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BOII.

ER WATER CHEMISTR~/ ANAL~SIS


Knowledge Requirement
1 . WHY TI-lE MEASUREMENT OF DISSOLVED OXYGEN IS SO IMPORTANT
FOR BOILER FEED WATER?

Dissolved Oxygen (Free) can and will corrode feed lines, economizers, steam drum(s) and downcomers. The corrosion can be general but is more likely evident as pitting of internal surfaces. Idle
boilers, not properly stored will corrode until either the oxygen has been used or the boiler returned to
service. In any case the boiler lffe will be shortened. That's why the measurement of dissolve oxygen
is so important for boiler and feed water.

2.

DESCRIBE TI-lE WORKING PRINCIPLE OF THE DISSOLVED OXYGEN


ANALY2ER ?

The measurement of dissolved oxygen is based on the well-known Clark cell principle.
An oxygen-permeable membrane isolates the electrodes from sample water, thus obviating the
need for sample conditioning. Other reducible or oxidizable ions do not interfere, because they cannot
pass through the gas -permeable membrane. A constant vo~age supply powers two electrodes,
maintaining each at a constant potential.
A gold working electrode (cathode) reduces the dissolved oxygen to hydroxyl ions.

0:! +21-1.20 + 4e- =40HA large silver counter electrode (anode) provides the oxidizing reaction which occurs at its surface.
4Ag+ + 4Br+- =4AgBr + 4eThe reduction of oxygen is the current lim~ing reaction, thus making the cell current linearly
proportional to the dissolved oxygen concentration. Electrochemical reactions and diffusion rates are
temperature-sensitive. The measuring cell, therefore, is equipped w~h a temperature sensor which
allows automatic temperature compensation.

3. WHAT TYPES OF CHEMICALS ARE DOSED IN FEED WATER SYSTEM,


WHAT IS THE FUNCTION OF EACH CHEMICAL?

The following chemicals are dosed in the feed water/condensate systems:

Phosphate

Hydrazine or Carbohydrazine

~ Amine.

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Phosphate is dosed directly into the IP and HP Steam/Water Drums to reduce scale formation and
to control drum water pH.
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As oxygen scavenger is dosed directly into the CEP discharge. Oxygen reacts with iron and other
metals to form a metal oxide. Oxygen dissolved in boiler water having traces of chlorides or solids can
cause pitting corrosion of metal surfaces. The resuning cond~ion may be severe, even at low pressure.
Oxygen and other gases are removed from the feed water before they can enter the boiler both
mechanically within the de aerating condenser and chemically Oxygen scavenger into the condensate
dosing w~h Hydrazine or Carbohydrazine also promotes the formation of a magnetite layer and
decomposes to form ammonia, which combines with condensate in the condenser to form NaOH and
assists in pH control.

Amine is dosed directly into the CEP discharge to maintain pH in the condensate system. Low pH
is one of the most common causes of localized corrosion. Corrosion in steam and condensate return
lines may be caused by a low pH induced by carbonic acid resuning from the association of C02
coming fran the boiler w~h water. The C02 itse~ may originate fran air leakage into the condenser or
bicarbonate alkalinity in the feed water. A buildup of acid reduces condensate pH leading to loss of
metal and grooving of the condensate piping (General Corrosion). The affect is accelerated in the
presence of 0-!.
Hydrogen can evolve in a low pH environment and can have the following effects:
~

It can diffuse into the boiler metal

React w~h ferrous carbide to produce methane

4. WHY SODIUM MEASUREMENT PLAYS A SPECIFIC ROLE COMPARED TO


PH, CONDUCTIVITY AND SIUCA TRACES ..?

Sodium measurement can indicate nthere is Sodium slippage from the lon Exchanger.

5.

WHY SAMPLE CONDffiONING IS NECESSARY IN SODIUM ANALYSIS ?

Providing the dematerialized water is of good qual~ and the dematerializing train is not
experiencing sodium slip, the saturated steam sodium analyzer should give the first indication of a
condenser tube leak.

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6. EXPLAIN ABOUT COORDINATE PHOSPHATE CONTROL PROGRAM AND


WHAT IS PHOSPHATE RANGE FOR HP AND IP DRUM?

High pressure boilers using demineralized make up water generally have a large percentage of
condensate returns and high heat transfer areas. These conditions, more than the operating pressure,
make high pressure boilers prone to caustic attack, requiring special treatment. Because high pressure
boiler make up is generally free of hardness, hardness deposits are not often found in the boiler.
However iron and copper deposits are common and can lead to severe problems. Porous iron or
copper oxide deposits on the radiant wall tubes or high heat transfer areas, act like miniature boilers.
Boiler water is drawn into the deposit and steam or pure water leaves the deposit; solids in the water
remain under the deposit. Extremely high levels of hydroxide or caustic can form beneath the deposit.
The protective magnetic layer and even the parent metal can suffer caustic attack. A treatment
approach known as Coordinated Phosphate Treatment was developed to limit the localized
concentration of caustic. Excess caustic combines with phosphate and effectively buffers the pH.
Proper P04 levels ensure the absence of free hydroxide or caustic. For the program to work, it is
essential to have sufficient phosphate available to combine with free caustic.
Coordinated phosphate treatment was simple process to monitor and control. To prevent the
formation of free NaOH, the operator had to keep below the upper line in the plot of pH vs. phosphate
concentration plot shown in Figure 1. That line corresponds to three sodium for each phosphate, i.e. the
Na/P04 ratio of 3.0 found in pure tri sodium phosphate.

10.0

r;=======:::;----------:::;:::::="--,
Coordinated Phosphat
Treatment Region Belo
Na/P()- 3.0 Line

.0

.0 ~

II)"

0.5

;!
2

"
0

l"l

I-Jiedium Preeoure
9.0

Congruent Phosphate
Tre<:~tment Region in
Shaded Area

3
;'

:I

--- ~

.2

PHOSPHATE (mg.ll)

Fig. 1 -Relationship Between pH and Phosphate in Boiler Water


Showing Coordin11ted and Congruent Phosph11te Tre11tmenl Regions

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Different form of phosphate consume or add caustic as the phosphate shifts to the proper form;
to monosodium phosphate consumes caustic as it reacts with caustic to form disodium
phosphate in the boiler water:
add~ion

Addition to tri sodium phosphate adds caustic, increase boiler pH;

Control is achieved through feed of proper type of phosphate to either raise or lower pH while
maintaining proper phosphate level.
HP DRUM PHOSPHATE (PO.) range is 2 -5 ppm, and
IP DRUM PHOSPHATE (PO.) range is 3 - 15 ppm.

7. WHAT IS THE PHYSICAL SIGNIFICANCE OF PH ..?


pH is short from for Power (p) of Hydrogen (H). pH is defined as the negative log of the Hydrogen
lon activity, a H+ or the effective Hydrogen lon concentration.
pH is a unit of measure that describes the degree of acidity or alkalin~ of a solution. Acidity is
defined as the concentration of Hydrogen Ions [H+] in solution and alkalinity as the concentration of
Hydroxyl Ions [OH-] in solution. As seen above the actual theoretical definition of pH is -Log11 0 a H+.
But, since the activity coefficient (a) for Hydrogen (H+) is 1 the practical defin~ion for pH can then be
defined as -Log1 0 [H+].

8. HOW THE PH METER/ ANALY2ER DO WORKS..?


There are two ways of measuring pH. The first is a Colorimetric Method, which uses color
indicators to indicate the pH of the sample. There lim~ations to this measurement technique. A more
effective way to measure pH in an industrial setting is the potentiometric method of pH analysis. The
potentiometric method allows continuous, on-line measurement and is not subject to operator bias.
Potentiometric analysis has four parts: 1) sample, 2) pH sensing electrode, 3) reference electrode and
4) signal ampl~ier J readout.

The pH sensing electrode acts as one half of a battery whose potential varies with the hydrogen
ion concentration in solution. The Standard Glass Electrode is commonly used in industrial application
because of its ruggedness and versatility. The glass electrode basically consists of four major
components: 1) The Glass Membrane, 2) The Internal Buffer Solution, 3) The Reference Wire and 4)
The Glass Stem.

The glass electrode is primarily composed of Alkali Silicates that are comprised of Sodium,
Potassium, L~hium, Silica, Oxygen and Hydrogen. All of these components are combined to form a
Hydrogen lon specific sensing glass: the amount of each const~uent in the glass determining its pH
sensing properties.

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When the glass is put into solution ~ undergoes a chemical reaction, which forms a leached layer.
This layer is the area at the surface of the glass where an ion exchange reaction takes place. In this
surface layer Hydrogen Ions migrate in and replace other pos~ively charged ions such as Sodium or
Potassium. This causes a Silica-Oxygen-Hydrogen bond to be set up which is essential for sensing
Hydrogen lon in solution.
The pH glass electrode actually works on a two-reference electrode basis, a reference inside the
glass and a reference that is in contact with the externals of the glass. pH measurement requires
measurement of the potential difference in the pH electrode system. The formation of a leached layer
actually occurs on both sides of the glass membrane. The difference in potential between the two layers
is called the Phase Boundary Potential, and is the potential difference that gives the pH signal.
In the pH glass there must also be a charge transport mechanism so that a millivo~ potential will be
seen. In between the two leached layers there remains a glass membrane layer that does not undergo
the ion exchange that occurs at the surface. In this membrane layer Potassium and Sodium, major
constituents of the glass, act as the charge carriers.
For best results a Symmetrical Cell is set up on both sides of the glass membrane. To set up the
Symmetrical Cell, the internal fill solution in the glass and the reference fill solution are similar in their
makeup. The symmetry is important so that the temperature curves for the two solutions are as close
as possible and minimizes the temperature effect. For Symmetry purposes the internal buffer is made
of KCI {Potassium Chloride) solution that is the same as the reference solution.

9.

WHAT DO YOU KNOW ABOUT PHOSPHATE HIDEOUT PHENOMENON?

When the concentration of phosphate in the boiler water is too high, phosphate will react with boiler
scale forming iron and iron sodium phosphates or precip~ate to form a solid phase on the hot boiler
tube surfaces and elsewhere. This phenomenon is called phosphate hideout and ~ can resu~ in
changes of pH, as well as the concentrations of phosphate and other chemical species in the boiler
water. Hideout usually first occurs in boiler tubes w~h the highest heat flux and low mass flow, where
departure from nucleate boiling (DNB) or under deposit concentration occur. Surprisingly, hideout and
boiler tube corrosion can also occur in HRSGs where the heat flux is much lower than in coal- or oilfired units. This is because there may be accumulation of corrosion products or inadequate mass flow
through some generating tubes; particularly during duct burner firing.
Because the solubil~ of phosphate decreases as boiler pressure increases, hideout is typically
only noticed during load changes. Elevated temperatures at the boiler tube wall or depos~s can resu~
in some precip~ation of phosphate which usually occurs when load increases. When the load reduced,
phosphate reappears.

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10.

WHAT IS THE PH AND CONDUCTIVITY LIMITS IN CONDENSER


WAlER, FEED WATER, DRUM WAlER AND STEAM?

pH and conductivity Range


pH Range

Conductivity Range

Condensate

9.3-10.0

6-20 IJS/an

LP Drum

9.3-9.7

6-151JS/an

IP Drum

9.3-10.0

<100 ~o~S/an

HP Drum

9.0-10.0

< 40 ~o~S/an

LPSH

9.0-10.0

1Q-25~o~S/cm

IPSH

9.0-10.0

1Q-251JS/cm

HPSH

9.0-10.0

1Q-251JS/cm

1 1.

WHY TEMPERATURE MEASUREMENT AND COMPENSATION IS


REQUIRED IN PH AND CONDUCTIVITY ANALYSIS ?

Temperature plays an important role in the characteristics of a solution. With the variation of
temperature the ionization rate of the solution varies. When we go for measuring pH, we are indirectly
measure the total Hydrogen ion in the solution. The more temperature of a solution the more H+ ion in it
and pH of the solution is the less and vice versa. Due to increasing of ionization w~h temperature the
charge carrying capacity of the solution increases which means increase in conductivity. Since
temperature has a direct effect in the measurement of pH & conductivity it needs to be measured and
compensated during the measurement of pH & conductivity

12.

WHAT ARE RECOMMENDED SIUCA UMIT IN MAKE UP WAlER,


CONDENSER WAlER, DRUM AND MAIN STEAM?

Silica range
Make up water

<0.02ppm

Condenser water

<0.02ppm

HP drum water

<2ppm

IP drum water

<40ppm

HP, IP & LP steam

<0.02ppm

13.

WHAT YOU WILL DO IF HP SUPER HEAlER SIUCA GOES TO 50


PPB ... ?

Open HP drum CBD to reduce silica concentration.

Check make-up water silica.

Reduce ST load.

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14.

IF HP DRUM WATER IS IN FREE CAUSTIC ZONE , WHAT ACTION


YOU WILL TAKE ?

>
>

Open CBD more


Stop phosphate pump.

1 5.

WHAT WILL BE YOUR ACTION IF PH FALLS WITH DOSING PUMPS


STILL RUNNING?

>

Check the running pump is pumping properly, if the running pump is not pumping
properly; change over to the stand by dosing pump.

>

Check running pump stroke position,~ the pump stroke minimum; increase the pump
stroke.

>

Check the dosing tank solution concentration and

less concentration solution, add

some N~P04 in the dosing tank.

>

Check HP drum blow down condijion.

1 6.

WHAT IS THE DIFFERENT CHEMISTRY PARAMETERS MEASURED


ONUNE?

Online Parameters
#
1

Condensate

Parameters
pH, conductivijy, Cation Conductivity

LP Drum

pH, conductivijy, Silica

IP Drum

pH, conductivijy, Silica

HP Drum

pH, conductivijy, Silica

LPSteam

pH, conductivijy

IPSteam

pH, conductivijy

HP Steam

pH, conductivijy

LP Economizer

pH, conductivijy

LP Saturated Steam

pH, Cation Conductivity, Sodium

10

IP Saturated Steam

pH, Cation Conductivity, Sodium

11

HP Saturated Steam

pH, Cation Conductivity, Sodium

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17.

WHAT IS TI-lE PURPOSE OF THE SPECTROPHOTOMETER.?


PLEASE EXPLAIN ITS WORKING PRINCIPLE.

Accurate, easy to use, and affordable! By design the spectrophotometer is ideally suited for both
routine testing and demanding analysis in water treatment, industrial processes, surface finishing, food
and beverage processing, pharmaceutical production, and chemical synthesis.
The DR/4000 Spectrophotometer provides dig~al readouts in direct concentration un~s.
absorbance, or percent transmmance. When a user generated or HACH programmed method is
selected, the on-screen menus and prompts direct the user through the test. This menu system also
can be used to generate reports, statistical evaluations of generated calibration curves, and to report
instrument diagnostic checks.

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