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Boiler Water Analysis
Boiler Water Analysis
Boiler Water Analysis
Corrosion due to H+
O2 + 2H2O +4e
Differential aeration
With metals forming protective oxide films, the presence of dissolved O2 will enhance oxide formation making the metal cathodic.Areas of higher O2 conc. will be more cathodic than areas of lower O2 conc. ex is boiler tubes, condenser tubes or in other situation where deposits can impede access of O2 to the underlying metal surface. Maintaining low O2 regime is important
Removal of O2:O2 + 2H2O +4e 4 OHcannot take place. Available H+ will be reduced atanode. If medium is alkaline, no H+ will be there & hence no corrosion.
Less corrosion Low dissolved O2 High pH
Acid
0.360.4 ppm
Alkali
As shown in the diagram, corrosion rate of steel is minimum at a point having pH of 9 to 12. At high temp above 360C & at high prs steel surfaces readily react with deaerated,alkaline water forming very stable iron oxide called magnetite. Fe + 2 H2O Fe 2+ + 2OH-+H2 3Fe2++ 4H2O Fe3O4 + 4H2
Phosphate treatment
Low, controlled levels of alkali to reduce phosphate hideout Low levels of potential acid forming impurities such as Cl High phosphate means high NaOH in boiler & steam causing corrosion in boiler & NaOH deposition & stress corrosion failure of turbine
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K at 25C Na+ (ppb) SO42- (ppb) DO2(ppb) Oil (ppb) N2H4(ppb) NH3 (ppb) pH at25C Crud Na+ (ppb)
3.5-4.5 <2 <2 <5 <200 2x DO2 <500 8.8-9.2 nil <5
CEPD CEPD CEPD Feed CEPD DAO DAO DAO Feed Steam
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Monitoring/control of feed pH
Always some losses of water & steam & ammonia from the steam-water circuit due to leakage Losses of ammonia from the circuit with the noncondensable gas removed from the condenser in order to maintain vacuum So, continuous monitoring of pH and/or K of CEPD & Feed to ensure that correct chemical conditions are being maintained
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Monitoring/control of feed pH
pH
4.2 3.6
ppm NH3
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Oxygen control
Low level of O2 in feed water avoids corrosion of economizer tubing minimize on-load corrosion of boiler tubing Physical deaeration: in condensate system through vacuum & at such temp & prs O2 solubility <50 ppb. Further deaeration could be achieved in the condenser by the injection of live steam in the bulk condensate in the bottom of the condenser ,producing a steam stripping effect in low pressure section of the feed system when the feed temp has been raised to 110-150C. Again steam stripping either by injecting live steam into the feed water or by spraying the feed water through an atmosphere of steam. The steam carrying the gas, extracted from the feed water ,is then vented to the main condensers. O2 level gets reduced to <10 ppb & frequently <2 ppb
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Oxygen control
Chemical deaeration: Last traces of O2 are removed. No solid dosing in feed as solid in boiler will increase. N2H4 Steam volatile Slightly basic Reacts readily with traces of O2 at above 150c producing only volatile or gaseous products: N2H4 + O2 N2 + H2O At higher temp:3 N2H4 4NH3 + N2
1. 2. 3.
4.
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Hide out
It is characterized by the steady loss of solutes from the boiler water on high load, reappearing when load is sharply reduced or when boiler is taken off load. This effect is observed with all soluble species in boiler water but is more pronounced with salts having low solubility in boiler water temp operating in high heat fluxes. Presence of porous oxide layers on tube surfaces or presence of crevices enhances hide out. Mechanism :wick boiling (cont)
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Hide out
1) 2) 3) 4) Initially pores & crevices are flooded with boiler water containing dissolved salts & alkali. When boiling occurs, water comes out as steam leaving behind conc. solution. As the pores approach dryness, the volume of steam produced falls away & the pores are re-flooded with boiler water & the cycle is repeated. This cycle will repeat indefinitely when the heat flux is applied on that section resulting in the deposition of less volatile salts like Na3PO4,NaCl,CaSO4 or the formation of very conc. solution of the more soluble salts or alkalis like NaOH. Conc. hike order 104 to 105 Corrosion rate conc. hike oxide layer thickness (cont)
5)
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Hide out
6) The oxide layer gradually thickens with increasing period of operation e.g. the oxide growth rate ~15m per 10000 hrs Cleaning of boiler tubes when oxide layer thickness reaches 50-100 m. The actual qty of deposited salts are much smaller & so doesnt affect heat transfer & the hide out of neutral salts (that dont produce any acid/alkali on hydrolysis when get concentrated) like Na2SO4, CaSO4, SiO2 do not pose any risk when oxide thickness is within limit because they dont attack oxide layer. Other salts (Na3PO4, Cl- of NaCl) produce strong acid/alkali attacking oxide layer & underlying metal & causing serious corrosion. Acid corrosion is more prevalent. Hence, maintaining of boiler water parameters.
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7)
8)
9)
Caustic attack
NaOH can concentrate up by hide out. TSP hydrolyses to produce NaOH. If at the same time TSP hides out NaOH gets concentrated because reverse rk cannot take place. Iron oxides have high solubility in such conc. NaOH solution & protective oxide film dissolves away & is carried away into the bulk boiler water leaving very little corrosion product in the corroding area. The overall effect is formation of clean corrosion pits in the tube surface----Caustic gouging.
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Scale formation
A scale is a deposited layer of slightly soluble salt formed on a heat transfer surface when the solubility limit of the salt is exceeded This can occur when boiler water, containing salts with inverse temp coeff of solubility, comes into contact with boiler tube surfaces having temp substantially higher than the bulk boiler water It can also occur when the prevailing boiler water chemistry leads to conversion of a soluble to a less soluble compound (cont)
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Effect of scale
Scale formation on boiler tube causes loss of heat transfer & hence a loss of boiler output If the scale thickness is allowed to increase it causes serious overheating & failure of boiler tube without any associated corrosion Deposition mechanism: scales consist of Ca &/or Mg combined with SO42-, CO32- or PO43- & may also contain silica (SiO2). These impurities enter the boiler as low (cont)
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Deposition mechanism
Level impurities in feed water, largely as soluble salts , & slowly accumulate in the boiler water. If this process is allowed to continue, the solubility limits of a particular salt will be exceeded & that salt will then deposit. Ppt may take place in the bulk boiler water, but as these salt have inverse temp/solubility relationship, the deposition of the salt will take place preferentially on the heat transfer surfaces that are at a higher temp than the bulk boiler water. Once a substantial scale has formed on a boiler tube surface, it can often only be removed by chemical cleaning of the boiler. (cont)
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TSP advantage
Advantage of using TSP to maintain boiler water alkalinity is that when ingress of Ca or Mg salts occurs, the phosphate present rapidly converts them into relatively insoluble Ca/Mg phosphates in the bulk boiler water. The salts precipitate as a loose flocculent material, rather than a scale, & can be removed from boiler by blowing down.
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Steam purity
Upper limits of Na+ & SiO2 in steam are <5 &<20 ppb respectively. If limits are exceeded, deposition of Na-salts & silica in SH, RH & turbines In general, solubility of salts & silica in steam increases with increasing prs at const temp but decreases with increasing temp at const prs Conc of solute in steam
Kp = Conc of solute in water At a const temp & prs
Steam purity
1 Kp 10-1 10-2 10-3 10-4 10-5 10-6 10-7
226
220
200
160 140
100
50
40
30
Drum prs
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Steam purity
If boiler water impurity levels are not exceeded & NaOH in boiler is not high, then the eqm SiO2 conc. in steam <20 ppb & Na+ significantly lower than set limits. So, SiO2 & Na+ in steam indicates the impurities in boiler water. But, this is an ideal condition & impurities can enter steam in at least three ways: a) By evaporation of impurities from boiler water, evaporation rate depending on Kp b) By mechanical carry over of boiler water droplets to the sat steam, salts going forward into the SHs & turbine c) As impurities present in feed water used in desuperheater sprays
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From the graph, it is clear that silica has a much higher Kp than other salts & so appears in steam at a much higher conc. for a given conc. in boiler water. As the steam passes through the turbine, steam pressure gets reduced & is least at LP turbine & study shows that solubility of SiO2 in steam over the range of temp & prs in operating turbines decreases with decreasing prs & SiO2 gets deposited on turbine blades (esp LP blades). No such deposition when steam SiO2 < 20 ppb. Such silica deposit causes serious loss of output because, then it is necessary to take turbines out of service & remove such deposits. (cont)
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1.6
1.4
1.2 0.8
P
M
0.4
0
90
170
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2)
3)
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Na2SO4 deposition in RHs:Though its conc. is very low as seen fron Kp graph, its conc. in steam could increase by mechanical carry-over of low qty of boiler water & then as the steam leaves the HPT & passes through the RHs due to increase in temp there is significant decrease in the salt solubility sufficient for its deposition
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THANK YOU
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