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Published by Ravi Deshmukh

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Published by: Ravi Deshmukh on Jun 28, 2012
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 Water Services © 2004 - All rights reserved
 Water Services © 2004 - All rights reserved
phosphate hideout
"Phosphate hideout" and "chemical hideout" are terms used to describe the loss of boiler waterphosphate residual that accompanies this solid phase formation problem.The phosphate hideout phenomenon can pose a significant chemistry control problem in highpressure boilers that experience load variations.Typically, phosphate tends to "disappear" as load (steaming rate load) is increased towardsmaximum. The pH will also vary, usually in an upward direction, although one would expect that thechange in pH would be consistent with the change in Na:PO4 ratio of the solution.The upward trend in pH may be explained by an interaction between phosphate and magnetite thatis also known to exist. Just as phosphate disappears with increasing load, so does it reappear withdecreasing load, with concurrent impact on the system pH. Dissolution of the solid phase occurs asload is reduced.Historically, "hide-out" had been regarded as an operating nuisance, which continually neededadditions of tri-, di-, and mono-sodium phosphates to keep the boiler water in the CPT control range.However, it has been recognized recently that serious corrosion (termed "acid phosphate corrosion")can result when these chemicals are added to boilers where "hide-out" and deposition are occurring.The acid phosphate corrosion also prompted Babcock & Wilcox to issue a service bulletin warning allutility customers of a potential chemistry control problem when using mono-sodium phosphate thatcould lead to serious furnace tube corrosion.Phosphate "hide-out" is characterized by the retention of phosphate in the boiler during conditions of high load, and its subsequent release when the load is reduced. Various studies of the pure sodiumphosphate water phase diagram suggest that "hide-out" is caused by the precipitation of sodiumphosphate phases at local hot spots and under deposits. Very high concentrations of phosphate accompanied by extreme pH excursions, may arise from incongruent precipitation reactions at local sites when "hide-out" takes place.The periods associated with severe pH depressions often correspond to times when the applied strainis the highest for corrosion fatigue at various locations throughout the boiler.
 Water Services © 2004 - All rights reserved
pH/phosphate programs
  A pH/phosphate program differs from a standard or residual phosphate program in that thephosphate is primarily added to provide a controlled pH range in the boiler water to provide abuffering counteraction against acid and caustic attack of the internal metallic surfaces, which isdescribed in more detail below. A pH/phosphate control program is very difficult and time consuming to control. The conventionalcontrol of such a program is normally based on many assumptions about feedwater phosphatedemand, actual boiler cycles and boiler feedwater sodium levels.Feedwater phosphate demand, as that terminology is used herein and generally understood in theboiler field, is phosphate that becomes insoluble within a boiler system, for instance upon theformation of insoluble phosphate species upon combination with calcium or iron ions, or which hides-out (discussed elsewhere) during system load transients. Feedwater phosphate demand is normally afairly steady value in a well controlled boiler system.
Caustic-Gouging Corrosion and pH/Phosphate Programs
  As noted above, when high purity standards govern feedwater quality, the internal water treatmentprogram of choice for control of scale deposition and corrosion within the boiler system is most oftena pH/phosphate program. Stringent feedwater standards are commonly employed for high pressureboilers, but not limited thereto.High pressure boilers are no longer restricted to utilities. The increasing cost of energy is makingcogeneration much more popular. The petrochemical, paper, and chemical industries now commonlyuse 1200-1800 psig boilers to provide cogeneration of both electricity and steam.Condensing and backpressure turbines are used to drive generators, compressors, and the like, whilesupplying extraction or exhaust steam for plant use. Waste-heat boilers receive heat from processstreams for the production of steam. These high pressure cogenerative and waste-heat boilers havefeedwater quality standards at least substantially comparable to that of high pressure utility boilers.In many cases, the initial design of high pressure waste-heat boilers may require even stricterfeedwater standards than a utility boiler of higher pressure. As boiler pressures and heat transfer rates have increased, water-side caustic corrosion of boilertubes (caustic gouging) has increasingly become a problem. Caustic gouging, or ductile gouging,starts to occur when caustic is allowed to concentrate against hot boiler metal surfaces, dissolvingthe normally protective magnetite.Normal boiler water hydrate alkalinity levels are harmless to boiler steel, but localized concentrationsof tens of thousands of ppm are very aggressive. At such points, the protective magnetite on the water-side surface of the boiler tube wall isdissolved, as shown in the following Equation 1.
Fe3O4 + 4 NaOH
Na2FeO2 + 2 NaFeO2 + 2 H2O
 Where the protective magnetite film is dissolved, the parent tube metal is exposed and is susceptibleto corrosion, as shown in the following Equations 2 and 3.Equation 2:
3 Fe + 4 H2O -> Fe3O4 + 4 H2
 Equation 3:
Fe + 2 NaOH -> Na2FeO2 + H2

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