WHY PURIFY?

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Contents
1.1 Why Purify ............................................................................................................................ 2
1.1.1 Overview ...................................................................................................................... 2

1.2 Basic Heat Transfer Theory ................................................................................................ 4

1.2.1 Modes of Transfer ...................................................................................................... 4
1.2.2 Conductance and Resistance.................................................................................... 4
1.2.3 Applications in Heat Transfer ................................................................................. 5

1.3 Phase Changes ...................................................................................................................... 6

1.4 Deposition and Scaling ...................................................................................................... 9

1.4.1 Scale .............................................................................................................................. 9
1.4.2 Effects of Scale ............................................................................................................ 9
1.4.3 Hideout....................................................................................................................... 12
1.4.4 Control Methods ...................................................................................................... 13

1.5 Corrosion ............................................................................................................................. 14

1.5.1 Fundamentals ............................................................................................................ 14
1.5.2 Effects ......................................................................................................................... 15
1.5.3 Control Methods ...................................................................................................... 15

1.6 Vaporous Carryover ........................................................................................................... 16

1.6.1 Mechanical Carryover ............................................................................................. 16
1.6.2 Chemical Carryover ................................................................................................. 17
1.6.3 Attemperation ........................................................................................................... 17
1.6.4 Results of Carryover ................................................................................................ 18

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 Module 1
WHY PURIFY?
1.1 Why Purify

Water used as a makeup source for steam generators (boilers) must be highly
purified. This protects the steam generator piping and equipment, such as turbines,
from scaling and corrosion caused by impurities. Turbines convert steam energy into
mechanical energy, which then drives electrical generators. Figure 1.1-1 below
shows a turbine with its covers removed and the turbine blades exposed. The
required purity of the makeup water for a steam generator depends on operating
conditions within the boiler, such as:

• operating pressure
• cycles of concentration
• mechanical and vaporous carryover
• chemical treatment within the boiler and steam cycle
courtesy of Siemens

Figure 1.1-1: Turbine with Blades Exposed

Figure 1.1-2: Water
Treatment Equipment
1.1.1 Overview

A purification system that is used to treat makeup water must be designed to purify
the water to the degree required by the steam generation system with which it is
used. Figure 1.1-2 above shows part of a water treatment system. The use of
improperly purified makeup water causes potentially costly and hazardous damage
to steam generator piping and equipment. Impurities in the makeup water of a
steam generator can cause damage through many mechanisms, including deposits,
corrosion cells, and stress corrosion cracking (SCC).

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 Suspended and dissolved contaminants in makeup water can form deposits if
permitted to enter a steam generator. Once formed, these deposits affect the heat
transfer capability of the boiler tube metal, which can cause rapid degradation and
failure of the boiler tube walls. Figure 1.1-3 below shows a boiler tube that has
suffered from overheating caused by accumulated deposits that insulated the tube.
Studies done by the Electric Power Research Institute (EPRI) describe the specific
effects of contaminants on the operating pressure of a boiler.

courtesy of Betz Dearborn

Figure 1.1-3: Overheated Boiler Tube

with Accumulated Deposits

Although substantial data exists to justify the purity levels required by a given steam
generator, the following material briefly discusses heat transfer, deposit mechanisms,
and corrosion as they apply to makeup quality requirements of a steam generator.
Once the principles of heat transfer are understood, failure mechanisms caused by
the insulative effects of deposits and corrosion cells can be readily explained. For this
reason, it is crucial for those designing, selling, and troubleshooting water treatment
systems to have a working knowledge of the boiler system components and the
functions they perform.

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 1.2 Basic Heat Transfer Theory

Heat can be thought of as the transmission of thermal energy. Energy, in the form of
heat, is transferred from an object or substance at a higher temperature to one at a
lower temperature. The difference in temperature between the substances is the
potential that creates the driving force in heat transfer.

1.2.1 Modes of Transfer

Heat transfer generally occurs by conduction, convection, or radiation, although

more than one of these processes can occur simultaneously. The following is a brief
explanation of each process:

Conduction is the transmission of thermal energy from atom to atom or molecule to

molecule within bulk material. Heat transfer through a solid object is by conduction.

Convection is the transmission of thermal energy between a solid and a moving

liquid or gas, through a combination of conduction, fluid motion, and energy storage.
Heat transfer in a boiler, from the heated tubes to the liquid, is by convection. If the
fluid is circulated by a pump, it is called forced convection. If the fluid circulates by
variations in density due to heating, it is called natural, or free, convection.

Radiation is the transmission of thermal energy by electromagnetic force. Heat

from the sun is radiant. Although radiant heat is the most significant form of heat
transfer on the fireside of the boiler tubes, it is usually not a factor on the waterside
of the tubes.

1.2.2 Conductance and Resistance

Conductance and resistance are important concepts in heat transfer. Conductance is

the measurement of heat flow through or across a boundary per unit time, per unit
area, and per degree difference in temperature. Resistance is the reciprocal of
conductance and measures the ability of a material to impede (resist) the flow of
heat.

Conductance is the sum of the individual components of the modes of thermal

energy transfers. When heat transfers through a material with multiple layers of
different materials, several modes of heat transfer may be required. The conductance
is the sum of those transfers through all the layers and materials. Insulators are
materials that exhibit very high levels of resistance to the transfer of heat. In a boiler,

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 it is necessary to maintain an efficient transfer of energy at a low cost. The materials
of construction, as well as the methods of heat input and transfer, are important
considerations in the design of steam generators.

1.2.3 Applications in Heat Transfer

When a fluid flows over a surface of a different temperature, heat transfer occurs
between the fluid and the surface. In steam generation, water, both as a liquid and
as steam, is the energy transfer medium. Water takes the heat energy given up by
the fuel source and delivers it to the turbine. Water is also effective at taking energy
from other sources, such as steam, and transferring that energy elsewhere, for
instance to a cooling tower or heat exchanger.

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 1.3 Phase Changes

A boiler heats water (the energy transfer medium) and converts it to steam. Water
travelling through the boiler in tubes removes heat from the tube surface by
convection, increasing in temperature but not boiling. Figure 1.3-1 below shows the
tubes inside one type of boiler. The temperature of the water increases until a small
portion of the fluid nucleates (boils) at the surface, forming a steam bubble. When
the bubble bursts, it releases the steam, and therefore thermal energy. Water has a
high latent heat, meaning that it has a high capacity for energy (heat) storage. By
causing a phase change of the energy transfer medium (water), the steam generator
optimizes the transfer of energy from the boiler tubes to the water. The transferred
energy is released in the steam and carried through the system.

courtesy of Betz Dearborn

Figure 1.3-1: U-Tube Configuration Inside a Boiler

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 The temperature of the tube’s inner surface, which is in contact with the boiler water,
must be higher than the boiling or saturation temperature for the local pressure of
the fluid. The fluid typically begins to boil at minute cracks or cavities on the surface
of the tube. The cracks and crevices retain dissolved gases and serve as nucleation
sites where bubbles are more easily formed. As more bubbles are formed, the fluid
progresses through the phase flow patterns illustrated below in Figure 1.3-2 until no
liquid remains. If the tube has a very smooth surface, with none of these
imperfections, it must be superheated to initiate boiling. With a smooth surface,
nucleation is usually explosive, due to rapid expansion of the steam bubble.

Intermittently Dry Tube Wall Dry

Single Bubbly Plug Slug Wavy
Phase Flow Flow Flow Flow Annular Flow

Figure 1.3-2: Phase Flow Pattern in a Horizontal Tube

(courtesy of ASME Handbook on Water Technology for Thermal Systems, Figure 6-11, p.261)

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 As more of the fluid converts to vapor, a film of vapor can occur at the surface of the
tube. This film can act as insulation and cause the local surface temperature to
increase dramatically. When the surface becomes vapor-blanketed, boiling does not
continue in the same manner. A condition known as Departure from Nucleate
Boiling (DNB) occurs and can be catastrophic. When DNB occurs, the tube metal
temperatures can rise very quickly due to the buildup of the vapor blanket, which
prevents the liquid from reaching tube surfaces. Eventually, tube failures can occur
due to overheating. To prevent DNB, tubes are usually ribbed in a helical fashion,
much like the rifling of a gun barrel, as shown below in Figure 1.3-3. The helical
ribbing creates a turbulent flow across the tube surface, preventing the formation of
a vapor blanket.

Figure 1.3-3: Ribbed Steam Generator Tube

(courtesy of ASME Handbook on Water Technology for Thermal Systems, Figure 6-20, p.275)

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 1.4 Deposition and Scaling

Regardless of the efforts taken to ensure the purity of makeup water to boilers, some
contaminants remain. As the water proceeds through the steam cycle over and over,
these contaminants concentrate in the boiler due to evaporation and steam
separation.

Intrinsic in the design of boilers is the need for steam/water separation to enhance
steam quality. As a result of this separation, most impurities present in the feedwater
remain in the boiler. As the system continues to cycle, these impurities continue to
concentrate due to additional contaminants that enter the boiler to make up for
steam and water losses. When the concentrations of the contaminants exceed their
solubilities, the contaminants precipitate out of the feedwater. This can occur
throughout the boiler system and tubes.

1.4.1 Scale

When these impurities come out of solution, they are usually in the form of salts that
have low solubility even at high temperatures. Some common forms of boiler scale
include:

• Calcium Carbonate
• Magnesium Hydroxide
• Calcium Sulfate
• Magnesium Silicate
• Calcium Phosphate
• Iron Oxide

Since these salts are crystalline in nature, the scale can bind tightly with surfaces,
particularly at surface imperfections. Once scale forms, it “seeds” the precipitation of
other scalants.

1.4.2 Effects of Scale

Once scale begins to form on tube surfaces, it creates another layer of material
through which heat must pass to get to the water. Two main problems occur due to
the insulative effect of the scale material: under deposit corrosion and overheating of
the boiler tube metal. Both are discussed below.

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 Under Deposit Corrosion

Under deposit corrosion occurs due to the increased temperature difference that
exists between the waterside tube metal and the newly formed deposit layer. Heat
transfer occurs less efficiently through the deposit layer, because the metal surface
below the deposit is not adequately cooled by boiler water. Figure 1.4-1 below
shows energy loss as a function of scale thickness for normal scale, along with high
iron and iron/silica scale. Because of this, the surface of the tube under the deposit
reaches a higher temperature than the surrounding tube surfaces. The water
between the tube metal and the deposit boils off or evaporates, leaving behind any
trace dissolved solids that were present in the water. These trace dissolved solids,
such as chloride or sodium ions, that remain below the deposit can concentrate to
form corrosive substances such as hydrochloric acid or sodium hydroxide. In time
these corrosive solutions form pits where harmful deposits can occur in the future.
Typical pitting of a metal sample is shown below in Figure 1.4-2.

3/32

courtesy of Chemical Engineering

5/84
Deposit thickness, in.

n
iro
1/16 %
ge h4 t n
ud wi iro
l sl d ge 8%
3/64 a s l u ith
m ew
or al
N or m dg
N l slu
a
1/32 rm
No iron
h 8%
d g e wit a
al slu d silic
1/64 Norm ssociate
n d a
a

0 1 3 3 4 5 6 7 8
Loss of heat through deposit formation, %

Figure 1.4-1: Loss of Energy Due to Scale

Courtesy of Betz Dearborn

Figure 1.4-2: Pitting

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 Pitting accelerates the evaporative mechanism that occurs below deposits due to the
even higher temperatures that exist in the pit. Higher temperatures occur because
the pit volume is located closer to the heat source than the original inner surface of
the tube. Although the depth of the pit may only be 1/16 inch, the corresponding
temperature increase could be over 200oF. As a pit deepens due to continued
corrosion, it can penetrate the entire boiler tube wall, causing a “fish mouth” type
failure to occur. These failures normally necessitate the shutdown of a high-pressure
boiler, as 400-800 gallons of water can pass through a 1-2 inch opening every minute
at normal operating pressures in excess of 1,500 psi. Deposits also prevent treatment
chemicals from reaching the metal surface to assist in corrosion resistance. Under
deposit corrosion can be self-perpetuating and, if left unchecked, can cause massive
and violent tube failures.

Overheating of Boiler Tube Metal

The boiler tube metal overheats due to the same insulative properties of deposit and
scale that cause under deposit corrosion and the resultant tube failures described
above. Figure 1.4-3 below shows an example of tube failure due to overheating.
Because heat does not pass through the deposit material as effectively as it passes
through the metal, an increase in metal temperature on both sides of the boiler tube
occurs. Consequently, the surface temperature on the fireside of the tube can
become so high that the actual properties of the carbon steel are altered as its
granular structure changes. A softening of the metal typically occurs due to
prolonged overheating and relatively slow cooling during operation and shutdown.
In some cases, operators over fire the boiler to overcome the insulative effects of the
deposits and to maintain the boiler’s rated steam and temperature output. The
increased temperatures due to over firing contribute to metal degradation and under
deposit corrosion.
Courtesy of Betz Dearborn

Figure 1.4-3: Tube Failure Due to Overheating

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 1.4.3 Hideout

Another form of deposition is hideout, a temporary or permanent disappearance of

chemicals within the boiler system. It can occur in any system component and is
caused by a variety of phenomena.

Calcium and magnesium exhibit retrograde solubility in the presence of anions such
as bicarbonate, carbonate or hydroxide ions. This means that their solubilities
decrease with increasing temperature and pressure. Because of this retrograde
solubility, calcium and magnesium form scale in the hottest locations within the
boiler first. These locations are also the most vulnerable areas of the steam
generator, due to its heat transfer requirements.

The most widely recognized hideout chemical is phosphate. Phosphate hideout can
take place at relatively low concentrations, which most often occurs in parallel with
silica hideout. Phosphate is commonly fed to boilers in the form of mono-, di- and
tri- sodium phosphate as a scavenger for hardness ions such as calcium and
magnesium, and as a pH buffer. Phosphate ions form a precipitate with calcium and
magnesium that does not adhere to boiler tube walls, and can therefore be removed
easily by blowdown of concentrated boiler water. Although mono-, di- and tri-
sodium phosphate is useful for boiler scale and pH control, it also exhibits retrograde
solubility. This means that phosphate levels must be controlled to prevent scaling
due to hideout and subsequent heat transfer problems within boilers.

As the demand for steam varies and the load on the boiler fluctuates, the level of
soluble phosphate and therefore the alkalinity of the boiler water are affected. For
example, in load reductions, phosphate levels increase due to the resolubilization of
phosphate held in deposits. When the phosphate level increases, alkalinity
decreases, threatening the boiler with lowered pH. When high phosphate levels and
low pH are observed, blowdown is used to remove the excess phosphate, and
trisodium phosphate is fed to raise the pH (increase the alkalinity). These actions
can cause abnormally low phosphate levels and abnormally high alkalinity if the
temperature and pressure are subsequently increased due to an increased demand
for steam.

The consequences of occasional pH fluctuations in boilers are significant. Permanent

phosphate hideout causes tube failures similar to those caused by corrosion and
scaling if proper controls are not exercised over all these factors.

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 1.4.4 Control Methods

Elevated concentrations of impurities in the boiler can be avoided through adequate

purification of makeup water and boiler blowdown. Blowdown headers are
designed to preferentially take water at locations where impurities can concentrate,
either at the surface of steam/water separation in the drum, or at some other location
depending on the contaminant.

Chemical treatments are also available to help limit deposition. Phosphate is one
example of a treatment chemical. It serves other purposes, such as pH control and
surface passivation, and it is very good at converting salts and suspended solids to
forms that are easily controlled through blowdown.

The most effective way to prevent scaling, corrosion and related problems caused by
impurities is to prevent impurities from entering the steam generator.

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 1.5 Corrosion

A certain percentage of water molecules dissociate into H+ and OH- ions. These ions
become a contributing factor to corrosion. This tendency to dissociate, combined
with the high pressures and temperatures found in boiler systems, make water an
aggressive fluid in the steam cycle. As a result, many alloys corrode in this
environment.

1.5.1 Fundamentals

Corrosion is the loss of a substance due to chemical or electrochemical interactions

with its environment. Corrosion involves a charge transfer across a metal/solution
interface where metal degradation occurs based on the kinetics of charge transfer
phenomena, shown below in Figure 1.5-1. As iron atoms migrate from the area of
attack, the material in the tube wall is reduced. The resulting dissolution of metal
from the tubes can cause them to weaken or fail.

Heated side of tube Unheated side

(acts as anode) (acts as cathode)

,,,,,,
OH (-)

z

y
Á,
À
A€

@
|, ,
{
y
Ã
Â
Á
À
ƒ
‚

€
C
B
A
@




, {
y
Â
À
‚
€
B
@

courtesy of Power Engineering

Neutral Fe OH (+)
atoms
migrate
from area
of attack Fe (++)

Deposit

H ions migrate to Steam/water

unheated side, mixture
neutralize, go off as H2

Figure 1.5-1: Deposition Corrosion

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 Several factors affect the process of corrosion in a boiler system. These include the
type of metal used for construction, the dissolved gases and ions present in the
water, and the temperature in the boiler and tubes.

1.5.2 Effects

Corrosion cannot be completely eliminated. However, it is possible to minimize its

effects and control the type of corrosion present in the system. Generalized surface
corrosion is preferable to other types, like pitting corrosion. A boiler can outlast the
economic life of the plant if water chemistry and passivation are controlled to limit
the type of corrosion to general surface corrosion. Accelerated pitting, on the other
hand, can lead to catastrophic tube failures in a very short period of time, sometimes
in a matter of hours.

1.5.3 Control Methods

As with deposit control, proper feedwater quality and chemical treatments are
instrumental in preventing boiler corrosion. It is necessary to define the type of
corrosion to which a system is most susceptible in order to develop the appropriate
corrosion control scheme. Limiting contamination from feedwater or other
component contributors is extremely important. Corrosion is best avoided by
maintaining system purity, rather than through chemical control alone.

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 Figure 1.6-1: Steam/Water Separation

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 1.6 Vaporous Carryover

Carryover and entrapment of water and impurities with the steam causes damage
and corrosion in steam piping, control valves, and turbines. Steam purity is essential
for maintaining these components, as minute concentrations of impurities can cause
severe and costly damage.

1.6.1 Mechanical Carryover

Mechanical carryover can occur due to several mechanisms: poor boiler design, poor
maintenance, high drum level, load surges, uneven firing, operating beyond capacity
and improper water composition. Only water composition can be controlled
chemically.

Steam/water separation in the boiler drum is the initial stage in attaining steam
purity. The primary separation of steam from water occurs here, followed by the
secondary separation, in which entrained water droplets are eliminated from the
steam. Control of the drum level and its operation is very important for eliminating
carryover.

Figure 1.6-1 on the opposite page illustrates the process of steam/water separation.
As steam separates from the water surface, it breaks through as a bubble, forming a
cavity as it escapes. As water rushes in to fill the cavity, it splashes about and creates
a mist that rises with the steam. The mist must be removed mechanically. A
meandering and tortuous path for steam travel is ideal for removing entrained water.
Baffles, chevron screens, and centrifugal separators are employed to “dry” the steam.
If these fail, or are poorly designed or maintained, the mist and any impurities in the
water continue on with the steam.

Mechanical carryover can also occur due to foaming and priming. Foaming occurs
when the water contains large amounts of solids and organic material. Priming is
the spouting and surging of water into the steam header due to improper boiler
operation or design. Both foaming and priming can cause impurities to be entrained
in the steam.

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 1.6.2 Chemical Carryover

Certain elements and compounds that are normally solids have vaporous tendencies
in boiler environments. These chemicals carry over as vapor with the steam into post
boiler components where they re-solidify. For instance, silica has the ability to
volatilize along with the steam at certain concentrations and at certain pressures and
temperatures. This capability can be shown by plotting steam silica concentrations as
a function of boiler silica concentrations at given temperatures and pressures. When
it is no longer soluble in steam, the silica forms deposits. This occurs selectively on
turbine blades, where the deposits cause vibrations. Silica is particularly hard to
remove once deposited, requiring a hydrofluoric acid wash or grit blasting.

Carryover can be prevented using preset guidelines to maintain chemical parameters.

1.6.3 Attemperation

Attemperation, or desuperheat spray, is a source of steamside contamination that

occurs even without carryover. Cycle water is injected directly into the steam to
control operating temperatures. If the quality of the cycle chemistry is questionable,
this water can contaminate the system, causing difficulties in the post-boiler
equipment, especially the turbine.

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 1.6.4 Results of Carryover

Solids carried over with steam can have a significant negative

Courtesy of Siemens
impact on post-boiler components. Deposits can form on steam
tube surfaces, valves, and turbines. Damage caused by upstream
deposits can also cause subsequent damage downstream. For
instance, deposit-caused corrosion products from the
superheaters can end up in turbine components with disastrous
results. Turbines are very sensitive to carry-over products.
Figure 1.6-2 on the right shows a close-up of turbine blades. If
the blades become corroded, the turbine can become
unbalanced and suffer reduced efficiency. Figure 1.6-2:
Turbine Blades
When chloride, fluoride and other halide ions are present in steam, they create an
environment in the turbine that is conducive to stress corrosion cracking (SCC).
Stress corrosion cracking of rotor blades and disks can result in turbine failure.
Other types of corrosion failure mechanisms include corrosion fatigue, pitting, and
erosion corrosion.

Deposition is another effect of carryover on turbines. The steam solubility of

carryover impurities determines where deposition can occur. Figure 1.6-3 below
shows the range of silica tolerances in boiler water where silica remains in the steam.
This range, known as the Wilson line, is a wet/dry transition area, in which the
constituent of interest is no longer soluble or volatile within the steam and lays out
on the turbine surface, usually on blades and rotors. Cyclic evaporation and drying
occurs at (or along) the Wilson line, resulting in the concentration and buildup of
deposits.
10
Range of silica tolerances
9
in boiler water (pH about 11)
8 to keep silica in steam
courtesy of Power Engineering
Silica in boiler water, ppm

7 below 0.015 to 0.02 ppm

6
5
4
3
2
1
0
1000 1500 2000 2500 3000
Boiler pressure, psig

Figure 1.6-3: Setting Limits to Prevent Silica Carryover

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 Low Pressure

2
Loss in Stage Efficiency (percent)

500 Mw Unit
200 Mw Unit
4 Intermediate Pressure
High Pressure

6 8 16 32 63 125 250 500

Surface finish, Micro-inches C.L.A. (Flow across cut)

8 16 32 63 125 250 500 1000

Surface finish, Micro-inches C.L.A. (Flow with cut)
900 600 400 240
10 Emery Grade

0.01 0.05 0.1 0.2 0.4 0.6 0.8 1.0 2.0 4.0 6.0 8.0 10.0

Equivalent Sand Grain Size (Mils)

Figure 1.6-5: Loss of Turbine Stage Efficiency Due to Surface Roughness
(courtesy of ASME Handbook on Water Technology for Thermal Systems, Figure 3-17, p.135)

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 Silica is an impurity that creates a major deposition problem. Silica is very adherent,
requiring extra effort to remove it from blade surfaces. Weight imbalances can occur
in the turbine if the deposits become significant. When these deposits create uneven
surfaces, turbine efficiencies are greatly reduced. Figure 1.6-4 below shows a turbine
with exposed blades. As steam flows across the blade surfaces to rotate the turbine,
poor flow distribution occurs as a result of the irregular surfaces. The energy
requirement to rotate the turbine increases and the efficiency of the energy transfer
from the steam to the turbine is reduced. Figure 1.6-5 on the opposite page shows
the loss of turbine stage efficiency due to blade surface roughness. The efficiency loss
occurs regardless of unit size or pressure rating.

Courtesy of Betz Dearborn

Figure 1.6-4: Turbine with Blades Exposed for Deposits and Corrosion Inspection

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