion and corrosion fatigue in
saturated steam areas.
Parameter Unit Normal operation Start-up

On-line conductivity of live steam condensate measured
continually at the sampling point at 25 C after passing
through a strong acid cation exchanger (H+ form),
-1
eventually deductiong the conductivity due to carbon S cm < 0.2 < 1.0
dioxide
-1
Silica (SiO2) g kg < 20 < 100
-1
Total iron (Fe) g kg < 20 < 100
Total copper (Cu)
-1
a) < 150 bar g kg <3 < 10
b) > 150 bar g kg
-1 <1 < 10
-1
Sodium and potassium g kg < 10 < 20

Water Chemistry
Protective Layer on Steel in W/S Cycle
Without A vital aim of water chemistry is the corrosion prevention in boiler and W/S cycle
Protection Layer components. This is realized in the best way by providing adequate conditions (pure
no long-term water, correct chemical conditioning) that help to build up a protective layer from
Integrity of Steel iron oxides on the steel surface.
Components
This layer must be thin, homogenous and without cracks and pores, so that there is
a thin barrier (magnitude 10m) against the water- or the steam side in the
component. In the ideal case, there is no material transport neither from the water
to the steel (any contaminants) nor from the steel to the water (iron ions).
(Black) In pure water without any oxygen, the protective layer consists of tiny magnetite
Magnetite gives crystals (Fe3O4, a black oxide). Nowadays it is known that a layer from magnetite
a good But not alone is not ideally tight but has tiny channels resp. pores that allow some passage
the best of ions on the way from water to the steel and vice versa. Nevertheless, it had been
Protective Layer the classical philosophy for many decades that a pure magnetite layer is the
optimum.
Magnetite Since appr. 1970 it became more and more known that a certain low level of
together with oxygen in the W/S cycle water helps to make the protective layer even more tight,
some (Red) by plugging the channels, see above, with another type of iron oxides, the
Hematite gives hematite (Fe2O3, red oxide).
the optimized As a result, the modern philosophy for achieving an optimized protective layer
Protective Layer means:
For best conditioning of the water use clean water, raise the pH by ammonia,
and have a controlled low level of oxygen.

Water Chemistry
Protective Layer on Steel in W/S Cycle (continued)
Deoxygenated The following figure shows a schematic of the oxide that forms in deoxygenated
iron based surfaces. It attempts to illustrate that the transport of oxygen is controlled
by the pores in the oxide:
H 2O
Fluid boundary layer Fe(OH)+ OH- H2
Oxide
protective
cover layer H2
H2
+
Fe(OH)
-
Fe
2+ OH +
Fe(OH) 2 3
2
1
Metal
CSXA403385.cdr
Figure 2: Oxides formed with Deoxygenated Treatment (Typical)
Oxygenated The oxide structure changes when the feedwater is oxygenated and FeOOH forms
both on the surface and within the oxide pores. The FeOOH on the surface reduces
the amount of corrosion products that enter the water because of the lower
solubility of FeOOH compared with Fe3O4.
The FeOOH in the pores affects the oxide growth by reducing the diffusion of
oxygen through the pores:
H 2O O2
Fluid boundary layer
Oxide
protective
cover layer
Metal Fe3O4 iy-FeOOH or a-Fe2O3
CSXA403386.cdr
Figure 3: Oxides formed with Oxygenated Treatment (Typical)

Water Chemistry
Supervision
General The water in the water/steam cycle must be constantly checked so that correctional
measures can be made in time should a problem occur.
Manual Part of the supervision is completed by manual analysis. This has to be performed
Supervision periodically.
On-line However, important parameters are checked constantly by monitors. For example,
Supervision monitors for conductivity of the water, which define the extent/degree of the
impurity, are constantly in operation.
The measuring-results of these so-called on-line instruments are then routed to
the main control room (DCS).
Every single measured value and its interpretation permits constant actual
evaluation of the chemical condition of the plant. In case of irregularities,
indications are given of the possible functional disorders of the plant components
(e.g. cooling water in-leakage, disturbances in the water treatment plant,
contamination by boiler carry-over).
The interpretation of analytical results requires some experience. Important:
Look for consistency of the values in the boiler and W/S cycle, because the
parameters have certain logical connections and dependancies.

Water Chemistry
Corrosion
Problem In industrialized nations, a cost of approximately 3 to 4 % of the gross national

product can be attributed to corrosion.
Apart from the economic aspect, there is also the aspect of human safety which can
be endangered by corrosion. E.g. stress corrosion caused the ceiling in the indoor
swimming pool Uster, Switzerland, to collapse and resulted in the deaths of many
people.
Definition In the corrosion standards, corrosion is defined according to DIN 50900 part 1 as
follows:
Corrosion is the reaction of a metallic material with an environment that causes
a measurable change in the material and can lead to corrosion damage.
A discoloration of a surface coming from any oxidation process and not giving any
suspicion of damage is not corrosion:
The wording corrosion is connected with damage.
Interaction Corrosion processes are influenced by interactions:

Corrosion not only depends on the material and its environment, but also on the
design of the components and their servicing and maintenance.
Plant
Maintenance
Design
Environment
Corrosion
Stress
Corrosion
Stress reversal Material

Cyclic loading
Design Design
Plant CSXA403387.cdr
Figure 4: Influence on the Corrosion Process by Various Interactions (Typical)

Water Chemistry
Types of Corrosion
Introduction Corrosion research shows many types of corrosion processes all of which operate in
different ways. Not every corrosion type is detectable by the naked eye
(for example when no rust is seen). Here the corrosion specialist is consulted to
determine the exact nature and type of corrosion.
The following table shows the different types of corrosion which predominantly
appear in the power plant field.
The most Type of Causes Occurrence

important Types Corrosion
of Corrosion
Erosion corrosion Too high flow rate Steam heater, pre-heater,
Too low pH value condensers
Water inlet area of pre-heater,
condenser piping
Erosion Impingement of droplets Last blade row on the periphery,
(mechanical components only) condenser piping
High flow Condenser structure elements
Crevice corrosion Concentration of corrosive salts in Tube sheet, flanges, gen. Cracks,
cracks, under deposits under coating/deposit residue
Pitting corrosion Especially where passive layers Corrosive salts on stainless steel.
are damaged Areas under deposits (similar crevice
corrosion)
Stress corrosion Combinations of stresses, Turbine blading,
corrosive salts or acids, alcaline Brass tubing.
solutions and material (stainless
steel)
Corrosion fatigue Stress Turbine blading
Corrosive salts Boiler piping
Vibration
Contact corrosion Contact between materials of Hardly in water steam cycle, rather on
different electrochem. potential components open to the air, p.e.
contact stainless steel and alu
Atmospheric corrosion Electrolyte film (contamination) Low-alloyed steel parts in case of
humid air humidity,
Brass piping.
Standstill corrosion Fall of temperature Low-alloyed steel parts in case of
as special case of (leads to condensation), humidity,
atmospheric corrosion Air penetration. Brass piping.

Water Chemistry
Types of Corrosion (continued)
Corrosion of The following table shows types of corrosion which can occur on turbine
Turbine Parts components during operation:
Dry Parts
Aggressive contaminant deposits, e.g.:
n NaOH deposits on stellite valve spindles

> attacks stellite (general corrosion)
n NaOH deposits on welding/welded joints in drain pipes

> attacks welded joints (stress corrosion)
First Condensate
High contamination/concentration, e.g.:

(all contaminants are concentrated in a small
water quantity of the primary moisture)
n Chloride on turbine blades

> Fatigue corrosion
Wet Parts
Erosion, e.g.:
n Erosion, caused due to high flow rate

> Erosion corrosion
CSXA403388.cdr
Figure 5: Corrosion of Turbine Parts (Typical)
Uniform Numerous base metals are unstable in both acidic and neutral environments and
Corrosion corrode at considerable to high speed.

Water Chemistry
Corrosion Rate Example

can relatively In the case of iron, one observes a distinct corrosion speed at low pH values
well be (< pH 4), which is strongly dependent on pH. In comparison, the rate of corrosion
estimated in the pH range 4 to 10 is much less dependent of the pH in aerated water,
i.e. a really signifcant corrosion rate drop occurs at pH >10.
8 H2 development 100
density
rate
6 50
Mass development
Corrosion current
[gm-2d-1]
[Acm-2]
4 20
2 10
0 0
2 4 6 8 10 12 14 1 2 3 4 5
pH pH
CSXA403392.cdr CSXA403393.cdr
Figure 6: pH-dependent Corrosion Speed (Typical) Figure 7: Corrosion Density Current

(Typical)
Uniform 10
Corrosion 20 8
(continued)
Corrosion velocity
6
[vkorr]
vkorr
10 4
0 0
0 2 4 6 0 2 4 6 8
Velocity of
-1
flow Oxygen content
[ms ] CSXA403394.cdr
-1
[mgl ]
CSXA403395.cdr
Figure 8: Velocity of Flow (Typical) Figure 9: Influence of Oxygen (Typical)
Corrosion velocity of steel pipes in seawater Influence of the acid concentration

is dependent on the velocity of flow. on the corrosion rate of alloy steel
in flowing 165 mgl-1 CaCl2
solution (Vkorr in g(m2)-1d).

Water Chemistry
Localised O2 + H2O + 4e 4 OH Passive film Corrosion resistant materials,

Corrosion, e.g. zinc or chromium are
protected from corrosion by a
Dangerous passive film. The passive film is a
because ++ +
very thin oxide layer that builds
Me + 2H2O Me(OH)2 + 2H
Corrosion Rate up in a natural way and protects
can hardly be the material below it from
e ++
e
Forecast Me Me + 2e
corrosion.
In case of localized corrosion the
e passive film has been damaged
CSXA403396.cdr locally by a particular substance
causing corrosion, especially by
Figure 10: Localized Corrosion (Typical)
chlorides.
Contact Copper Contact corrosion can occur

Corrosion when two different metals come
in contact. When the two metals
Dangerous and Iron have different free corrosion
Quick, but less potentials, there is a higher
Frequent in W/S CSXA403397.cdr
corrosion rate in the baser
Cycle and Boiler material (the so-called sacrificial
Figure 11: Contact Corrosion (Typical) effect).
Contact corrosion is also known as galvanic corrosion. It occurs when a metal

comes into contact with another body, which is electrically conductive.
Potentials Free Corrosion Potential Potential of a corroding electrode in a medium.

(Definition) Equilibrium Rest Potential Potential of a non-corroding electrode in a medium.
Example Equilibrium potential of copper: 10 mV

Equilibrium potential of iron: 300 mV
Iron is the metal of low nobility and will therefore corrode more strongly when
coupled with copper, whereby the corrosion rate of the copper diminishes.
The equilibrium potential of common metals in phthalate buffer solution and in
artificial seawater are listed in the following tables.

Water Chemistry
Table 1 Equilibrium rest potential of common metals in phthalate buffer solution:

pH 6, 25 C, air saturated changes. Values in brackets:
Equilibrium rest potential changes with time to positive values (Elze and Olsner).
Metal R Metal R
(mV) (mV)
Gold (+306) Remanit 1620 (120 kg.mm2) (+7)
G AlSiMg with casting (+274) Beryllium nickel , soft (-40)
Silver +194 V2A Steel (-84)
Titan (+181) AlMgSi (-124)
Silverin (+164) Aluminium Al 99.5 (-169)
New-silver Ns 6218 +161 Tin (plate metal) (-175)
Silver solder 4505 +156 hard chromium coating (50 m) on steel (-249)
Bronze SnBz8 +156 Tin Solder lsn 90 (-258)
Cr AlSig with casting (+155) Tin Sn 98 (-275)
Silver solder 4404 +154 Tin solder Sn 60 (-279)
Yellow brass soms 70 +153 Lead Pb 99.9 (-283)
Silver solder 2500 +152 Cylinder iron GG-22 with coating (cupola furnace) -346
Monel (+148) Steel Mu St 4 -350
Silver Solder 4003 +145 Machine iron GG-18 with coating (electric furnace) -376
Yellow brass Ms 63 +145 Steel 1.26 % C -377
Elmedur +144 Carbonyl iron -389
New silver Ns 6512 (+141) Machine iron GG-18 with coating (cupola furnace) -389
Copper +140 Cylinder iron GG-22 with coating (electric furnace) -404
Beryllium copper, hard +140 Cadmium (plate metal) -574
AlMBz10 (+139) GK ZnAl6Cu1 with coating -762
Beryllium copper , soft +135 GK ZnAl6Cu1 without coating -773
Monel K +131 Zinc coating(100 m cyan) on steel -794
Yellow brass G Ms 64 +126 Zinc Zn 99.975 -807
Nickel Ni 99.6 +118 Zinc Zn 99.5 -815
Yellow brass Ms 63 Pb +117 Zinc Zn 98.5 -823
Remanit 1620 (+76) Zinc Zn 99.995 -827
Beryllium nickel, hard (+64) GD Zn Al4 -853
AlCuMg (+21) Electron AM503 -1460

Water Chemistry
Table 2 Equilibrium rest potential of common metals in sea water:

pH 7.5, 25 C, air saturated, changes the value in brackets:
equilibrium rest potential changes with time to positive values (Elze and Olsner).
Metal R Metal R
(mV) (mV)
Gold (+243) Lead Pb 99.9 -259
Silver +149 Zinc Zn 98.5 -284
Nickel Ni 99.6 +46 Hard chromium coating -291
Silverin +44 Machine iron GG-18 with coating (cupola furnace) -307
Yellow brass SoMs 70 +28 Steel Mu St-4 -335
Yellow brass Ms 63 +13 AlCuMg -339
Monel K +12 Cylinder iron GG-22 with coating (cupola furnace) -347
Copper +10 Cylinder iron GG-22 with coating (electric furnace) -351
Beryllium copper, hard +0 Machine iron GG-18 with coating (electric furnace) -455
New silver Ns 6218 -1 Cadmium (plate metal) -519
AlMBz10 -1 Aluminium Al 99.5 667
Elmedur -8 AlMgSi -765
Silver Solder 4404 -15 Zinc coating (100 m acid) on steel -794
Beryllium nickel, hard -46 Zinc coating (100 m cyan) on steel -806
V2A Steel -45 Zinc Zn 98 -809
Titan (-111) GD Zn Al4 -935
Remanit 1620 -134 GK ZnAl6Cu1 without coating -987
Zinc (plate metal) -184 Electron AM503 -1355
Crevice Crevice corrosion deals with localized intensive corrosion in devices e.g. below
Corrosion deposits.
In cases where there is a difference in the concentration in the corrosion medium, it
gives rise to a galvanic corrosion system.
Dangerous and O2 + 2H2O 4OH

Quick
Fe(OH)2+ 2H+
Fe++ + 2H2O
e
e
e Fe++ Fe++ e
e Fe++ e
CSXA403391.cdr
Figure 12: Crevice Corrosion (Typical)

Water Chemistry
Influence of Chloride
Introduction Crevice corrosion and localized corrosion are initiated mainly by anions. In this
sense chloride is a very corrosive anion and it is present in practically all types of
water.
Corrosions Given the equilibrium rest potential of various materials in water with a certain
chloride content, one can estimate the probability of corrosion. This plays an
important role in the selection of the material that components are constructed from
(e.g. condenser-pipes).
Example If the chloride concentration amounts to, e.g. 10 mg . kg-1, then the free corrosion
potential amounts to approximately 200 mV when the pH - value is 8. Here the risk
of crevice corrosion is very small.
When the pH value sinks to 5, then the potential in this area reaches the point
where crevice corrosion begins.
10
10
108
Chloride concentration
Crevice and localised corrosion
106
[mgkg-1]
No corrosion
104 Corrosion crevice
102
pH 8
pH 7
0 pH 5
10
free potential with O2 free water
- 0.5 0 + 0.5 1
V (SHE) CSXA403390.cdr
Figure 13: Crevice and Local Corrosion Potentials for Stainless Steel 304 L (DIN 1.4306) (Typical)

Water Chemistry
Cathodic Protection
Principle If the potential lies in the critical range then with the help of baser materials a
galvanic coupling can be made. In doing so, contact corrosion is initiated with the
purpose of lowering the potential of the endangered substance into the uncritical
area.
Single potential Stainless materials in seawater (ERP): approximative range 0 mV to +500 mV

Low alloyed steel in seawater (ERP): approximative range 0 mV to 600 mV
Mix potential Resulting mix-potential by coupling of several materials:

<0 mV to approximately 200 mV

Water Chemistry
Galvanic Coupling
Principle Heat exchanger pipes are processed out of Titanium or other rust free material.
(plated with stainless steel, e.g. DIN 1.4439)
Galvanic Coupling
Voltage measurement
[mV] range
Fe-
10 20 50
Anodes
5 10
0
20
1
0 50
WT
0 1k
OFF
pipes
V A
Pipe plate
Electrode Details
Pipe plate
Cathode
Cathode Anode
CSXA403389.cdr
Figure 14: Cathodic Protection (Typical)

Water Chemistry
Deposits
Introduction
When deposits form on some power plant components, the efficiency of the entire
power plant is impaired (e.g. on blades or in condenser pipes).
Impairment The deposits as such do not cause any permanent damage as they can be removed
by periodic cleaning. In condensers this is done by using rubber ball cleaning
devices and in gas turbines it is done by washing the compressor and turbine
blades.
Damages But the deposits can indirectly lead to permanent damage. They change the
chemical surroundings and encourage the corrosion processes, which are
irreversible. The problem here is that these chemical changes are not detectable by
on-line measuring techniques.
Conclusion So deposits should be avoided. Besides following the specification for water purity,
periodic inspection of the components is imperative.
Exceeding of the Solubility Product
Solubility Basically deposits develop when the solubility product of a substance is exceeded.
Product This solubility product (L) is constant at a given temperature.
Salt AB A + + B
L = (A) (B) = constant
SaltA 2B 2A + + B 2
L = (A) 2 (B) = constant
If L is exceeded, it leads to deposits.
Example: mol2
Gypsum (CaSO4) L = (Ca) (SO 4 ) = (0.0153) 2
I2
If Ca or SO4 are very high, it leads to deposits.

Water Chemistry
Exceeding the Solubility Product (continued)
Vaporization The concentration of the salts in the remaining water increases by vaporization.
Thereby the solubility product is exceeded and deposits develop.
Deposits
Heating zone Zone of elevated temperature and concentration Water

CSXA403398.cdr
Figure 15: Formation of Deposits: Bubbling (Typical)
Heating Boiling
Incipient Boiling Nucleate Boiling Film Boiling
Saturated
Steam
Boiler Water
Superheated
Steam
Risk of Depositis
Superheated Liquid
Heating Zone
CSXA403399.cdr
Figure 16: Formation of Deposits: Mechanism (Typical)

Water Chemistry
Exceeding the Solubility Product (continued)
Condensation High Pressure Turbine Low Pressure Turbine

Some substances like sodium and
silicate are steam volatile to a certain
degree under high pressure and
temperature. They enter the turbine
with the steam.
In contrast to the vaporization process
where salts become volatile during
CuOn
NaCl
steam expansion, the opposite
process is applied:
NaCl
NaOH
Substances with steam solubility
Na2SiO3
SiO2
(HCl)
condense again so that there is a
CSXA403400.cdr precipitation of a salt film on the dry
part of the turbine.
Figure 17: Deposits on the Steam Turbine (Typical)
According to the solubility the deposits are distributed variously on the turbine. Due
to this the efficiency level is decreased and the risk of corrosion increases.
Carry-Over:
Amount of contaminants that leave the boiler with the steam.
Definition
Explanation Carry-over can deal with solid or liquid contaminants. The most frequent case of
carry-over is when a small amount of water droplets is taken away with the steam.
In this way the dissolved or suspended (= undissolved, finely distributed) substances
find their way into the water/steam cycle.
Description The carry-over is defined by the comparison of the sodium content in steam and
boiler water:
Sodium in steam [mg kg-1]

0.1% *
Sodium in boiler [mg kg-1]
* pressure dependent
Higher value leads (e.g.) to the known deposits on the superheater pipes or on the
turbine blades.
Causes There are various causes for the carry-over:

Mechanical Bad water/steam separation in boiler.
Chemical The feed water contains excess organic contamination
(e.g., decomposition products of corrosion protective agents)
These can cause foaming of the boiler water.

Water Chemistry
Dosing & Sampling Points
General The dosing and sampling points for a triple pressure reheat combined cycle power
plant are indicated in the following diagram.
Depending on the number of gas turbines used for combined cycle operation
additional sampling and dosing points are implemented for each boiler drum and
each steam line.
Triple Pressure Feedwater sampling

Ammonia dosing
Reheat Hydrazine dosing

Combined Cycle
Sat. Steam sampling
Power Plant
Phosphate dosing
Blow-down sampling
Sat. steam
sampling
Ammonia dosing
Phosphate dosing
Hydrazine dosing
Blow-down sampling
To once through coolers
Condensate sampling
Sat. steam
sampling
Phosphate dosing
Blow-down sampling
IP live
steam sampling
From once through coolers
HP live steam sampling
Demin water
Oil no 2
Natural gas Make up water
CSXA403442.cdr
Figure 18: Dosing and Sampling Points (Typical)

Water Chemistry
Chemical Dosing System

General
Introduction Apart from the removal of salts, the conditioning of the water is an important
protection against corrosion.
Addition of base By the addition of a strong base, the pH value of the water is increased: By doing so
the occurrence of H+ ions in higher concentration, which lead to corrosion, can be
prevented. Normally ammonia and phosphate are added for conditioning. This is
done with the help of a dosing system.
Definition pH value Negative logarithmic of H+ ion concentration in moll-1

Acids Substance which produce H+ (= lower pH values )
Example H2SO4 H+ + HSO-4 2 H+ + SO2-
4
Bases Substances which accept H+ or give out OH (= higher pH values)

Example NaOH Na+ + OH
10-1 M 10-1 M
H Cl HOH Na OH
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
1 M HCl 0 mV 1 M NaCl
mV @ 20 C
D pH D pH
+ 58.16 mV - 58.16 mV
D pH
- 58.16 mV x 2
Acidity rising Alkalinity rising
CSXA403401.cdr
Figure 19: Normal pH Scale (Typical)

Water Chemistry
General (continued)
Steel and 8 The graph shows that with

Corrosion increasing pH a decreasing
7
corrosion rate of steel is achieved.
6 This is true for water with a low
oxygen content.
vK [g.(m2.d)-1]
5 With air saturated water, the
corrosion rate is still catastrophic
4 unless very high pH values are
reached.
3
2 T = 75 C
t = 24 h
= 1.6M m.s
-1
VM
= 0.02 mg.kg
-1
1 CO2
0
7 8 9 10
pH value
CSXA403402.cdr
Figure 20: Rate of Corrosion as a Function of pH Value

of Water (Typical)

Water Chemistry
Ammonia & Hydrazine Dosing
General Ammonia is fed into the water/steam cycle in order to increase the pH value. Values
between 0.2 and 2.0 mg kg-1 are necessary to obtain the desired pH value
between 9 to 9.6.
Hydrazine is only used if the oxygen content of the water/steam cycle is too high.
Additionally it can be used for wet preservation.
Hydrazine is a reducing agent that removes dissolved oxygen by the following
reaction:
N2H4 + O2 2 H2O + N2
This reaction is much faster at higher temperatures. Usually it is necessary to use

between 1 and 2 mg kg-1 of Hydrazine for the removal of 1 mg kg-1 dissolved
oxygen.
Feed Pipe The ammonia and the hydrazine can be typically injected with two dosing pipes:
Dosing into the feed water tank.
Dosing into the condensate line.
P&ID Condensate Condensate
Feed water tank Feed water tank
Demin. water
M M
M M
LFN20 LFN40
M M M M
Ammonia 1-10% Hydrazine 1-10%
CSXA403403.cdr
Figure 21: P&ID: Ammonia & Hydrazine Dosing (Typical)

Water Chemistry
Ammonia & Hydrazine Dosing (continued)
Feeding Point The liquid ammonia spreads rapidly through the water/steam cycle. Thus it is
sufficient to dose ammonia into the feed water tank.
In case of a problem, the dosing pipe into the condensate line can be used. It
should always be ensured that water flows through the corresponding pipeline to
avoid a high local concentration of ammonia.
The same applies for the hydrazine.
Ammonia
Dosing
Figure 22: Ammonia & Hydrazine Dosing System (Typical)
Types of The ammonia and the hydrazine dosing systems can be operated manually by the
Operation local control panel or automatically from the control room.
When in manual operation mode, the pumps can be individually switched ON
and OFF: As a safety measure, the pumps do not switch ON when the tank is
empty.
When the system is in automatic operation mode, the pumps are switched ON
and OFF based on various criteria from the control room.

Water Chemistry
Ammonia Logic The ammonia dosing pump will be switched ON automatically if:
At least one condensate pump is in operation.
The condensate discharge control valve is >10 % open.
The switch on the local control panel is in REMOTE position.
The conductivity of the feed water is low.
The ammonia dosing pump is switched OFF if:
No condensate pump is in operation.
The condensate discharge control valve is <10 % open.
The level in the dosing tank is very low.
The switch on the local control panel is changed from REMOTE to LOCAL.
The conductivity of the feed water is high.
Hydrazine Logic The hydrazine dosing pump will be switched ON automatically if:
No condensate pump is in operation.
The condensate discharge control valve is <10 % open.
The pump will be switched OFF if:
At least one condensate pump is in operation.
The condensate discharge control valve is >10 % open.
Local Control
Panel
Figure 23: Ammonia & Hydrazine Dosing Local Control Panel (Typical)

Water Chemistry
10.0 30
9.5 25
9.0 20
Conductivity [Scm-1]
IpH [-]
8.5 15
pH
8.0 10
Conductivity
7.5 5
7.0 0
0 2 4 6 8 10
NH3 [ppm] CSXA403406.cdr
Figure 24: Ammonia & Hydrazine Dosing (Typical)
Relation of pH, conductivity and ammonia concentration.

(Presumption: There is no considerable contamination in the water)

Water Chemistry
Filling If the ammonia tank is empty, then the signal Level-Ammonia tank low will be
indicated. After that there is sufficient time to refill the system:
Approximately 50 liters of concentrated ammonia solution (approximately 25 %) per
m3 is pumped into the tank and diluted with pure water. After the mixing with the
stirrer, the solution in the storage tank corresponds to about 1 %.
The same procedure can be applied for the filling of the hydrazine tank, using
approximately 50 liters of hydrazine solution.
Figure 25: Filling of the Ammonia Tank (Typical)
Ammonia and hydrazine are strong bases.

The filling of the tanks must be handled by at least two persons.
Hand gloves must be worn when handling the pumps.
At any cost the eyes should be protected: Protective glasses are imperative. It is
advisable to wear a gas mask with an ammonia filter.
If any part of the body comes into contact with any of these chemicals, it should
immediately be washed with water.
Additionally, hydrazine is listed as a "possible human carcinogen" and should
therefore be handled very carefully.

Water Chemistry
Phosphate Dosing
General Phosphate is not fluid and therefore it is dosed only into the boiler drums. The
addition of phosphate keeps the pH value of the boiler water higher than the water
in the water/steam cycle. In this way, the boiler is protected against any possible
corrosion. Furthermore, the phosphate acts as a buffer against a quick pH value
drop that could be caused by contamination.
The pH value of the boiler - water should be between 9.1 to 9.6, which corresponds
to a phosphate content of 2 to 6 mg kg-1.
As the boiler loses water with the blow down, a continuous addition of phosphate is
necessary.
Figure 26: Phosphate Dosing Pumps (Typical)

Water Chemistry
Phosphate Dosing (continued)
P&ID Demin. water HP boiler drum IP boiler drum LP boiler drum
LFN01 M M M M
Phosphate sol. 1-5%
CSXA403409.cdr
Figure 27: P&ID: Phosphate Dosing for Triple Pressure Stage Power Plant (Typical)
Types of The phosphate dosing system can be operated manually by the local control panel
Operation or automatically from the control room.
When in manual operation mode, the phosphate pumps can be individually
switched ON and OFF: As a safety measure, the pumps do not switch ON when the
tank is empty.
When the system is in automatic operation mode, the pumps are switched ON and
OFF based on various criteria from the control room.
Switch ON The pumps run in accordance with the following switching ON criteria:
Criteria The GT is in operation.
The continuous blow down valve is open.
The wheel chamber pressure is > 10 %.
The re-circulation pump is in operation (if available).
The pH value in the boiler drum is low
(each boiler drum is controlled individually).

Water Chemistry
Switch OFF The pumps are switched OFF under the following criteria:
Criteria The GT is not in operation.
The continuous blow down valve is closed.
The wheel chamber pressure is < 10 %.
The re-circulation pump is not in operation (if available).
The pH value in the boiler drum is high.
Relation 10 45
between pH,
Conductivity and
9.9 40
Phosphate
Concentration
9.8 35
9.7 30
Conductivity [Scm-1]
9.6 25
IpH [-]
9.5 20
9.4 15
pH
9.3 10
Conductivity
9.2 5
9.1 0
0 2 4 6 8 10
PO4 [ppm] CSXA403410.cdr
Figure 28: Relation of pH, Conductivity and Phosphate Concentration (Typical)
(Presumption: Molar Ratio of Na/PO4 = 3 and NH3 Content = 0.5 mg kg-1)

Water Chemistry
Filling The filling of the dosing tank is completed by adding Na3PO4 10H2O to the
solvent tank and filling it up with water.
The agitator is then switched ON for a couple of minutes. The resulting solution is
about 1 %.
Figure 29: Phosphate mixing Basket with Agitator (Typical)
Tri- sodium phosphate is a strong base and is highly soluble.

While handling phosphate the eyes should be well protected: It is imperative to
wear protective goggles at all times.
Hand gloves are necessary to protect the skin.
If any part of the body comes into contact with phosphate it should be washed
immediately!

Water Chemistry
Sampling System
General The supervision of the water/steam cycle requires special monitors that are provided
to continuously check the water.
In addition to the continuous measurements, further tests are carried out manually
and analyses are made in the laboratory.
Parameter Following parameters are supervised/checked continuously.

pH value
Conductivity
Acid conductivity
Oxygen
Conditioning The steam and boiler samples are too hot to use directly with the online equipment.
Therefore, the water is routed through special sampling coolers, resulting in sample
temperatures of below 40 C. The sampling coolers themselves are connected to
the closed cooling water cycle.
Figure 30: Sampling Conditioning Rack (Typical)

Water Chemistry
Sampling System (continued)
Typical Process LP SAT steam

11QUL10
IP SAT steam
11QUL13
IP superheated steam
11QUL14
HP SAT steam
11QUL15
HP Live steam
11QUL16
Flow Sheet
Legend:
CC = Cation conductivity
CC = Acid conductivity
C = Conductivity
O2 = Dissolved oxygen CC CC
= Grab sample QIRA QIRA
LP Boiler blow-down IP boiler blow-down HP boiler blow-down

11QUL01 11QUL03 11QUL05
C C C
QIRA QIRA QIRA
pH pH pH
QIRA QIRA QIRA
Condensate Feedwater Closed cooling water Make-up water

18QUL30 18QUL40 19QUP50 18QUL80
C
QIRA
CC O2 CC
QIRA QIRA QIRA
CSXA403413.cdr
Figure 31: Process Flow Sheet: Sampling System for Triple Pressure Stage Power Plant (Typical)

Water Chemistry
CSXA403414.cdr
Figure 32: Dosing and Sampling Points Example (Typical)

Water Chemistry
Figure 33: Water/Steam Cycle Sampling Rack (Typical)

Water Chemistry
Disturbances This applies to all monitors:

During the continuous inspection
and supervision, the flow should
be checked repeatedly.
During choking or change of
pressure by change in load, the
flow could block. This leads to
measurement errors causing
incorrect results.
The signals controlling the dosing
station should always be
accurate.
Figure 34: Flow Adjustment (Typical)

Water Chemistry
Direct Conductivity
Monitors In standard plants, these monitors indicate the direct conductivity. There is one
monitor for each boiler and one for the feed water.
Boiler Water The conductivity of the boiler water indicates the level of
contamination and/or the amount of phosphate in the
drum. The value for all the these boilers should be
< 40 S cm-1
Feed Water The direct conductivity of the feed water shows the
ammonia content.
The corresponding monitor should be attended to,
without fail and at any cost. As the control of ammonia
dosing depends on this value, an incorrect measurement
(e.g. In case of insufficient flow) could cause dosing
errors.
Figure 35: Measurement of

direct Conductivity
(Typical)

Water Chemistry
Acid-Conductivity
Monitors These monitors are used to continuously measure the

Acid-Conductivity. The proportion of dissolved salts can
be derived; i.e. the purity of the examined water can be
determined from the obtained results.
Cation- In contrast to the direct conductivity, while measuring the

Exchanger acid conductivity the water flows through the Cation-
exchanger before entering the conductivity sensor.
Here all the cations are exchanged by/through H+.
Depending on the purity of the water different acids may
be found e.g. HCl, H2SO4, H3PO4 or H2CO3.
Ammonia Now, what happens to Ammonia present in the

water/steam cycle, which is in high proportion in case of
direct conductivity?
Ammonia (NH3), which breaks itself with water in both
the Ions NH4+ + OH-, remains in the Cation-exchanger;
at the end of the Cation-exchanger only H+ + OH-
(Water) ions come out. This does not influence the acid
conductivity at all.
Figure 36: Measurement of

the Acid-
Conductivity
(Typical)

Water Chemistry
Acid-Conductivity (continued)
Regeneration of Depending on the concentration of ammonia in the

the Cation- water/steam cycle, the Cation- exchanger will exhaust
Exchanger sooner or later. Either this can be detected by a color
change in the column, or when only one monitor shows
a steady conductivity increase.
The exhausted Cation-exchanger can be regenerated,
using a solution of hydrochloric acid. (approximately
once per month).
Figure 37: Regeneration

Panel (Typical)
Measurement of The highest purity requirement is required on the superheated high-pressure steam,
HP Steam as the impurities are deposited on the steam turbine. This is why during the
operation of the steam turbine; the steam needs to be below 1 S cm-1 during start
up and under normal operation conditions below 0.2 S cm-1.

Water Chemistry
Measurement of the pH Value
Monitors In a standard plant, there is a continuous monitoring

facility for the pH value of each boiler blow-down water.
This pH value should be between 9.1 and 9.6.
Figure 38: pH Monitor

(Typical)

Water Chemistry
Measurement of the pH Value (continued)
Maintenance Proper functioning of these monitors is essential as they control the phosphate
dosing. An incorrect signal, e.g.: during insufficient flow, causes incorrect dosing.
Qualified employees should calibrate the pH monitors once in every two weeks. For
this calibration two different solutions with known pH values (pH buffer) are used.
Maintenance
Figure 39: pH Sampling Probe (Typical)

Water Chemistry
Measurement of Oxygen
Monitor The inlet line of the Oxygen monitor can be switched

between the condensate and the feed water. With the
help of this monitor, the amount of dissolved oxygen can
be determined.
Start If the plant is not in operation, the water / steam cycle is

saturated quickly with oxygen. After starting the plant, the
oxygen content in the feed water should fall below
10 gkg-1. If this is not the case, then there is a
possibility that the deareator is not working properly or
that air has been sucked in through a narrow point.
Calibrator The oxygen monitor can be calibrated manually or once

a week automatically. The water supply is automatically
stopped and the sensor on the air is calibrated.
Figure 40: Oxygen Monitor

(Typical)

Water Chemistry
Measurement of Silicate
Monitor Silicate does not break-up into ions in water therefore, it cannot be detected by the
acid-conductivity.
A silicate monitor can be used for the automatic measurement of the steam: By
adding different reagents, a blue - coloring develops in relation to the silicate
concentration. This can be checked photo metrically. If this monitor is not available,
manual measurement of the silicate concentration can be performed in the
laboratory.
Figure 41: Silicate Monitor (Typical)
Maintenance This monitor is very sensitive and should be checked every four weeks. While doing
so, the reagents are exchanged. A chemist should perform such maintenance.

Water Chemistry
Closed Cooling Water
General The closed cooling water usually consists of demineralized water. The chemicals for
the conditioning of this water are added with a special chemical lock.
The supervision of this water is completed manually in the laboratory.
Chemicals One of the following chemicals/mixtures is added to the closed cooling water cycle:
Hydrazine, N2H4 (100-300 mg kg-1)
Caustic Soda, NaOH (4 mg kg-1)
Glycol with 0.15 % NaBO2 and 0.3 % NaNO2
Hydrazine is often used because of the good oxygen removal effect of this chemical.
In countries where the use of hydrazine is not allowed, caustic soda is used in order
to adjust the pH to 10.
The demineralized water is fully saturated with air/oxygen. Therefore, any loss of
closed cooling water is to be avoided or at least minimized. The oxygen being
transported into the system will be quantitatively transformed into rust deposits if
caustic soda is used.
If the temperatures of the closed cooling cycle can drop to below zero, glycol
instead of demineralized water is used to fill the closed cooling water system.
Chemical Lock
Figure 42: Chemical Lock (Typical)

Water Chemistry
Closed Cooling Water (continued)
Parameter The following parameters are supervised/checked manually.

pH value
Conductivity
Copper
Oxygen
Chloride
Total hardness
Iron
If the pH or the concentration of the required chemical falls below a certain limit,
more chemical has to be added though the chemical lock. This often happens after
a leakage or after a longer period of operation.
Specification for The following 2 tables shows 2 standard specificsations for the conditioned closed
Conditioning cooling water. For freeze protection, glycol water mixtures have to be used. They
with Caustic necessitate a special conditioning (neither caustic nor hydrazine can be used).
Caustic conditioning
Parameter Unit Normal Value
pH 9-10
-1
Spec. conductivity S cm <40
Iron mg kg-1 < 0.5
Copper mg kg-1 -
-1
Oxygen g kg <20
-1
Chloride mg kg < 0.1
Total Hardness as ppm CaCO3 <2
Specification for Hydrazine conditioning

Conditioning with Parameter Unit Normal Value
Hydrazine
pH 9-10.5
-1
Spec. conductivity S cm <40
-1
Hydrazine mg kg 100-300
-1
Iron mg kg < 0.5
-1
Copper mg kg -
-1
Chloride mg kg < 0.1
Total Hardness as ppm CaCO3 <2

Water Chemistry
Introduction to Main Cooling Water Chemistry

General
Cooling Waters Raw waters show very different analytical compositions, and no raw water is
Differ strongly identical with any one else, because each raw water is a unique product the
composition of which is given by the natural environment and man-made influences
like waste waters. The qualities range from rain water-like types (10-100 S/cm) to
sea water (45000-55000 S/cm). Therefore , a raw water must be specifically
checked for use as a cooling water. Based on water analysis, the treatment of the
raw water must be designed.
Different On the one hand, the treatment has to assure that the inorganic constituents of the
Treatments are water are prevented form forming deposits and being corrosive. On the other
to be considered hand, the biological potential of the water must be controlled.
Prevent Deposits Deposits can widely influence the performance of a plant, be it by lowering the
power output or endanger the function of components ands systems.
Lowering of heat transfer by p.e. scaling in heat exchangers.
Plugging of heat exchanger tubes.
Plugging of cooling tower packs.
Providing Corrosive conditions under deposits.
Prevent The materials in contact must be either designed for corrosion resistance against
Corrosion the water or must be specially protected.
The composition of the cooling water must be carefully supervised to take measures
in time if the concentration of aggressive constituents exceeds the set limits.

Water Chemistry
Types of Water Treatment
Water For once through cooling systems, the treatment is generally restricted to dosing of
Treatments biocides. An additional water treatment is not necessary because there is no
concentration resp. change of chemical composition when passing the condenser
or other heat exchangers.
Easy for once The treatment of make up water for cooling tower systems is much more
through Cooling complicated. In dependance of the selected concentration factor and the given
materials, the make up water must be treated.
With normal water qualities and moderate concentration factors, acid dosing to
control hardness scaling and biocide dosing may be completely sufficient.
Complication With salty, high turbidity and dirty waters, an intensive make up water treatment
expected for involving one or more of the following steps may be necessary.
higher loaded Flocculation to remove high turbidity and colloids.
Waters
Full flow or side stream softening by lime dosage.
Filtration.
Acid dosing.
Hardness stabilizer dosing (mostly as replacement of acid dosing).
pH adjustments.
Oxidation processes to remove iron/manganese.
Biocide treatment.
Biological pretreatments.
Such treatment steps are costly and require adequate maintenance. So, the selected
concentration factor is a compromise between cost of water consumption and
investment/chemicals consumption/maintenance for the treatment.

Water Chemistry
Types of Water Treatment (continued)
Critical The following components and systems can be affected by corrosion and deposits:
Components
System Issues
Which Cooling tower packs Deposits can increase weight up to collapse of cooling tower.
Components
Cooling tower wood Wood is chemically attacked by too high chlorine level.
structure elements Wood fouls by intrusion of biological materials (molds, yeast)
Condenser water In case of stainless steel tubing pitting corrosion if water
side aggressive.
Under-rubber lining corrosion in case of mechanical deficiencies
of lining.
Plugging
Intercooler same as condenser, but possibly worse because no rubber ball
cleaning device available.
Pumps, pipes Erosion and erosion corrosion.
Mechanical wear and tear.
Cooling water basin If not controlled, a reservoir for sludge and fouling biology.
Danger by development of bacteria causing Legionaires disease
Impact by Biology
Biological The biological life forms are numerous and have ideal conditions for development
Potential of in the warm water flowing through a condenser. In hot climate countries the
Water biological growth is stimulated additionally by favourable temperatures. Nutrients
as a precondition for biological life is normally not a limiting factor because in
open cooling systems more than enough organic material is delivered by the make
up water. Cooling towers wash contaminants from the air that contributes also to
the organic inventory of the system.
Which biological The biological contamination can roughly classified as:

Life Forms? Macrofouling: by mussels, see weeds.
Microfouling: by bacteria, algae, fungi as yeasts or molds.

Water Chemistry
Impact by Biology (continued)
Macro Fouling Macro fouling can encrust entire surface areas beginning from the intakes and
traveling belt filters to the condenser chambers and tubes as well as other
components.
Some typical sea water macro fouling species are given by:
Blue mussels:
a world wide generic problem, colonize in thick clusters
Oysters
Barnacles
Encrusting bryozoa
Sea weed:
sometimes a mass phenomenon plugging completely intake filter systems
etc.
The species of the mollusks travel as tiny larvae and can pass filters.
This is the dangerous time period, in which a biocide program must mitigate the
beginning of the infestation. If once settled on suitable surfaces, they grow very
quickly.
Barnacles cement themselves within apprr. 20 minutes on a surface and a quick
shell formation gives them soon a protection against a hostile environment
(in appr. 20 h).
The spawning period of the blue mussel depends from temperature and local
conditions, but it occurs mainly in the spring.
Fresh water macro fouling species:
The following 2 types are of special interest because they are spreading now to
many countries.
Asian clam (Corbicula fluminea):
This species is difficult to remove. Once established, it literally clams up if the
water is conditioned with biocides.
Zebra mussels (Dreissena. polymorpha):
Forms dense thick layers of mussel accumulations

Water Chemistry
Impact by Biology (continued)
Micro Fouling The micro fouling is primarily given by the formation of bacterial slime and even if
this film is hardly visible it can reduce clearly the heat transfer in the cooling system.
The process of film formation starts normally with a surface that absorbs some
nutrients, and microbes are attracted. The result of this attachment process is the
formation of extra cellular debris and a certain reproduction rate of the different
species. Later, a secondary population of other bacteria or macro fouling forming
protozoa or shellfish may grow on top of the primary film. The rate of growth may
be exponentially increasing. Bacteria films even trap other sediments like sand and
silt. They work as kind of glue.
Yeasts and molds are troublesome because they like to settle on wood elements
and tend to degrade the material.
Most bacteria, yeast and mold need organic material for their metabolism, whereas
algae are photosynthetic microbes and need light for growth and reproduction.
Bacteria may prefer very different environments for living and reproducing. This has
to do with their specific metabolism. Some species live anaerobic (like the sulfate
reducing bacterias or the sulfide bacterias). They grow in sludge or in dead
microbial film, with their metabolism producing corrosive products.
Biocide Dosing
Process Rarely the temperature shock method is applied, which means lifting the
temperature of the intake lines and the condenser by about 10 C to kill (only) the
macro fouling.
More common is however the use of a dosing station by which chemical solutions in
the magnitude of 1ppm are injected into the water.
The mostly used biocide is chlorine, which is applicated
As chlorine gas (rarely, from safety reasons),
As hypochlorite solution with 10-12 % active chlorine (dosing station, normally
for cooling towers) or
As on site produced hypochlorite solution (sea water eloctrolysis, with appr.
0.1 % active chlorine)

Water Chemistry
Biocide Dosing (continued)
Chemicals A vast number of biocides is offered by chemical suppliers. Their application can be
successful or not, depending of the water conditions.
There are oxidizing and non-oxidizing biocides. A new type of biocide is based on
the film-forming character of a chemical that should prevent the macro fouling
species from cementing themselves on the surface.
The most used chemicals/methods are:
Chlorine, see above.
Chlorine-bromine mixtures.
Hydrogen peroxide.
Hydantoine derivatives.
Ozone.
UV light
The cleanliness in the cooling system resp. removal of biological products can be
improved by adding biodispersants.
Chlorine: The standard biocide is chlorine, as hypochlorite solution, either supplied as a

Alstoms chemical by trucks or produced by electrolysis on site.
Standard
Biocide
Chlorine Dosing Cooling towers are treated by shock dosing: 2 ppm, p.e. 4x per day 15 minutes.
Philosophy If the cooling system cannot be controlled by this level, it might be elevated
temporarily up to 5 ppm Cl.
Sea water is normally chlorinated continuously. This requires a much higher
chlorine consumption per day, although the level of chlorine applied is relatively
low. 0.2 ppm should be measured as a minimum at the condenser inlet.
The concentration can be easily measured by hand held instruments (photometer)
directly at the sampling point/site.
Control Apart from the routine analysis of the biocide, the best way to check for cleanliness
Philosophy is the inspection. If the condenser is shut down, or an intercooler or another heat
exchanger with cooling water contact is opened, these are the best occasions to
check for deposits.
Micro fouling/biological slime:
Can take some efficiency of the cooler. Optimizing biocide dosing, maybe
improvement of rubber ball cleaning device will help.
Macro fouling: may plug tubes partially or completely. The function of the
Component may be put in question. Immediate action is required:
shock dosing, mechanical cleaning.

Water Chemistry
Preservation
Atmospheric Corrosion
Steel Corrosion The atmospheric corrosion of steel is characterized by the following graph:
in Humid Air
0.4
Corrosion rate of carbon steel [g m-2 d-1]

0.3 Clean air
Air 0.01% SO2
Air 0.01% So2 + soot
0.2
0.1
0.0
0 25 50 75 100
Rel. humidity [%] CSXA403425.cdr
Figure 43: Steel Corrosion in Humid Air (Typical)
The corrosion rate is nearly zero below 40 % relative humidity. Clean surfaces of
steel remain clean for many years without any traces of rust.
The Corrosion is very slow below 55 % relative humidity. However, above 55 % the
relative humidity the corrosion increases considerately.
Even if there is a low concentration of gaseous contaminants in the atmosphere, we
observe a substantial increase of the corrosion rate.
This effect of gaseous contaminants is strengthened by particles such as soot.
As the corrosion rate is dependent on gaseous contaminants, it varies in various

areas:
Climate Corrosion Rate [mm a-1]

Rural 0.01 0.05
Urban 0.03 0.1
Sea 0.05 0.2
Industry 0.1 0.3

Water Chemistry
Dry Preservation
Introduction The corrosion rate depends on the relative humidity of the air.
By providing a dry atmosphere for the metal surfaces, atmospheric corrosion can
be prevented. This is called dry preservation.
Drying Agents Drying agents like silica gel can provide a dry atmosphere. These agents absorb
moisture from the air. As a rule of thumb they absorb 10 to 20 % of their own
weight in water.
Dry Air Blowers Preservation can also be completed by the continuous absorption of humidity by dry
air blowers. The working principle of dry air blowers is to absorb the humidity in the
air by means of a continuously working device. It blows the dry air into the
components that are to be protected.
Figure 44: Dry Air Blower (Munters) (Typical)
Instrument air can also be used if the humidity of this Air is low enough.
Nitrogen Corrosion can be prevented by providing a dry atmosphere of nitrogen to the

components. This is done by closing them with a slight overpressure of 0.1-0.3 bar.
Hot Draining Corrosion can be prevented by draining water filled systems as long as they are still
warm. This helps removing local wetness by evaporation. This draining procedure is
often combined with the filling of nitrogen and provides protection for long
standstills.

Water Chemistry
Dry Preservation (continued)
Warm Air Warm air blowers can also be used to lower the relative humidity and provide a dry
Blowers atmosphere. This process is however doubtful from the practical point of view:
In this process parts of components get exposed to sufficiently dried warm air, but
colder parts may be confronted with higher humidity or even condensation
Wet Preservation
General Besides dry conservation, internal atmospheric corrosion can also be prevented by
filling components with suitably conditioned water.
This is called wet preservation.
With wet preservation, corrosion of components can be prevented by raising the pH
value, by conditioning agents, adding oxygen scavengers such as hydrazine if
necessary and closing of the system. No contact with CO2, air or oxygen is allowed.
Components
General The following table shows the main actions for maintaining acceptable Lay up
conditions:
Component Short Outage Long Outage

Turbine Natural ventilation. Natural ventilation.
If turbine is dirty (salts) use dry air
blower.
Condenser Open manholes to get Open manholes to get natural ventilation
natural ventilation of air of air (Steam and water side)
(Steam and water side)
Piping Keep filled with water Keep filled with water.
Raise the pH value by ammonia injection
or add hydrazine.
Feed water Tank Keep filled with water Keep closed and filled with water.
Raise the pH value by ammonia injection
or add hydrazine.
Drain and provide natural ventilation.

Water Chemistry
Steam Turbine Protection
General For lay up of a turbine with contaminated surfaces, a mobile air dryer is used. The
blow out of the air should be sufficient to change the air volume of the turbine 1 to
2 times per hour.
The achieved relative humidity should be a least below 40 %
The preservation of the low-pressure turbine should be started within 48 hours after
shutdown.
The high pressure and the low-pressure parts of the turbine will be connected to the
air blower as soon as the temperature falls below 100 C.
Preservation Supervision
Supervision The following points show the important parameters to be supervised in steam
turbines:
Measure the relative humidity periodically (target value <40 %)
Check the oil and the hydraulic liquids for water content once every six months.
Operate the lube oil pumps and hydraulic oil pumps for at least a few hours
every 15 days.
Check the turbine areas accessible for visual and endoscopes inspections once
every 3 months.
Figure 45: Visual Inspection of Steam Turbine (Typical)
This type of preservation provides high safety against corrosion even for dirty
turbines for a long period. The requirement of manpower and investment for
equipment is also relatively low.

Water Chemistry
Condenser Lay-up
General In a condenser, the steam and water sides are exposed to different environments.
Thus, design, materials and surface protection are correspondingly different.
Water Side The water quality ranges from river water to seawater with different compositions of
salt content and amount of Suspended Solids. Remnants of this water or even
sludge can produce a very salty and aggressive surface film on tube sheets, around
rolled tube inlets and inside the tubes.
Figure 46: Condenser Water Side (Typical) Figure 47: Condenser Tube Sheet (Titanium)
(Typical)
The rubber limed water chamber surfaces however are normally completely
corrosion resistant and do not require special lay up considerations.
The type of water side preservation chosen is dependent upon the material the tube
is constructed from. ALSTOM Power gives specific instructions that are dependent
upon the material and water quality for the water side preservation.
A copper alloy tube condenser will be very sensitive for the correct lay up
procedure. Stainless steels are much more permissive.
Yet, both may be prone to pitting corrosion and other localized forms of corrosion.
Even titanium tube condensers require some care for lay up with respect to
minimize crevice corrosion between tube connections and the sheet.
Steam Side The steam is absolutely pure during operation and only light deposits of iron oxides
may be found in the condenser. If exposed to air, the low-alloyed steels will rust
only as long as the components concerned are wet.

Water Chemistry
General Supervision
Introduction
General For the supervision of the water/steam cycle, some parameters need to be checked
manually in the laboratory. Additionally it is important to double-check some
parameters from the online analyzer in the laboratory in order to ensure the correct
function of these analyzers.
The following table gives an indication of the Instruments used for the analysis of
the chemical parameters:
Instruments Parameter Instrument

Direct Conductivity Online analyzer.
Portable conductivity meter.
Laboratory Conductivity Meter.
Cation Conductivity Online analyzer.
pH Online analyzer.
Portable pH meter.
Laboratory pH Meter.
Iron Spectrophotometer (DR2000)
Filtration Equipment (Millipore)
Sodium Online analyzer (optional)
pH Meter with Sodium Electrode.
Oxygen Online analyzer.
Silica Online analyzer (optional)
Spectrophotometer (DR2000)
Phosphate Spectrophotometer (DR2000)
Hydrazine Online analyzer (optional)
Spectrophotometer (DR2000)

Water Chemistry
Conductivity Meter
General Apart from the online analyzers it is also possible to check the direct conductivity in
the laboratory. However for ultra pure water it is nearly impossible to take a grab
sample and analyze it in the laboratory without contamination. It is better to use a
portable conductivity meter in order to check the conductivity at the sample point
with a flow through cell.
Conductivity
Instruments
Figure 48: Laboratory Conductivity Meter (Typical) Figure 49: Portable Conductivity Meter
(Typical)

Water Chemistry
pH Meter
General The pH can be checked in the laboratory as well as with the online instruments. If
the pH is checked using a grab sample, special care must be taken with the
sampling procedure:
The sampling bottle needs to be filled completely with water and closed
immediately. This should prevent the contamination of the sample water with
carbon dioxide from the air, causing the pH to drop.
pH Instruments
Figure 50: Laboratory pH Meter (Typical) Figure 51: Portable pH Meter

(Typical)

Water Chemistry
Spectrophotometer
General The spectrophotometer is one of the most important instruments in the laboratory:
Several different chemical parameters can be checked using this instrument in
combination with special chemicals.
Spectro-
photometer
Figure 52: Spectrophotometer (Typical)

Water Chemistry
Spectrophotometer (continued)
Example The following drawing shows as an example the method for the analysis of
phosphate in water.
PHOSPHORUS, REACTIVE (0 to 30.00 mg/L PO4 )

3-
For water, wastewater, seawater
(Also called: orthophosphate) amino acid method*
1. 2. 3. 4.
Enter one of the following Rotate the wavelength dial Press: READ/ENTER Fill a 25-mL mixing
stored program numbers for until the small display shows: graduated cylinder with
the reactive phosphorus, 530nm The display will show: 25 mL of sample.
3-
amino acid method. mg/1 PO4 AA
or
Press: 4 8 5 READ/ENTER mg/1 P AA
3-
for units of mg/L PO4 OR
4 8 6 READ/ENTER for units
of mg/L P
The display will show:

DIAL nm TO 530
5. 6. 7. 8.
Add 1 mL of molybdate Add 1 mL of amino acid Press: SHIFT TIMER Pour 25 mL of sample
reagent using a 1-mL reagent solution. (the blank) into a sample
calibrated dropper. Stopper and invert several A ten-minute reaction period cell.
times to dissolve will begin.
(the prepared sample).
9. 10. 11. 12.

When the timer beeps, the Press: ZERO Pour the prepared sample Press: READ/ENTER
display will show: into a sample cell.
3-
mg/1 PO4 AA The display will show: Place the prepared sample The display will show:
or WAIT into the cell holder. Close the WAIT
mg/1 P AA then: light shield. then the result in mg/L
3-
0.00 mg/1 PO43- AA PO4 or mg/L P will be
Place the blank into the cell or displayed.
holder. Close the light shield. 0.00 mg/1 P AA
CSXA403435.cdr
Figure 53: Example of Phosphate Testing (Typical)

Water Chemistry
Importance of Chemical Parameters
Introduction Some chemical parameters are more important for the supervision of the water
chemistry in a power plant than others. The following points provide some
guidelines for the interpretation of chemical results.
Acid Conductivity The cation exchanger takes up the ammonia (which reacts as cation), but the
Cation contaminants pass the cation exchanger. The level of these contaminants is very
Conductivity small compared to ammonia. After the removal of ammonia, these contaminants
can be measured separately and easily.
Too high conductivity after cation exchanger means:
To many contaminants in steam/feed water/condensate. These contaminants
can be corrosive in the steam water cycle, especially in the turbine.
Very critical: The blades can crack if the contaminants are traces of acids that
condense with the first steam ("early condensate") in the turbine.
The turbine might not only suffer corrosion, but might get deposits that lower the
efficiency of the plant.
The Conductivity after cation exchanger is the most important parameter for
supervision because it shows immediately if the water chemistry is normal or not
and if actions are necessary or not.
pH Feed water, Condensate, Steam (Target pH 9...9.6)

The pH is given by ammonia. It is not important if the pH is higher as steel and
titanium (condenser tubes) can cope with higher pH values. Many power stations
are operating successfully with the pH range 9...9.6. Some apply pH 10.
Higher pH values mean higher costs and a larger environmental impact (more
ammonia in the wastewater), which is senseless. But it is not detrimental unless
copper materials are used.
Lower pH is not recommended, because of the missing alkaline effect in the
condensing steam.
Boiler water (Target pH 9.1...9.6)
Higher values are not acceptable, because the boiler can suffer from caustic
embrittlement corrosion.
Lower pH values give not enough protection against corrosion.

Water Chemistry
Importance of Chemical Parameters (continued)
Iron, Fe Iron is present as iron oxide in the water and steam. If the level is too high, the
water chemistry is not optimized. With good water chemistry, iron oxides are
present only in traces
(<20 g kg-1) in water and steam.
Too much iron has a detrimental effect in the feed water:
Formation of deposits can occur inside the boiler. This is not good for the
necessary heat transfer. Conditions for corrosion might develop. Local
overheating might also damage pipes.
Too much iron has a detrimental effect in the steam:
Formation of deposits can occur on the blades. This might increase the pressure
drop and lower the turbine efficiency.
Sodium, Na Sodium is limited in the steam only.

If the level is too high, the turbine develops corrosive deposits. Cracks might
develope on the blading or on the casing. The blade roots may also corrode.
The blades are especially endangered due to high stress caused by the rotating
speed.
Silica, SiO2 Silica is not corrosive.

Silica is limited inside the water/steam cycle:
If the level is too high, deposits form on the turbine that lower the efficiency.
Silica is limited in the boiler:
This keeps the steam clean, as silica is partially volatile under the boiler
conditions. If there is too much silica in the boiler, too much silica evaporates
into the steam. When the steam passes through the turbine and loses
temperature and pressure, silica is again deposited.
Oxygen, O2 Too high oxygen level in the feed water (oxygen is specified only in the feed water)
may enhance corrosion in the economizer of the boiler.
Oxygen in clean feed water is not so critical as formerly stated. In the contrary, a
moderate level of oxygen (up to >100 g kg-1) contributes to the formation of a
protecting iron oxide layer in the steam water cycle. This is true for clean feed water.
So, one should only worry about oxygen if the level is constantly too high and the
feed water is dirty.
Copper, Cu This parameter is only important if some heat exchangers contain copper.
Otherwise, copper can only enter the steam/water cycle with dirty make-up/return
condensate.
If the level is too high, the boiler suffers from corrosion (corrosion under deposits).

Water Chemistry
Trend-lines
Introduction For the supervision of the water chemistry it is often important to know the history of
the observed parameter. Therefore, all of the continuous monitors have signal
outputs to the main control room. The parameters are recorded and can be viewed
in order to observe changes in time.
Figure 54: Main Control Room (Typical)
Example
Figure 55: Trend of different Chemical Parameters During Start-up (Typical)

Water Chemistry
Troubleshooting
Introduction If the chemical parameters are outside of the defined limits, the following tables
give some indication as to possible reasons for it:
Steam Effect Reason Action

Acid conductivity too Boiler has too high carry- Increase boiler blow down
high over, is eventually foaming.
See "boiler"
Decomposition of organics Eliminate source of organics
produce volatile acids
Air inleakages into Eliminate air inleakage
condenser. O2 level in
condensate high, carbon
dioxide of air circulates in
loop
Make-up water picks up too Install CO2-trap at atmosphere.
much carbon dioxide in opening of storage tank
storage tank by too
intensive mixing with air
Feed water purity is low, Check feed water
and continuous injection
lowers steam quality
Raw conductivity too Dosing of ammonia too high Check pH, should be too high
high (feed water conductivity is decrease dosing of ammonia
as well too high)
Condensate Effect Reason Action

Acid conductivity too Steam impure Check HP- and LP- steam. See
high "Steam"
Cooling water inleakage Reduce load to find that
conductivity increases. Check in
lab chloride content in boiler.
Prepare reparation
Oxygen too high Inleakage of air Find leaks (mostly suction side
condense. pumps in water)
Orifice in deaerator too Enlarge orifice
small or plugged

Water Chemistry
Troubleshooting (continued)
Feed Water Effect Reason Action

Acid conductivity too Make-up water impure Check demineralization plant
high
Condensate impure See "Condensate"
Low pressure boiler has too Check LP boiler conductivity at
high carry over. boiler sampling panel, check LP-
Conductivity in low pressure steam.
boiler too high/pH too high. Increase LP-blow down
LP- steam contaminates
feed water .
Boiler Effect Reason Action

pH too low Dosing of phosphate Check phosphate pumps
insufficient Overflow valve opens too early
Solution in tank too diluted
Wrong chemical: Tri-sodium-
phosphate is correct
Acidic feed/make-up water. Check pH
Chemical accident
Too many organics in boiler Check "COD" in lab
pH too high Temp. Dosing of phosphate too Check phosphate in lab
drops eventually in high. Foaming of boiler Open blow downs to decrease
Steam possible
danger of caustic embrittlement in
boiler
Solution in tank too concentrated.
Dilute
Conductivity too high See above "pH too high"
Blow down(s) closed Adjust blow down
Feed water contaminated Check condensate and make-up
by Condensate: Cooling (see there)
water inleakage
General Effect Reason Action

One acid conductivity Harmless. The one cation Replace resin. Be prepared so
too high, steadily resin of sampling panel is every month per column.
increasing over hours. being exhausted. If resin
All other readings nor- with indicator is used,
mal. exhaustion is visible at
colour change

Water Chemistry
Summary
General Dissolved or undissolved substances (salts) in water can lead to corrosion and the
formation of deposits in the water / steam cycle of a power - plant. That is why the
purity and the chemical conditioning of the water is imperative for the efficient and
effective operation of a plant.
Prevention of In order to prevent damages caused by corrosion and the formation of deposits, the
Damages following points should be fulfilled.
The water/steam cycle water must be clean.
The water of the must be conditioned i.e. particular chemical substances should
be mixed/added.
The water/steam cycle should be maintained.
Dosing System The conditioning of the water with ammonia and phosphate is completed by the
dosing system, which is operated either automatically or manually.
Measurements The water is checked with the help of monitors, which carry out the water - tests
automatically and which examine them for particular values. This continuous
maintenance / checking is done manually.

Water Chemistry
Annexs
Annex 01: Units of Water Chemistry
Concentrations
1 mg/kg = 1 ppm
1 g/kg = 1 ppb
1mg/kg = 1 mg/l
1 g/kg = 1 g/l
1 meq/l = 1 mmol/l = 50 ppm as CaCO3
1 meq/l = 2.8 dH = 5 fH
Conductivity
1 S/cm = 1 MHO/cm
1 S/cm = 100 S/m
Examples
Atomic weight Na = 23
Cl = 35.5
200 ppm NaCl 78 ppm Na

122 ppm Cl
3.4 meq/l Na
3.4 meq/l Cl
170 ppm Na as CaCO3

170 ppm Cl as CaCO3

Water Chemistry
Annex 02: Conductivity of Pure Water
Ion product of Water
H2O H+ + OH -
Kw = (H+) x (OH -) = 10 14
Temperature and Conductivity
T C C S/cm
___________________________________________________________________________
0 0.016
10 0.029
25 0.055
35 0.090
Specification of steam purity is 0.2 S/cm
Correlation impurities - conductivity
0.016 ppm HCl 0.2 S/cm
0.021 ppm H2SO4 0.2 S/cm
0.030 ppm Acetic acid 0.2 S/cm
1 ppm NaCl 2 S/cm

Water Chemistry
Annex 03: Types of Chemical Boiler Water Treatment
CHEMICAL TREATMENTS
ALCALINE TREATMENT
DRUM BOILER
Feedwater:
PH 9.0 9.6
Oxygen <10 ppb
Conductivity after cation exchanger < 0.2 S/cm
Dosing of ammonia (volatile) for alcalizing W/S cycle

Dosing of scavenger (volatile) to minimize oxygen ( project specific)
Dosing of phosphate (solid) for alcalizing boiler
OXYGENATED TREATMENT
ONCE THROUGH BOILER
Feedwater:
PH 8.0 9.0 special case ALSTOM ICS 9.0 9.60

Oxygen 50 150 ppb

Dosing of oxygen (volatile) for lowering corrosion by optimizing protection layer
ALL VOLATILE TREATMENT

ONCE THROUGH BOILER AND DRUM BOILER
Feedwater:
PH 9.0 9.6
Oxygen <10 ppb

Dosing of scavenger (volatile) to minimize oxygen ( project specific)
NO SOLIDS (PHOSPHATE) DOSING INTO THE BOILER DRUM

Water Chemistry
Annex 04: Magnetite Solubility / Thickness of Protective Layer
90 Ippm NH3
80
70
60
Magnetite (ppb Fe2)

50
40
30
20
10
0
0 50 100 150 200 250 300 350 (C)
32 122 212 302 392 482 572 662 (F)
Temperature
CSXA403438.cdr
Figure 56: Magnetite Solubility (Typical)
Magnetite solubility in water as a function of temperature and PH value.
m m
15.0
12.5
10.0
7.5
5.0
2.5
0
I t in h
2000 4000 6000 8000
CSXA403439.cdr
Figure 57: Thickness of Protective Layer (Typical)
Dependence of growth of Fe3 O4 layer (D) from operation time.

Dependence of corrosion release rate from operation time (K).

Water Chemistry
Annex 05: Sacrificing Anodes
Sacrificing UWK
Anodes AmV
-100
Cl2: 4h, 0,5mg/l
(residual)
- 200
- 300
d
- 400
150 155 160 164
CSXA402750.cdr
Figure 58: Example of Efficiency Decrease (Typical)
If there is no chlorination, the anodes are gradually covered by biological material.

This has some isolation effect, and the (wanted) corrosion of the anodes is
impaired.

Water Chemistry
Annex 06: Expansion Curves of Steam Turbines
ENTROPIE / ENTROPY [s] = kJ/kg K

6.0 6.5 7.0 7.5 8.0 8.5
3800 3800
Expansion curves of 4 different turbines

3700 3700
3600 3600
3500 3500
3400
Without RH 3400
RH-supercrit.
3300 3300
3200 3200
3100 3100
3000 3000
2900 2900
2800 2800
2700 PWR 2700

Satur
ation
2600
line 2600
2500 2500
Wilso
n line
2400 MAGNOX 2400
2300 2300
2200 2200
2100 2100
2000 2000
6.0 6.5 7.0 7.5 8.0 8.5
ENTROPIE / ENTROPY [s] = kJ/kg K
CSXA403440.cdr
Figure 59: Expansion Curves of Steam of 4 Different Turbines (Typical)

Water Chemistry
Annex 07: Description Ammonia/Hydrazine Dosing System
Description and function of equipment

Storage and dilution tank
If the level in storage tank 28LFN20 BB002 or 28LFN40 BB002 drops below < MIN1 (CL002),
new dosing medium must be prepared.
Both chemicals will be supplied in a concentration which is higher than that required for dosing.
The solution will be prepared by adding a predetermined amount of dematerialized water
into the storage tank.
The level gauge on the storage tank shall be used as a filling control device. A solenoid valve is installed
to fill the tank with dematerialized water. The valve can be opened and closed locally on the panel.
To prevent an overfilling of the tank the solenoid valve closes automatically at high level MAX1 (CL004)
and interrupts the dematerialized water supply.
Also the barrel pump is switched off.
After the water has been added, the required amount of Ammonia or Hydrazine will be added with the
corresponding feed pump to the dilution tank (see annex 8 concentrated storage and dosing).
After the required amount of chemical has been added, the stirrer can be operated briefly for approx.
15 - 60 seconds to mix the contents of the tank. After this mixing the stirrer should be switched off because
continued stirring would only produce further vapors which would unnecessarily be absorbed by
the vent filter.
The level gauge is used to indicate the level of the tank content as well as to determine the delivery rate of
the dosing pumps. The level measurement positions can be manually adjusted.
The level gauge has 2 scales. One shows the content of the tank in m3 and the other shows the volume of
standpipe. Second can be used for determining the delivery rate of the pumps.
Dosing pump operation and status indication
2 x 100 % (duty and standby) dosing pump are installed for each HP boiler of HRSG 1, 2 and 3.
The output is adjustable by stroke length.
Ammonia
The stroke length of the dosing pumps is adjusted manually.
The stroke length should only be adjusted while the pump is in service.
Hydrazine
The stroke length of the dosing pumps is adjusted by an stroke positioning system. The stroke length can
be adjusted by a signal 4 -20 mA from the main control room or local on the control panel.
The stroke length should only be adjusted while the pump is in service. A key switch (Local/Remote-mode
selector switch) is available to select the operating mode. On Remote mode, the system and the duty
pump (pump selected and released by internal timer for change over) can be switched on and off from the
control room by means of a COMMAND ON pulse signal. On local mode the dosing pumps can be
started manually.
A changeover of the dosing pumps is achieved by a timer in the control cabinet. This timer ensures that
each
of the 2 x 100 % pumps is in operation from time to time. In case of a duty pump failure an auto change
over will suddenly bring the stand by pump in operation.
For maintenance the current circuit breaker of the corresponding dosing pump must be switched off.
In that case the change over initialized by the integrated timer in the control cabinet is not activated.
The second pump will run until the dosing pump is put back into operation by switch on by the pump
circuit breaker.
Drawing number 7071-SD01 19.02.02 page 5/16

Water Chemistry
Annex 07: Description Ammonia/Hydrazine Dosing System (continued)
Reagent low low level

In the Remote mode the pump will not operate if the tank level is <MIN2 (low low level).
Local mode
If the key switch is set to Local, the pumps can be taken into operation locally.
If the local mode is selected, the pumps will not recognize an ON/OFF signal pulse sent from the main
control room. Separate Stop/Start push buttons are provided for the purpose of operating the pumps.
Indicators and electrical equipment

See also Signal and Flow Diagram 280-7071-93729- E/S-01-02
Motors
Run and Trip lamps are provided on the control console for the dosing pumps and the stirrers.
No volt run contacts are provided.
From each pump an ON and OFF signal is sent to the main control room.
Mains on
A panel lamp and no-volt contact are provided for panel on indication.
Reagent low level

A reagent lamp and a no volt contact are provided for the below <MIN1 (low level; refill) condition.

A local lamp is provided for the <MIN2 (low low level) condition, which will also shut down
the dosing pumps.
A no volt contact is provided to the main control for dosing system disturbed.
Common system alarm

A common system alarm will be given when the level drops below the <MIN2 (low low level), or if any of
the dosing pumps indicates a power or trip failure.
The alarm will be forwarded to the main control room and processed in the main control panel.
The system alarm remains active until the failure is remedied.

Water Chemistry
Annex 08: Description Ammonia/Hydrazine Storage System

Description and function of the equipment
Concentrated Storage tank
If the level in storage tank 28QCE10 BB001 or 28QCE20 BB001 drops below < min 1 (CL002),
new dosing medium must be added.
Both chemicals will be supplied in containers. The container will be placed on a platform above the
concentrated storage tanks. The container will be connected with the filling line (flex. hose with Camlock
Connector 1 ) to the storage tank. If possible a second line (gas compensation line) should be
connected on top of the container and opened (28QCE10 / 28QCE20 AA250)
On the control panel in the dosing container the pneumatic valve (28QCE10 / 28QCE20 AA050) must be
opened manually. The chemicals run into the storage tank until the container is empty. If the level in
storage tank (>max 1 or overfilled) is reached the pneumatic valve will close immediately.
After a certain time the release for the pneumatic valve (open) will be canceled and the valve must be
opened on the panel again.
Two feed (dosing) pumps are installed to transfer the concentrated chemicals into the dilution tank.
To fill the system two suction side pulsation damper are installed.
This pulsation dampers serve as a suction side pulsation damper, to fill the suction line as well to
determine the delivery rate. (see section: Dosing pump operation and status indication) Until the feed
pump is working properly and the suction line is bled, the chemical can be pumped back to the
concentrated storage tank.
The amount of chemicals fed to the dilution tanks will be controlled by counting the number of strokes. For
the determination of the delivery rate a defined amount of chemical is pumped from the suction vessel to
the dilution tank or back to the concentrated storage tank. The strokes are shown on the panel. To
determine the total delivery of the feed pump which is necessary the total strokes are calculated. On the
panel the strokes can be set on a counter. After starting the pump, a second counter shows the actual
number strokes.

Water Chemistry
Annex 08: Description Ammonia/Hydrazine Storage (continued)

The dosing pumps can also serve to feed the opposite chemical into the other dosing tank.
(Ammonia Feed pump from Hydrazine storage tank to Hydrazine dosing tank)
For each chemical one feed (dosing) pump is installed. The output being adjustable manually by stroke
length.
A key switch is incorporated for each feed (dosing) pump on the local panel in the container.
Beside the concentrated feed pumps a small local panel is installed with the push bottoms for each as well
as an Emergency switch off.
The key switches on the Panel in the container have the following positions:
0 = Off
Local = The feed pumps can be started and stopped on the small panel
in the concentrated chemical feed compartment.
Delivery rate = Determination of the delivery rate
The feed pumps will be started and stopped on the panel
in the concentrated chemical feed compartment.
A third push button is installed to reset the counter to zero
when the level passes the upper marking on the suction vessel
At the lower level the pump is switched off.
Automatic = The pump will deliver the amount according the counter after a
manual start on the panel in the container.

See also Signal and Flow Diagram 280-7071-93729- E/S-01-02
Motors
Run and Trip lamps are provided on the control console for the feed (dosing) pumps.
Reagent low level
A reagent lamp and a no volt contact are provided for the below <min 1 (low level; refill) condition.
Reagent high, low low level and overfilled
A Local lamp is provided for the:
MIN2 (low low level)
MAX1 (high level)
MAX2 (overfilled)
Common system alarm
Only one common system alarm is given for the whole system (Dosing and concentrated storage part)

Water Chemistry
Annex 09: Control Philosophy Ammonia/Hydrazine Dosing
Ammonia Dosing System

Description of the Control System
The systems shall be ready for automatic operation if the mode selector switch (on the local control panel)
is on remote. In this case the system shall be able to be started/stopped from the main control room by
the signals CMD ON / CMD OFF.
The CMD ON / CMD OFF signals depends on:
One condensate pump on (28LCB10AP001 or 28LCB20AP001)

Condensate discharge control valve >10 % open (28LCA30 AA002)
Actual conductivity value of feed water (28QUL40CQ011)
This conditions are only relevant for the DCS (Distributed Control Systems).
If the mode selector switch (KSW) is on local, the selected pumps shall be able to be started manually
from the local control panel.
KSW ammonia NOT REMOTE shall give a signal to the DCS.
In three cases incidents low low level alarm, motor failure or power failure shall provide a common
system alarm DISTURBED to the main control system DCS. The low low level alarm (indicated only
locally) shall switch off the pumps.
Low level-, low low level- and high level- alarms and switches shall be marked on the terminal list
and connection diagram as level < MIN 1, level < MIN 2 and level > MAX 1 so that the marking
corresponds with the ALSTOM-Signal list.
The alarm signal low level (level < MIN 1) shall also go to the DCS.
One (1) pump shall be considered as a standby pump and one as a duty pump. One injection pump is
normally in operation. If the duty pump breaks, the standby pump shall replace the failed pump by an
automatic change over. If the standby pump once is in operation it shall be under the influence of the
CMD ON / CMD OFF signals. In the manual/local mode it shall be possible to have both pumps
simultaneously in operation. A programmable timer installed in the electrical panel shall allow that each
pump is frequently in service.
The CMD ON / CMD OFF signals (one shot) will start and stop the dosing pump (28LFN21AP001 or
28LFN22AP001).
From the dosing unit two signals SYSTEM ON and SYSTEM OFF shall be generated. SYSTEM ON
actually indicates that one dosing pump is running. It includes automatically power on for the dosing
system and tank level is not < MIN2 (low low level). These signals shall be forwarded to the DCS to
provide information concerning the status of the system.
From each dosing pump the signal PUMP ON shall be generated. This signal shall be forwarded to the
DCS to provide information concerning the status of the pumps.
The injection rate of the pumps shall be adjusted/corrected manually.
A green lamp shall indicate RELEASE (one condensate pump on) for dosing into the condensate line
pump discharge or into the feed water tank.

Water Chemistry
Annex 09: Control Philosophy Ammonia/Hydrazine Dosing (continued)
Additional requirements regarding bulk container:

The bulk tank shall be equipped with a supersonic level indicator including following information:
High-level, low level and low low level.
High-level, low level and low low level alarm, shall be marked on the Terminal list and connection
diagram as level >MAX1, level < MIN 1and level < MIN 2, so that the marking corresponds with
the ALSTOM-signal list.
The alarm signal low level (level < MIN 1) shall also go to the DCS.
An overfilling supervision (level > MAX2) e.g. Vaga swing type shall be provided.
For a certain redundancy high level (level >MAX1) and overfilling indication (level > MAX2) shall close the
respective pneumatic filling valve between IBC container and bulk container.
The "overfilling" alarm indication (level > MAX2) as well as the "low low level alarm (level < MIN 2) shall
be part of the common system alarm DISTURBED.
Further over filling (level > MAX2) shall provide an acoustic alarm and initiate a flushing light.
After recognition it should be possible to mute the acoustic alarm by a push-button.
Hydrazine Dosing System
As per Ammonia Dosing
Exception:
One condensate pump on (28LCB10AP001 or 28LCB20AP001)
Condensate discharge control valve >10 % open (28LCA30 AA002)
No automatic operation with controlling device. Manual on/off from DCS for special cases is required.
The injection rate shall be automatic flow controlled via a 4 20 mA signal of the condensate flow
(28LCB20CF051). This signal will be sent to the skid mounted p-controller which adjusts the pump stroke.

Water Chemistry
Annex 10: Description Phosphate Dosing System
Description and function of equipment
Storage- and dilution-tank

If the level in storage tank 29LFN01 BB001 drops below MIN1 (CL002), new dosing medium must be
prepared.
Phosphate will be supplied in solid form (powder) for preparation of a solution in the mixing/dosing tank.
The solution will be prepared by adding a predetermined amount of demineralised water into the storage
tank. The level gauge on the storage tank shall be used as a filling control device. After a certain amount
of phosphate powder shall be added into the tank basket. Then the stirrer will be started and run for
approximately 15 minutes, or for a sufficient time to ensure a complete dissolving of the powder. The
mixing time can be adjusted on the timer in the local control panel. Finally the storage tank can be filled
up to the top of the storage tank. A solenoid valve is installed to fill the tank with demineralised water.
The valve can be opened and closed locally on the panel. To prevent an overfilling of the tank the
solenoid valve closes automatically at high level MAX1 (CL004) and interrupts the demineralised water
supply.
During the dissolving operation no dosing should take place and the outlet isolation valve of the tank
should be closed. Otherwise solid material can flow into the dosing lines.
The level gauge is used to indicate the level of the tank content as well as to determine the delivery rate of
the dosing pumps. The level measurement positions can be manually adjusted.
The level gauge has 2 scales. One shows the content of the tank in m3 and the other shows the volume of
standpipe. Second can be used for determining the delivery rate of the pumps.

2 x 100 % (duty and standby) dosing pump are installed for each HP boiler of HRSG 1, 2 and 3.
The output is adjustable by stroke length.
The stroke length of the dosing pumps is adjusted manually at the pump.
A key switch (Local/Remote-mode selector switch) is available to select the operating mode. On Remote
mode, the system and the duty pump (pump selected and released by internal timer for change over)
can be switched on and off from the control room by means of a COMMAND ON pulse signal.
On local mode the dosing pumps can be started manually.
A changeover of the dosing pumps is achieved by a timer in the control cabinet. This timer ensures that
each of the 2 x 100 % pumps is in operation from time to time. In case of a duty pump failure an auto
change over will suddenly bring the stand by pump in operation.
For maintenance the current circuit breaker of the corresponding dosing pump must be switched off.
In that case the change over initialized by the integrated timer in the control cabinet is not activated. The
second pump will run until the dosing pump is put back into operation by switch on by the pump circuit
breaker.

Water Chemistry
Annex 10: Description Phosphate Dosing System (continued)

In the Remote mode the pumps will not operate if the tank level is <MIN2 (low low level).
Local mode
If the key switch is set to Local, the pumps can be taken into operation locally.
If the local mode is selected, the pumps will not recognize an ON/OFF signal pulse sent from the main
control room. Separate Stop/Start push buttons are provided for the purpose of operating the pumps.
See also Signal and Flow diagram E/S-02
Mains on
A panel lamp and no-volt contact is provided for panel on indication.
Motors
Run and trip lamps are provided on the control console for the dosing pumps and the stirrer.
From each pump an ON and OFF signal is sent to the main control room.
Reagent low level
A reagent lamp and a no volt contact are provided for the below <MIN1 (low level; refill) condition.
A local lamp is provided for the <MIN2 (low low level) condition, which will also shut down the dosing
pumps.
A no volt contact is provided to the main control for dosing system disturbed.
Common system alarm
A common system alarm will be given when the level drops below the <MIN2 (low low level), or if any of
the dosing pumps indicates a power or trip failure.
The alarm will be forwarded to the main control room and processed in the main control panel.
The system alarm remains active until the failure is remedied.

Water Chemistry
Annex 11: Control Philosophy Phosphate Dosing
Trisodium Phosphate Dosing System

The systems shall be ready for automatic operation if the mode selector switch (on the local control panel)
is on remote. In this case the system shall be able to be started/stopped from the main control room by
the signals CMD ON / CMD OFF Each boiler-drum gets his own CMD ON- resp.CMD OFF-signal.
GT flame on (21CJB20EU910)
Circulation pump on (if circulation pump available for forced circulation)
Continuous blow down valve open (21LCQ21/41/61AA001)
Wheel chamber pressure > MIN (10 %)
Actual pH value of the blow down water (21QUL01/03/05CQ031)
A combination of the above conditions depending on the type of HRSG will be used.
If the mode selector switch (KSW) is on local, the selected pumps shall be able to be started manually
from the local control panel. KSW tri-sodium-phosphate NOT REMOTE shall give a signal to the DCS.
One KSW for each boiler-drum is necessary.
In three cases incidents low low level alarm, motor failure or power failure shall provide a common
system alarm DISTURBED to the main control system DCS. The low low level alarm (indicated only
locally) shall switch off the pumps.
Low level-, low low level- and high level- alarms and switches shall be marked on the terminal list
and connection diagram as level < MIN 1, level < MIN 2 and level > MAX 1 so that the marking
corresponds with the ALSTOM-Signal list. The alarm signal low level (level < MIN 1) shall also go to the
DCS.
One (1) pump of each of the three sets shall be considered as a standby pump and one as a duty pump.
One injection pump is normally in operation. If the duty pump breaks, the standby pump shall replace the
failed pump by an automatic change over. If the standby pump once is in operation it shall be under the
influence of the CMD ON / CMD OFF signals. In the manual/local mode it shall be possible to have
both pumps simultaneously in operation. A programmable timer installed in the electrical panel shall
allow that each pump is frequently in service.
The CMD ON / CMD OFF signals (one shot) will start and stop the dosing pump
(21LFN51AP001 or 21LFN52AP001).
From each dosing unit (autonomous dosing system for each boiler drum) two signals SYSTEM ON and
SYSTEM OFF shall be generated. SYSTEM ON actually indicates that one dosing pump is running. It
includes automatically power on for the dosing system and tank level is not < MIN2 (low low level). These
signals shall be forwarded to the DCS to provide information concerning the status of the system.
From each dosing pump the signal PUMP ON shall be generated. This signal shall be forwarded to the
DCS to provide information concerning the status of the pumps.
The injection rate of the pumps shall be adjusted/corrected manually.
A green lamp shall indicate RELEASE (GT flame on and/or circulation pump on, if circulation pump
available for forced circulation) or wheel chamber pressure > MIN (10 %) for dosing into the boiler-drum.


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Steam Turbines Water Chemistry

ALSTOM (Switzerland) Ltd ABCD

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(Continued next page)

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Table of Contents (continued)

Figure 1: Causes of Infringement of Function on Turbines (Typical) ....................................................... 7

(Continued next page)

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Table of Figures (continued)

Figure 22: Ammonia & Hydrazine Dosing System (Typical) ................................................................. 32

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Upon completion of this section, the trainee should be able to:

Name the measures that should be undertaken in order to prevent damage of

Understand the function of the chemical dosing and sampling systems.

Understand the safety devices and handle them correctly.

Interpret the test readings.

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Introduction to Water Chemistry

Figure 1: Causes of Infringement of Function on Turbines (Typical)

A study on turbines at US plants shows the main causes of infringed functioning:

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(Continued next page)

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Treatment, Purification (continued)

Parameter Unit Nominal Value

(Continued next page)

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(Continued next page)

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Steam Turbine Requirements

Parameter Unit Normal operation Start-up

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Protective Layer on Steel in W/S Cycle

(Continued next page)

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Protective Layer on Steel in W/S Cycle (continued)

Fluid boundary layer Fe(OH)+ OH- H2

Figure 2: Oxides formed with Deoxygenated Treatment (Typical)

Fluid boundary layer

Metal Fe3O4 iy-FeOOH or a-Fe2O3

Figure 3: Oxides formed with Oxygenated Treatment (Typical)

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Problem In industrialized nations, a cost of approximately 3 to 4 % of the gross national

Interaction Corrosion processes are influenced by interactions:

Stress reversal Material

Figure 4: Influence on the Corrosion Process by Various Interactions (Typical)

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The most Type of Causes Occurrence

(Continued next page)

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Types of Corrosion (continued)

Aggressive contaminant deposits, e.g.:

n NaOH deposits on stellite valve spindles

n NaOH deposits on welding/welded joints in drain pipes

High contamination/concentration, e.g.:

n Chloride on turbine blades

n Erosion, caused due to high flow rate

Figure 5: Corrosion of Turbine Parts (Typical)

(Continued next page)

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Types of Corrosion (continued)