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Water treatment

Good water treatment will: 1.prevent scale deposits in boilers 2.prevent


corrosion in boiler surfaces 3. Prevent caustic embrittlement 4.Ensure good
steam purity.
In the process of evaporation of water to form steam,scale and sludge deposits
form on heated surfaces. The chemical substances in water concentrate in a film
at the evaporation surface.Soluble substances are redissolved by the water
displacing the steam bubbles at the point of evaporation.Insoluble substances
deposit on surfaces.Most scale forming substances have a decreasing solubility
with temperature.The higher the temperature more rapidly will a heat deterrent
scale will form.
Principal scale forming materials are calcium and magnesium
carbonates,sulfates and silicon salts. Salts of sodium,potassium,aluminium may
also be present. Both carbonates and sulfates precipitate when heated.
Carbonate scale is soft and removed as sludge,while silica scale is hard.
In addition to salts,oxygen is also controlled as it leads to pitting corrosion; also
to minimize formation of pre-boiler corrosion products,which end up as deposits
in the boiler.
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Water treatment basics


Internal treatment is used to prevent scale formations caused by hardness salts and to
provide PH control to prevent boiler corrosion. There are several methods for internal
treatment: 1.Phosphate-hydroxide or conventional treatment,2.Co-ordinated phosphate
3.,chelant method.Methods(organics).,4.polymers. 1 and 2 control the PH of boiler water and
to precipitate the calcium and magnesium compounds as a flocculant sludge,which can be
removed by blow down.Method 1 maintains an excess of hydoxide alkanity.Method 3
involves use of EDTA.
Phosphate-hydoxide method involves addition of phosphate and caustic to boiler water.PH
maintained in the range 10.5-11.2.This is widely used in low pressure boilers up to 1000
psig.Phosphate precipitates hardness salts such as calcium,magnesium.At higher
pressures,lower phosphate residuals must be maintained to avoid hideout.(this is a
temporary disappearance of phosphate in the boiler water upon increase in load and reIn corordinated phosphate method ,no
appearance upon load reduction.
free caustic is maintained.Fig shows
PO4 vs resulting PH when trisodium
phosphate is dissolved in water.To
insure no free caustic,PO4 that
corresponds to a mole ratio of Na to
PO4 of 2.6 is recommended above
1000 psi.Chelants react with Ca,Mg to
form soluble complexes,which are
removed by blow down.Used for
P<1500 psi
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Commonly used Chemicals


Chemical

Purpose

comment

NaOH

Increase alkanity

Precludes formation of CO2

Na2Co3

Increases alkanity,PH

Lower cost some CO2 released in


steam

N23PO4

Precipitates Calcium

Alkanity,PH must be high for this reaction

Chelants EDTA

Controls scale by forming heat


stable Ca,Mg complexes

Prevents precipitation of scale forming


compounds on surfaces;.dissociate at
high Pressure

polymers

Disperse sludge ;prevents


fouling

May be used in conjunction with


phosphates

Hydrazine

Prevents O2 corrosion

Removes residual O2 to form N2 and


H2O

Sodium sulfite

Prevent O2 corrosion

Forms sulfate and neutralizes


O2.decomposes at high P,T to form H2S

Filming amines

Controls return line corrosion


by forming protective film

Protects against O2,CO2 attack

antifoams

Reduces foaming tendency

Usually added with other chemicals for


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scale,sludge control

Water Quality
Drum press, psig
Fw diss oxy,mg/l
Total iron
Total cu
Total hardness
PH preboiler
Non volatile TOC
Oily matter
Boiler water
Silica
Total
alkanity(caco3)
Sp cond,mho/cm

0-300
<0.04
<.1
<.05
<.3
7.5-10
<1
<1

301-450
<.04
<.05
<.025
<.3
7.5-10
<1
<1

451-600
<.007
<.03
<.02
<.2
7.5-10
<.5
<.5

601-750
<.007
<.025
<.02
<.2
7.5-10
<.5
<.5

751-900
<.007
<.02
<.015
<.1
7.5-10
<.5
<.5

<150
<350

<90
<300

<40
<250

<30
<200

<20
<150

<3500

<3000

<2500

<2000

<1500

Asme 1979 guidelines -for boilers with heat flux<150,000 Btu/ft2h. For
higher fluxes, values for next pressure to be used
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Water Quality
Drum press, psig
Fw diss oxy,mg/l
Total iron
Total cu
Total hardness
PH preboiler
Non volatile TOC
Oily matter
Boiler water
Silica
Total
alkanity(caco3)
Sp cond,mho/cm

901-1000
<0.007
<.02
<.015
<.05
8.5-9.5
<.2
<.2

1001-1500
1501-2000
<.007
<.007
<.01
<.01
<.01
<.01
Not detectable
9-9.6
9-9.6
<.2
<.2
<.2
<.2

<8
<100

<2
<1
Not specifed

<1000

<150

<100

No values given for steam purity as it is a function of so many


variables and depends on application.
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Water Chemistry
Scale forming substances have a decreasing solubility in water with an increase in
temeperature.Depending on tube temperatures,heat flux and solubility of these
compounds of calcium,silica,magnesium, these compounds can form deposits inside
boiler tubes.Calcium carbonate deposits quickly forming white friable
deposits.Magnesium phosphate is a binder that can produce a hard adherent deposit.
Insoluble silicates are present in many boilers.
Vaporous carryover is governed by the steam density and can be controlled only by
controlling the boiler water solids,whereas mechanical carryover is governed by the
efficiency of steam separators.
Steam purity requirements for saturated steam turbines is not stringent. The saturated
steam begins to condense on the first stage of the turbine ,water soluble contaminants
carried with steam do not deposit. With superheated steam,steam purity is
critical.Salts that are soluble in superheated steam may condense or precipitate and
adhere to the metal surfaces as steam is cooled. Deposits from steam can cause
blade failures.Deposition can occur at the salt zone just above the saturation line and
on surfaces in the wet steam zone. The solubility of all low volatility impurities such as
salts,hydroxides,silicon dioxide and metal oxides decreases as steam expands and is
lowest at the saturation line. The moisture formed has the ability to dissolve most of
the salts and carry them down. The critical region for deposition in turbines is the
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blade row upward of the Wilson line..

Solubility of Salts
Steam pressure and
temperature which
affects its density have a
strong effect on its ability
to dissolve solids. As
steam temp increases at
constant
pressure,density
decreases as also the
dielectric permittivity of
water and a lower
polarity of water.
Dissolving power of steam first decreases .With further increase of temperature,the
bonds in the solids weaken and solubility of Nacl increases. At higher pressure,steam
has higher dissolving power due to higher density.Na2so4 and Caso4 have similar
trends.If the concentration of a substance is lower than its isobaric solubility,it will be
dissolved and carried off by steam and form deposits in turbine. If the concentration is
higher the excess will be deposited in the superheater and remainder in the turbine.
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Distribution Ratio of some Chemicals

Steam Turbine requirements:


EPRI: 10 ppb -sodium 6ppb-chlorides 20ppb -silica 100ppb-TOC
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Effect of water level ,inlet quality

As the drum level


increases,the static
head is higher and
hence the pressure
loss at downcomer
inlet can be
overcome and no
bubbles will be
formed. This is an
aspect to consider in
sizing downcomers.
As water level increases,chances of carry over are high. Due to the higher static
head,chances of carry under are less. Also as inlet feed water quality
increases,more carry over and carry under!

Effect of Boiler water PH on Silica carryover

PH-8

Steam pressure psi vs ratio of silica in steam to silica in water,%


As boiler water pH increases silica carryover will be less. This is vaporous
carryover and effectiveness of drum internals will not help. Only keeping boiler
water limits to a low level will help minimize silica in steam.
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Throttling Calorimeter
Throttling calorimeter is used to obtain estimates of steam
quality in low pressure boilers generating saturated
steam.A sampling nozzle is located in the vertical section
of pipe.Steam enters the calorimeter through a throttling
orifice and passes into a well insulated expansion
chamber.Throttling is an isoenthalpic process.
hs=hm=xhg+(1-x)hf where hs,hm,hf,hg refer to
enthalpies of steam,mixture,sat liquid and sat vapor
and x=steam quality,fraction.
The steam temperature is measure after throttling and the enthalpy is obtained
from steam tables.The steam is usually superheated at atmospheric pressure after
throttling.
Example:A throttling calorimeter measures 250 F when connected to a boiler
operating at 100 psia.Determine the steam quality.
From steam tables,at atm pressure and 250 F,h=1168.8 Btu/lb and at 100
psia,hg=1187.2 and hf=298.5. 1168.8=1187.2x+(1-x)298.5 or x=.98 or 98 %.
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Relating quality with Purity


Steam purity refers to impurities in steam in ppm ; it is also expressed as
conductivity in micromhos/cm or as sodium in steam etc.Conversion to
ppm is available using these values.High pressure boilers with
superheated steam require high steam purity on the order of 0.02 to 0.1
ppm if the steam is used in a steam or gas turbine,while higher
values,around 1pmm,can be tolerated for low pressure saturated steam.
This is due to the fact that as superheated steam expands the solubility of
solids decreases and hence these can deposit on the blades, while
saturated steam can hold more solids. Due to the wetness.
Steam quality refers to wetness in steam. Conversion is done as follows.
If steam has 0.5 ppm solids when the boiler water has 2500 ppm,the
moisture in steam=0.5/2500x100=0.02 % or steam quality=1000.02=99.98 %

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Relating steam by volume and weight


A steam water mixture is described by the term quality,x, or dryness
fraction.x=80 % means that in 1 lb of steam 0.8 lb is steam and .2 lb is water.
Circulation Ratio R=1/x. If x=25%,the CR=4.
Steam by volume,SBV, is also required in some discussions on DNB.
SBV= 100/[1+{(100-x)/x}vf/vg] where
vf,vg=specifc volume of saturated water and steam,ft3/lb
At 1000 psia, vf=.0216,vg=.4456 and at x=80 %,
SBV=100/[1+{20/80}x.0216/.4456]=98.8 %

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Flow in Blow down lines


100

P=160 atm

40 atm

Using Bernoullis equations and critical flow equations,the two phase flow
through blow down lines may be estimated. The above chart is developed
from the above procedure. It shows the mass flow of water that can flow
through blow down lines based on resistance of the blow down line.At 40 ata
and with K=.023x150x12/2=20.7,m=7000 kg/m2s. So blow down flow is:2 in
ID=50 mm=.05 m.Flow=(3.14x.05x.05/4)x7000x3600=49500 kg/h.Hence
valve may be throttled to control blow down quantity if flow required is less.
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Cost of Blow Down

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Steam purity problems


System chemistry changes:changes in boiler water conductivity-indication of
steam contamination
Superheated steam temperature drops: Sudden carryover of water into
superheater decreases the steam temperature. Priming could be the problem
or sudden load changes,poor drum internals,high load etc.
High or fluctuating drum level: cause of many carry over problems.Load
changes have to be checked or drum to be designed for large load changes.
Header pressure variations:causes carryover. Priming also occurs.
Low steam temperature: The superheater could have deposits which can lead
to tube failure.Fouling also decreases duty.Turbine efficiency also suffers.
Increasing superheater tube wall temperature: can be due to carryover and
deposit formation.
Turbine pressure: An increase in first stage turbine pressure is a sign of turbine
fouling.By maintaining a record of steam flow vs inlet pressure,changes in
turbine pressure can be related to carryover.
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Monitoring System Chemistry


Steam nozzles should be used to collect saturated or superheated samples as in
ASTM D-1066,ASME PTC 19.11. The steam should be condensed and sampled
to avoid deposition.
Sodium: It is about a third of total solids and provides a good indication of steam
purity.By measuring sodium content in condensed steam sample,purity is
estimated.
Specific conductivity: It is a measure of the ability of aqueous solution to conduct
electrical current. The greater amount of dissolved solids in solution,more the
electrical current the solution can conduct.Good method for high level steam
contamination. When low level contaminant detection is required,the specific
conductance should be measured on a degassed sample since dissolved gases
such as ammonia,carbon dioxide have a great influence on conductivity.
Silica: monitored photometric methods.
Chlorides: Special electrodes are used or chromotography.
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Water chemistry Problems


Causes of foaming: excessive solids,alkanity and presence of organic
matter,oil.Add antifoam agents. Coordinated phosphate treatment controls
PH of boiler water and precipitates Ca,Mg compounds as sludge.
Caustic corrosion-due to free Naoh which attacks magnetite layer mostly in
water cooled tubes in high heat flux regions ,horizontal,slanted tubes are
susceptible.
Keep the concentration of an impurity below its solubility in superheated
steam. Turbine steam should be monitored for sodium and cation
conductivity and periodically for chloride,sulfate,TOC and Sio2.
Turbine deposits should be sampled and analyzed.Presence of Nacl,Naoh
above 0.25 % are cause for concern.

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Failure Mechanisms
Caustic attack: localized wall loss on tube ID surface. High PH
corrosively attacks and breaks down the protective magnetite layer
Oxygen pitting:localized corrosion and loss of tube wall-eco inlet.flooded
or non-drainable surfaces susceptible. Occurs with presence of
excessive oxygen in boiler water.Wetted surface oxidized as water
reacts with iron to form iron oxide
Hydrogen damage:loss of ductility or embrittlement of tube. Low PH of
boiler water.atmoic hydrogen migrates into tube wall,reacts with carbon
in steel and causes intergranular separation.
Stress corrosion cracking:brittle type crack.mostly with austenitic
stainless steels.occurs when high tensile stresses and corrosive fluid
are present.protective magnetite layer is destroyed on ID,exposing tube
to corrosion.

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