BOILER WATER ANALYSIS

Boiler water chemistry

The corrosion of metals An electrochemical cell Daniel cell (Zn|ZnSO4||CuSO4|Cu) A single corrosion cell (Fe|NaCl|Cu)
Without O2 in alk medium slow corrosion rate as no H+ In O2 Atmosphere With alkaline mediumalso high corrosion rate due to ppt of Fe(OH)2

in neutral or acid solution

Corrosion due to H+

Without alkaline medium high corrosion rate 4 OH-

O2 + 2H2O +4e

Boiler water chemistry

Electrode potential: Cu 2+|Cu: 0.34 V & Zn 2+|Zn:(-)0.76 V. Cell pot:(+)1.10 V Galvanic corrosion: It is bimetallic corrosion. For practical purposes it is usual to take pairs of metals &/or alloys, and determine by observation which is anode & which is cathode in the solution under consideration. From the results, a table can be drawn up, giving a galvanic series for the particular environment.

Boiler water chemistry

The corrosion of single metals: Anodic & cathodic areas in a single metal. Protective oxide films Abraded,cracked,porous or thin (in one place) oxide films Less oxygenated area is anode & more oxygenated area is cathode. Ex:steel with protective oxide layer dipped in dil HCl & the same with abraded oxide layer.

Boiler water chemistry

The formation of anodic & cathodic areas is also promoted by lack of homogeneity in the metal due to surface imperfections, localised stresses etc. & may also be a result of variations in the local environment.

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

Factors controlling corrosion rates

Factors controlling corrosion rates

Corrosion rate

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

Formation of protective oxide films

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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Feed water treatment

Feed water is major source of impurities in boiler water. So, feed water treatment to reduce such impurities Insoluble impurities from corrosion of plant i.e. construction material of condensed & feed system & are very largely metal oxides & soluble impurities from cooling water leakage & corrosion of condenser. So feed water pH & hydrazine to reduce above corrosion. Feed water crud test & continuous monitoring of other parameters to control such impurities
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Feed water testing

parameter Range Analysis type Sample location

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

OL OL M OL M+OL M+OL M+OL OL M OL

CEPD CEPD CEPD Feed CEPD DAO DAO DAO Feed Steam
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Control of insoluble impurities in feed

pH of feed: 8.8-9.2 & N2H4(ppb)=2x DO2 to reduce plant corrosion & hence insoluble impurities for our ferrous & copper alloy system Any non-volatile salt present in feed will rapidly increase in conc. in boiler Such salts in feed could also lead to contamination of steam where spray desuperheaters are used So, volatile alkali like ammonia is used Ammonia is cheap, readily available & stable at high temp One disadvantage of ammonia because of its high volatility in steam & being weak alkali at high temp is that initial condensates formed at high temps (e.g. in feed heaters) may have relatively low pH values resulting in only limited protection from corrosion
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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

9.2 >9.1 9.0

0 0.4 0.5

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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Soluble impurities in feed water

These impurities reach boiler, excessive chloride will cause corrosion of boiler tubing. So feed impurity control. Excessive/modest conc. of Cl- & SO42- will increase boiler blow down leading to loss of (a) heat & (b) pure water Sources: Cooling water leakage of main condenser or other cooling systems. Immediate detection & rectification necessary Make up water quality deterioration: a particular situation arises with some raw waters having non-reactive silica & nonionic organic compounds which are not removed in water treatment & can cause rapid build up of SiO2 and/or Cl- & SO42- in boiler waters. Dosed alkalis such as ammonia, hydrazine, TSP. Monitoring: KH at CEPD & Feed & Na in CEPD (KH for Cl- & SO42- )
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Insoluble impurities in feed water

Mainly metal oxides & their production is controlled by maintaining low DO & high pH in feed & steam/condensate as discussed earlier. To determine the effectiveness of feed water conditioning, the levels of individual metals (Cu,Fe,Ni) in boiler & feed are determined regularly. Cu in CEPD regularly (if condenser is of Cu). Inferences: (1)Cu results in CEPD can give early indication of corrosion problems on the steam side of the condensers.(2) if changes are made to the chemical treatment regime of feed, the cu level change in condenser will indicate the effectiveness of the change.(3) feed crud level increase will indicate corrosion problem & decrease will indicate deposition problem.(CONT)
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Insoluble impurities in feed water

During plant start up after a period of off-load or following sharp changes of feed water flow rates, the debris levels may be very much higher than normal. To prevent these debris from passing to boiler would need the putting of large quantity of water to drain. To get rid of this, filters/CPUs as filters are used.

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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)

Acid chloride corrosion

Boiler Cl- levels are closely monitored & the aim is to maintain a modest excess of alkali assuming that all the Cl- could be converted to acid. The formation of acid can occur in two ways: 1) When contaminants (from feed or condensate) leaking into the boiler water contain hydrolysable chloride (MgCl2, CaCl2) producing HCl 2) MgCl2 + H2O MgO + 2HCl 3) By interaction of neutral NaCl with an oxidizing agent. Oxidizing agents can be high DO or transition metal oxides (variable valence) like copper oxide. In high heat flux zones the acid solutions can concentrate in the porous oxides, attacking the protective oxide & then the underlying metal Fe3O4 + HCl FeCl2 + FeCl3 + H2O(1 ) Fe + 2HCl FeCl2 + H2 (cont)
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Acid chloride corrosion

Under operating conditions the chlorides are not stable & as they diffuse away from corrosion site rk (1) is reversed leading to reformation of HCl & further attack. The rk sequence produces the rapid thickening of the iron oxide layers which in turn increase the effects of hide out The net effect is rapid attack of the boiler tubing with the formation of thick non-protective iron oxide layers on the corrosion site. Hydrogen embrittlement: hydrogen formed in the corrosion process converts the carbon of steel to methane. This reduces ductility of steel & in extreme cases thick section failure can occur i.e. large pieces are blown out of the tubing.
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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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Stress corrosion cracking

Tube failures resulting from increase in local concentration of dissolved salts may be due to stress corrosion cracking Stress corrosion requires the tube metal to be in a highly stressed condition-----(a) due to operating conditions, (b) residual stress in the tubing & structural constraints Stress corrosion is not so frequent but when occurs, the crack moves through the grain boundaries & penetrates the tube very rapidly Stress corrosion can occur in acid or alkaline solution but has been found to be more frequent in conc. alkali such as NaOH.
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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

& the changes in Kp with prs is as follows:

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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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Effects of high steam impurities

Excessive conc. of SiO2 or Na+ in steam leads to 1) Reduced turbine performance 2) Serious corrosion of super heaters, reheaters & turbines

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Effects: silica in steam

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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Effects: silica in steam

Kp of SiO2 is substantially reduced by the presence of solid alkalis (NaOH) in boiler water due to the formation of silicates. This data along with data where no solid alkali is used, working curves have been prepared indicating the maximum conc. of SiO2 in boiler water that can be tolerated if the steam is to contain <20 ppb SiO2

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Effects: silica in steam

1.8 S I L I C A P

1.6
1.4

1.2 0.8

P
M

0.4
0

90

130 BOILER PRESSURE

170
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Effects: silica in steam

Under normal operating conditions, SiO2 in boiler can be controlled by blow down but, when a boiler is returned to service after overhauling or outage for boiler tube repairs, as a result of silica rich debris left behind in the water side of the boiler (e.g. insulating material, coal ash ) the boiler can be safely operated for restricted periods with SiO2 in steam up to 50 ppb because then even extensive blow down cannot control SiO2 level. However, if high SiO2 level persists, the boiler should be operated at reduced prs & load until normalization.

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Effects: sodium salts in steam

Even within limit in steam, some Na deposition occurs on the surfaces of SH tubing but, this cannot destroy the protective oxide layer. If excessive levels of Na are persistently present in steam, a no of problems could result depending on the actual levels of impurities present & their nature i.e. whether it is NaOH or natural salts such as Na2SO4

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Effects: sodium salts in steam

NaOH in austenitic super heater---stress corrosion: the substantial increase in steam temp in the SHs results in the reduction of solubility of salts in steam & their deposition on tube surfaces. If Na in steam is NaOH/NaCl, then the deposited NaOH/NaCl being highly soluble in water can form conc. solution which at high SH temp causes serious stress corrosion cracking. a) O2 needs to be present with conc. NaOH or NaCl solution b) Metal area should be in a stressed condition such as residual stresses from fabrication or stresses due to operating conditions.
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Effects: sodium salts in steam

1) Deposition of Na salts in turbines: As superheated steam passes through the HP turbine, due to fall in prs solubility of salts in steam reduces causing their deposition on the metal surfaces of the turbines. The deposition of NaOH or NaCl could result in, as in SHs, stress corrosion failures. In general, due to sharp fall of prs in turbines unlike SHs decrease of salt solubility is more significant & so if steam Na+ exceeds limit slightly but persistently there will be deposit In HP turbines deposition is less, having deposition of only salts of very low solubility e.g.Na2SO4. In lower prs stage more deposition.

2)

3)

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Effects: sodium salts in steam

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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