Hydrex Experts

Hydrex Experts
Phosphate Hide-Out in Boilers
Phosphate treatment is used in most drum-type The severity of phosphate hideout mainly depends
boilers for pH control and protection against scale. It on: boiler design, heat flux, pressure, temperature
is, however, difficult to control in transient situation. and specifically on cleanliness. In clean and
Changes caused by hideout, and variations in water conservatively designed boilers these flux swings do
volume, affect the phosphate concentration. Not all not result in any tube corrosion or deposition
boilers experience phosphate hideout. Whether or problems.
not it will occur and depend on the relationship
between phosphate concentrations, metal How to understand ‘Na’ to ‘PO4’ ratio to avoid
temperatures, and the availability of concentrating hideout?
sites and deposits. Hideout is the apparent loss of
chemical inventory in a steam generator during an A widely used approach for high pressure boilers is
increase or decrease in power and subsequent high purity feed water, which is balanced by alkalinity
recovery upon a decrease in power. control with pH range of 9-11 so that a protective
magnetite film can form, as per ‘Schikorr’ reaction.
What is Phosphate Hideout?
3Fe + H2O → Fe3O4 + H2

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A mechanism relates to the change in solubility of
phosphate and disappearance by precipitation or Phosphate treatment has gone through various
adsorption, during conditions of increased or stages of evolution. The “Coordinated Phosphate
decreased heat flux (Load / temperature) Treatment” was based on the specifications by
‘Whirl and Purcell’[1] who defined pH-phosphate
When hideout happens? concentration conditions which would prevent the
existence of free alkalinity while maintaining the high
Hideout usually noticed during load changes, when a pH necessary to minimize corrosion. However, the
suitable concentration of phosphate is present in bulk phenomenon of “hide-out”, local deposition of
water at high temperature, this phosphate will react sodium phosphates on boiling - caused free caustic
with boiler scale forming iron and its oxides. This soft to be generated in the boiler water when using the
sludge will be drained or precipitate to form a solid coordinated phosphate treatment. Studies by ‘Ravich
phase on boiler tube surface or elsewhere and this & Shcherbakova’ on the solubility equilibria in sodium
phenomenon can result change in pH as well as phosphate solutions showed that precipitation from
concentration. Consequently during load increment sodium phosphate solution was incongruent.
(high temperature) phosphate concentration will
decrease and pH will increase, while during load
reduction (low temperature) phosphate concentration
will increase and pH will decrease, these conditions
are called hideout and hideout return respectively.

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Hydrex Experts

As shown in above figure ‘PO4‘ molar ratio of the 2Na2HPO4 + Fe +1/2O2 → NaFePO4 + Na3 PO4 + H2O [6]
precipitate did not correspond to that of the solute in
the solution, except at a certain composition the The fact that hydrogen evolution can result from both
congruence point. The congruence point composition caustic gouging and acidic phosphate attack requires
corresponded to Na/Po4 = 2.86 for the conditions a rigid operation control and a good monitoring
studied. Above the congruence point precipitation schedule.
increased the Na/P04 ratio and hence also the
alkalinity of the solution. ‘Marcy and Halstead’ on
the basis of the Russian study, suggested an How to mitigate hideout by phosphate balance?
improved water treatment method - the “Congruent
Phosphate Treatment” (CPT) in which the sodium When using phosphate boiler water treatment, the
to phosphate molar ratio in the water is concentration of phosphate should not exceed
maintained lower than that corresponding to the the equilibrium concentration. This is the
congruent composition. Studies by ‘Pansonet’ maximum concentration of PO4 in the boiler water
indicated a lower congruent point as well at a Na/PO4 that the boiler can tolerate under the highest heat flux
ratio of 2.15. Further, the Na/P04 ratio in solution conditions (full load). This concentration can be
remained at 2.15 to 2.8. Hide-out from solutions in experimentally determined by increasing the
which the Na/PO4 ratio is less than 2.15 would phosphate feed to the point where there is no further
lead to increasingly acid conditions in the increase in the PO4 concentration in the boiler
solutions and more than 2.8, then caustic corrosion water. This is the equilibrium concentration and the
may occur. The ratio shifts the equilibrium from one normal boiler water phosphate maximum limit should
type of phosphate to another, accompanied by a pH be approximately one-half of this concentration.
shift. Load swings can make control difficult.
The equilibrium phosphate concentration should be
What are the reactions happen during normal determined once per year because it changes with
operation and hideout? the boiler cleanliness. In addition, a phosphate

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balance should be performed once per year using
Mono-sodium phosphate can also lower pH of boilers several weeks of chemistry data to determine the
water by generating hydrogen ions as shown in amount of hideout that is occurring. The total amount
equation [1] of phosphate fed into the boiler and the amount being
removed through blowdown, plus sampling, should be
NaH2P4 + H2O → 3H + + PO4 3− + OH− + Na+ − [1] approximately equal. If the feed is greater than the
removal, hideout is occurring.[6]
The mechanism of alkalinity control of boilers water,
is based on reaction of di-sodium and mono-sodium
phosphate with free hydroxide generated by tri
sodium phosphate as shown in equations. Sufficient
di-sodium and mono sodium phosphate must be
available to combine with all free caustic in the boiler
water, which will result in prevention of caustic build-
up beneath deposits or within Crevices.

Na3 PO4 + H2O → Na2 HPO4 + NaOH [2]

NaH2 PO4 + NaOH → Na2 HPO4 + H 2O [3]
Na2HPO4 + NaOH → Na3 PO4 + H 2O [4]

Phosphate hideout at high heat flux area still occurs

that lead to a very significant shift of pH and
phosphate concentration with load. Since solubility of
phosphate increases progressively with a drop in This is the well-known coordinated phosphate
Na/PO4 ratio below 2.0 the addition of di-sodium or diagram. It has been published in many different
mono-sodium phosphate, could result in the forms, but program operating principles remain the
formation of strongly acidic environment that will same. The diagonal black and red lines in Figure are
react with both magnetite film and the base metal [1], lines of constant Na/PO4-3 mole ratio. A good program
as shown in equations ( 5 and 6) is controlled between 2.3:1 and 2.8:1 mole ratio. The
objective to avoid hideout during phosphate treatment
2Na2HPO4 + Fe3O4 → NaFePO4+ Na3PO4+Fe2O3+H2O is to buffer the pH so that there can be no free caustic
in the boiler water. Localized boiling sometimes
[5]
causes precipitation of boiler solids on tube surfaces.
Water trapped beneath these deposits can become
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Hydrex Experts

very concentrated. Avoiding free caustic in the water References:

helps to ensure that caustic gouging of steel will not
occur in these situations. For this reason, equilibria 1. Purcell, T.E. and Whirl, S.F., Protection against
understanding of particular boiler is most important caustic embitterment by coordinated phosphate pH
and the maximum boundary line in Figure shows a control, Transactions of The Electrochemical
Na:PO4 mole ratio of maximum 3.0 beyond this Society, 83, pp279295 (1943).
hideout will occur. 2. Marcy, V.M. and Halstead, S.L., Improved basis for
coordinated phosphate pH control of boilers water,
The data points in Figure are from three boilers Combustion, 45, pp 4547 (1964).
operating in parallel in a 900 psig cogeneration plant. 3. Economy, G. et al., Sodium phosphate solutions at
Although most of the data points are within the control boiler conditions: Solubility, phase equilibria and
box, overall control of the coordinated phosphate interactions with magnetite, Proceeding of 35th
program in this plant was poor. All three boilers operated International water Conference, pp 161173,
at times below the minimum Na:PO4 ratio, above the Pittsburgh (1975)
maximum phosphate level, and well into the free caustic 4. Jonas, O. and Layton, K.F., Phosphate boiler water
range. This is not acceptable control, and over time, treatment for high pressure boilers, Proceeding of
serious phosphate deposits, caustic gouging corrosion Second Fossil Plant Cycle Chemistry Conference,
and boiler tube failures developed in this plant Seattle, GS-6166, Aug(1988).
5. Layton, K.F., Water side corrosion in the water wall
Attempts to prevent hideout by very closely controlling tubes of hunter unit 3, Proceeding of EPRI
boiler water chemistry are usually fruitless and may Conference on Boiler Tube Failures in Fossil Plants,
make the problem worse. It is best to stay well within the EPRI – 1890, pp2-272 to 2-286, Nov.(1987).
control ranges in Figure, and to use as low a total 6. Principles of industrial water treatment, second
phosphate level as possible while still maintaining good edition, Pub. Drew Chemical Corporate, USA, p
pH buffering in the water. 221(1978).
7. Tremaine, P.R., et al., Phosphate interactions with

Bulletin-001- 2017
Phosphate hideout, how can we cope? metal oxides under high pressure conditions,
Proceeding of 54th International Conference,
• The treatment of boiler water by congruent pp.186- 196, Pittsburgh(1993).
phosphate in the equilibrium phosphate region
shown an effective protection of general, pitting
corrosion and prevention of scale deposition.
Study your boiler behavior and maintain Written by:
equilibrium phosphate control all the time.
Muhammad Zeeshan Ahmad
• If frequent change of load is happening in your Chemical (WT) Engineer
boiler, do not feed mono-sodium phosphate in www.linkedin.com/in/muhammad-zeeshan-ahmad-
boiler as it’s more acidic than typical di or tri 82507750
sodium phosphate. Dose only 1 PPM of sodium
hydroxide if required.

• Reduction of added sodium hydroxide to

congruent phosphate and Na/PO ratio will prevent
caustic cracking and gouging and acid phosphate
attack for high pressure boilers.

• Reduce flow disruptions in tubes, Reduce burner

impingement. Limit or eliminate phosphate feed
during hide out condition and do not feed
phosphate below or over to Na: PO4 ratio.

• Evaluate the loss pf phosphate from the system

by material balance calculation-chemical feed,
feed water and blowdown.

• Chemically clean the waterside to remove deposit

build-ups. The more iron present the more
phosphate uptake and degree of chemistry
change will abrupt boiler efficiency in longer run.

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