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Corrosion found in the Boiler and feed systems

Corrosion and tube failure caused by water chemistry
Metals obtained from their oxide ores will tend to revert to that state. However, if on
exposure to oxygen the oxide layer is stable, no further oxidation will occur. If it is
porous or unstable then no protection is afforded.


Iron+O2 --- magnetite (stable and protective) + O2----ferrous oxide

Two principle types of corrosion
Direct chemical-higher temperature metal comes into contact with air or other
gasses (oxidation, Sulphurisation) Electrochemical-e.g. Galvanic action, hydrogen
evolution, oxygen absorption

Hydrogen Evolution (low pH attack)

Valency = No of electrons required to fill outer shell

The Protective film of hydrogen gas on the cathodic surface breaks down as the hydrogen combines and bubbles off as diatomic hydrogen gas. Acidic water has an excess of hydrogen ions which leads to hydrogen evolution For hydrogen absorption to occur no oxygen needs to be present. Oxygen Absorption (high O2 corrosion) .Pure water contains equal amounts of hydrogen and hydroxyl ions. a pH of less than 6. Impurities change the balance.5 and so an excess of free hydrogen ions is required.

the area under a deposit being deprived of oxygen become anodic. More common in horizontal than vertical tubing and often associated with condensers. in soot blower lines where vibration stresses are developed .l.pH between 6. -Usually due to poor shape -In HP boilers found also in screen and generating tubes and in superheater tubes after priming. at oxygen pits in waterline or feed water lines. Once started this type of corrosion cannot be stopped until the rust scab is removed. Trans crystalline more in depth: Occurs in any location where cyclic stressing of sufficient magnitude are present Rapid start up and shut down can greatly increase susceptibility. desecrators. One special type is called deposit attack. Leads to pitting. end of the membrane on water wall tubes. and in blow down lines.10. in welds at slag pockets or points of incomplete fusion . either by mechanical means or by acid cleaning. economizers. Boiler corrosion Common in boilers having an open feed system. -Most serious form of corrosion on the waterside Pitting -Often found in boiler shell at w. Common in wall and superheater tubes. Also common on areas of rigid constraint such as connections to inlet and outlet headers Other possible locations and causes are in grooves along partially full boiler tubes (cracks normally lie at right angle to groove ). . . General Wastage . Oxygen present. at points of intermittent steam blanketing within generating tubes. Corrosive environment aggravates. Very troublesome and can be due to ineffective feed treatment prevalent in idle boilers. Corrosion fatigue cracking Cases found in water tube boilers where due to alternating cyclic stresses set up in tube material leading to a series of fine cracks in wall.

Concentrations of the corrodent may build up in a similar way to those caustic corrosion i. some soluble silica and a tensile stress is all that is required to form the characteristic inter-granular cracks in carbon steel. The combination of NaOH . The required stress may be applied ( e. thermal.e. superheater and reheat tubes and in stressed components of the water drum.40 % Failure is of the thick walled type regardless of ductility.Corrosion cracking (or caustic embrittlement) has all but been eliminated. welding) Boiler steel is sensitive to Na OH . Whitish highly alkaline deposits or sparkling magnetite may indicate a corrosion sight.g. bending etc. • • • • DNB Deposition Evaporation at water line And also by small leakage Caustic corrosion at temperatures less than 149oC is rare NaOH concentration may be as low as 5% but increased susceptibility occurs in the range 20.Caustic cracking (embrittlement) or stress corrosion cracking Pure iron grains bound by cementite (iron carbide).g. It can however be found in water tubes. . Occurs when a specific corrodent and sufficient tensile stress exists Due to improved water treatment caustic stress. ) or residual ( e. stainless steel is sensitive to NaOH and chlorides A large scale attack on the material is not normal and indeed uncommon.

. backing rings) Caustic ( or ductile ) gouging refers to the corrosive interaction of concentrated NaOH with a metal to produce distinct hemispherical or elliptical depressions. Avoid DNB .To eliminate this problem either the stresses can be removed or the corrodent. Caustic corrosion • • Takes place at high pressure due to excessive NaOH In high temperature. Magnetite layer broken down Soluble compound formed which deposits on metal as a porous oxide Local concentrations may cause a significant overall reduction in alkalinity. 3. high evaporation rates leading to local concentrations nearly coming out of solution and form a thin film near heating surface. Water cooled in regions of high heat flux Slanted or horizontal tubes Beneath heavy deposits Adjacent to devices that disrupt flow ( e. Depression is often filled with corrosion products that sometimes contain sparkling crystals of magnetite.g. The stresses may be hoop stress( temp'. Proper water treatment is essential. avoid undue deposits prevent leakage of corrodents. 4. Iron oxides being amphoteric are susceptible to corrosion by both high and low pH environments. pressure) which cannot be avoided bending or residual weld stresses which must be removed in the design/ manufacturing stage. prevent carryover. • • • • More in depth: Generally confined to 1. Avoidance of the concentrations of the corrodents is generally the most successful. 2. If evaporation rate reduced alkalinity restored.

Departure form nucleate boiling (DNB) ii.) Method of concentration. ( e. • • the availability of NaOH or of alkaline producing salts. intentional by water treatment or unintentional by ion exchange resin regeneration.e. and at higher still rate. Boiler water solids develop near the surface . The area under the film may be relatively intact.High pH substances such as NaOH dissolve the magnetite then attack the iron. i. . Evaporation i) Departure form nucleate boiling (DNB) Under normal conditions steam bubbles are formed in discrete parts. However on departure of the bubble rinsing water flows in and re-dissolves the soluble solids However at increased rates the rate of bubble formation may exceed the flow of rinsing water . a stable film may occur with corrosion concentrations at the edge of this blanket.g. i. The two factors required to cause caustic corrosion are. The magnetite layer is then attacked leading to metal loss. one of the following. Deposition iii.

high temperature hydrogen atoms diffuse into the metal. Usually occurs in regions of high heat flux. Deposition A similar situation can occur beneath layers of heavy deposition where bubbles formation occur but the corrosive residue is protected from the bulk water iii) Evaporation at waterline Where a waterline exists corrosives may concentrate at this point by evaporation and corrosion occurs.ii). Reduce free NaOH by correct water treatment Prevent inadvertent release of NaOH into system (say from an ion exchange column regenerator ) Prevent leakage of alkaline salts via condenser Prevent DNB Prevent excessive waterside deposits Prevent creation of waterlines in tubes.slanted or horizontal tubes are particularly susceptible to this at light loads were low water flows allow steam water stratification. Hydrogen attack If the magnetite layer is broken down by corrosive action. beneath heavy deposits. prevention's • • • • • • • Rifling is sometimes fitted to prevent DNB by inducing water swirl. combine with the carbon and form methane. in slanted and horizontal tubes and in heat regions at or adjacent to backing rings at welds or near devices that disrupt flow . more in depth: Generally confined to internal surfaces of water carrying tubes that are actively corroding. . Large CH-3 molecules causes internal stress and cracking along crystal boundaries and sharp sided pits or cracks in tubes appear.

Acidic water has an excess of hydrogen ions which leads to hydrogen evolution. steam drum internals most susceptible. or externally on superheater tubes Chelant corrosion Concentrated chelants ( i.P. of less than 70 bar A typical sequence would be . a pH of less than 6. it may be very smooth and coated with a glassy black like substance Horse shoe shaped contours with comet tails in the direction of the flow may be present. • • • • • • • NaOH removes the magnetite free hydrogen is formed ( hydrogen in its atomic rather than diatomic state) by either the reaction of water with the iron reforming the magnetite or by NaOH reacting with the iron This free hydrogen can diffuse into the steel where it combines at the grain boundaries to form molecular hydrogen or reacts with the iron carbide to form methane As neither molecular hydrogen or methane can diffuse through the steel the gasses build up . A surface under attack is free of deposits and corrosion products . . Impurities change the balance . high temperature in steam atmosphere. May occur due to heavy salt water contamination or by acids leaching into the system from a demineralisation regeneration.e. increasing pressure and leading to failure at the grain boundaries These micro cracks accumulate reducing tensile stress and leading to a thick walled failure. Alternately deep discrete isolated pits may occur depending on the flow and turbulence The main concentrating mechanism is evaporation and hence DNB should be avoided Careful watch on reserves and O2 prescience should be maintained Low pH attack Pure water contains equal amounts of hydrogen and hydroxyl ions . See previous notes on Hydrogen Evolution For hydrogen absorption to occur no oxygen needs to be present. Sections may be blown out.Uncommon in boilers with a W. The Protective film of hydrogen gas on the cathodic surface breaks down as the hydrogen combines and bubbles off as diatomic hydrogen gas. amines and other protecting chemicals) can attack magnetite .5 and so an excess of free hydrogen ions is required. where high pH corrosion has occurred the possibility of hydrogen damage should be considered High temperature corrosion. Loss of circulation . This form of damage may also occur in regions of low pH For boilers operating above 70 bar .

Entire boiler susceptible . The corrosion is of a similar appearance to caustic gouging Prevention is the same as for caustic attack . The boiler is then flushed with warm water until a neutral solution is obtained. in areas where water may accumulate then any trace oxygen is dissolved into the water and corrosion by oxygen absorption occurs( see previous explanation ) Oxygen Absorption in addition to notes above pH between 6. but most common in the superheater tubes (reheater tubes especially where water accumulates in bends and sags ) In an operating boiler firstly the economizer and feed heater are effected. However . Constant testing of dissolved iron and non ferrous content in the cleaning solution should be carried out.Localized attack may occur however where evaporation causes the concentration of acid forming salts . Proper maintenance of boiler water chemicals is essential Vigorous acid attack may occur following chemical cleaning . Once started this type of corrosion cannot be stopped until the rust scab is removed . One special type is called pitting were metal below deposits being deprived of oxygen become anodic . The ensuing pitting not only causes trouble due to the material loss but also acts as a stress raiser The three critical factors are . Oxygen corrosion Uncommon in operating boilers but may be found in idle boilers. either by mechanical means or by acid cleaning. Distinguished from other forms of pitting by its being found on all exposed areas Very careful monitoring whilst chemical cleaning with the temperature being maintained below the inhibitor breakdown point. In the event of severe contamination of oxygen areas such as the steam drum water line and the steam separation equipment In all cases considerable damage can occur even if the period of oxygen contamination is short Bare steel coming into contact with oxygenated water will tend to form magnetite with a sound chemical water treatment program. This helps to prevent surface rusting . Leads to pitting. Oxygen present. After acid cleaning a chelating agent such as phosphoric acid as sometimes used . The mechanism is the same as for caustic attack. Very troublesome and can be due to ineffective feed treatment prevalent in idle boilers. More common in horizontal than vertical tubing and often associated with condensers.10.

Tin has some improving effects Exfoliation (denickelfication) Normally occurs in feed heaters with a cupro-nickel tubing ( temp 205oC or higher) Very low sea water flow condensers also susceptible. Graphitization Cast iron . black) But holidays or cracks exist in the coating. antimony or phosphorus can be used . hence oxygen required to provide corrosion. but are ineffective at higher temperatures. Hence only possible at the lower temperature regions where the hydrazine is less effective or inactive. The copper travels to the boiler and leads to pitting. ii. ii. Nickel oxidized forming layers of copper and nickel oxide Ammonium corrosion Ammonium formed by the decomposition of hydrazine Dissolve cupric oxide formed on copper or copper alloy tubes Does not attack copper. corrodes and the copper is redeposited. this may be due to mechanical or thermal stressing. following acid cleaning surface covered by a marginally or non protective iron oxide such as Hematite (Fe2O3) The metal surface is covered with a protective iron oxide such as magnetite (Fe3O4 . ferrous materials corrode leaving a soft matrix structure of carbon flakes Dezincification Brass with a high zinc content in contact with sea water . . the prescience of water or moisture prescience of dissolved oxygen unprotected metal surface The corrosiveness of the water increases with temperature and dissolved solids and decreases with increased pH Aggressiveness generally increases with increased O2 The three causes of unprotected metal surfaces are i. However. FEED SYSTEM CORROSION. During normal operation the environment favours rapid repair of these cracks. iii.i. with high O2 prescience then corrosion may commence before the crack is adequately repaired. Inhibitors such as arsenic . iii.