Hydrex Experts
Hydrex Experts
Phosphate Hide-Out in Boilers
Phosphate treatment is used in most drum-type
boilers for pH control and protection against scale. It
is, however, difficult to control in transient situation.
Changes caused by hideout, and variations in water
volume, affect the phosphate concentration. Not all
boilers experience phosphate hideout. Whether or
not it will occur and depend on the relationship
between phosphate concentrations, metal
temperatures, and the availability of concentrating
sites and deposits. Hideout is the apparent loss of
chemical inventory in a steam generator during an
increase or decrease in power and subsequent
recovery upon a decrease in power.
What is Phosphate Hideout?
A mechanism relates to the change in solubility of
phosphate and disappearance by precipitation or
adsorption, during conditions of increased or
decreased heat flux (Load / temperature)
When hideout happens?
Hideout usually noticed during load changes, when a
suitable concentration of phosphate is present in bulk
water at high temperature, this phosphate will react
with boiler scale forming iron and its oxides. This soft
sludge will be drained or precipitate to form a solid
phase on boiler tube surface or elsewhere and this
phenomenon can result change in pH as well as
concentration. Consequently during load increment
(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.
WATER TECHNOLOGIES
The severity of phosphate hideout mainly depends
on: boiler design, heat flux, pressure, temperature
and specifically on cleanliness. In clean and
conservatively designed boilers these flux swings do
not result in any tube corrosion or deposition
problems.
How to understand ‘Na’ to ‘PO4’ ratio to avoid
hideout?
A widely used approach for high pressure boilers is
high purity feed water, which is balanced by alkalinity
control with pH range of 9-11 so that a protective
magnetite film can form, as per ‘Schikorr’ reaction.
3Fe + H2O → Fe3O4 + H2
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Phosphate treatment has gone through various
stages of evolution. The “Coordinated Phosphate
Treatment” was based on the specifications by
‘Whirl and Purcell’[1] who defined pH-phosphate
concentration conditions which would prevent the
existence of free alkalinity while maintaining the high
pH necessary to minimize corrosion. However, the
phenomenon of “hide-out”, local deposition of
sodium phosphates on boiling - caused free caustic
to be generated in the boiler water when using the
coordinated phosphate treatment. Studies by ‘Ravich
& Shcherbakova’ on the solubility equilibria in sodium
phosphate solutions showed that precipitation from
sodium phosphate solution was incongruent.
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As shown in above figure ‘PO4‘ molar ratio of the
precipitate did not correspond to that of the solute in
the solution, except at a certain composition the
congruence point. The congruence point composition
corresponded to Na/Po4 = 2.86 for the conditions
studied. Above the congruence point precipitation
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
improved water treatment method - the “Congruent
Phosphate Treatment” (CPT) in which the sodium
to phosphate molar ratio in the water is
maintained lower than that corresponding to the
congruent composition. Studies by ‘Pansonet’
indicated a lower congruent point as well at a Na/PO4
ratio of 2.15. Further, the Na/P04 ratio in solution
remained at 2.15 to 2.8. Hide-out from solutions in
which the Na/PO4 ratio is less than 2.15 would
lead to increasingly acid conditions in the
solutions and more than 2.8, then caustic corrosion
may occur. The ratio shifts the equilibrium from one
type of phosphate to another, accompanied by a pH
shift. Load swings can make control difficult.
What are the reactions happen during normal
operation and hideout?
Mono-sodium phosphate can also lower pH of boilers
water by generating hydrogen ions as shown in
equation [1]
NaH2P4 + H2O → 3H + + PO4 3− + OH− + Na+ − [1]
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
Na/PO4 ratio below 2.0 the addition of di-sodium or
mono-sodium phosphate, could result in the
formation of strongly acidic environment that will
react with both magnetite film and the base metal [1],
as shown in equations ( 5 and 6)
2Na2HPO4 + Fe3O4 → NaFePO4+ Na3PO4+Fe2O3+H2O
[5]
2Na2HPO4 + Fe +1/2O2 → NaFePO4 + Na3 PO4 + H2O [6]
The fact that hydrogen evolution can result from both
caustic gouging and acidic phosphate attack requires
a rigid operation control and a good monitoring
schedule.
How to mitigate hideout by phosphate balance?
When using phosphate boiler water treatment, the
concentration of phosphate should not exceed
the equilibrium concentration. This is the
maximum concentration of PO4 in the boiler water
that the boiler can tolerate under the highest heat flux
conditions (full load). This concentration can be
experimentally determined by increasing the
phosphate feed to the point where there is no further
increase in the PO4 concentration in the boiler
water. This is the equilibrium concentration and the
normal boiler water phosphate maximum limit should
be approximately one-half of this concentration.
The equilibrium phosphate concentration should be
determined once per year because it changes with
the boiler cleanliness. In addition, a phosphate
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balance should be performed once per year using
several weeks of chemistry data to determine the
amount of hideout that is occurring. The total amount
of phosphate fed into the boiler and the amount being
removed through blowdown, plus sampling, should be
approximately equal. If the feed is greater than the
removal, hideout is occurring.[6]
This is the well-known coordinated phosphate
diagram. It has been published in many different
forms, but program operating principles remain the
same. The diagonal black and red lines in Figure are
lines of constant Na/PO4-3 mole ratio. A good program
is controlled between 2.3:1 and 2.8:1 mole ratio. The
objective to avoid hideout during phosphate treatment
is to buffer the pH so that there can be no free caustic
in the boiler water. Localized boiling sometimes
causes precipitation of boiler solids on tube surfaces.
Water trapped beneath these deposits can become
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very concentrated. Avoiding free caustic in the water
helps to ensure that caustic gouging of steel will not
occur in these situations. For this reason, equilibria
understanding of particular boiler is most important
and the maximum boundary line in Figure shows a
Na:PO4 mole ratio of maximum 3.0 beyond this
hideout will occur.
The data points in Figure are from three boilers
operating in parallel in a 900 psig cogeneration plant.
Although most of the data points are within the control
box, overall control of the coordinated phosphate
program in this plant was poor. All three boilers operated
at times below the minimum Na:PO4 ratio, above the
maximum phosphate level, and well into the free caustic
range. This is not acceptable control, and over time,
serious phosphate deposits, caustic gouging corrosion
and boiler tube failures developed in this plant
Attempts to prevent hideout by very closely controlling
boiler water chemistry are usually fruitless and may
make the problem worse. It is best to stay well within the
control ranges in Figure, and to use as low a total
phosphate level as possible while still maintaining good
pH buffering in the water.
Phosphate hideout, how can we cope?
• The treatment of boiler water by congruent
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
equilibrium phosphate control all the time.
• If frequent change of load is happening in your
boiler, do not feed mono-sodium phosphate in
boiler as it’s more acidic than typical di or tri
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.
References:
1. Purcell, T.E. and Whirl, S.F., Protection against
caustic embitterment by coordinated phosphate pH
control, Transactions of The Electrochemical
Society, 83, pp279295 (1943).
2. Marcy, V.M. and Halstead, S.L., Improved basis for
coordinated phosphate pH control of boilers water,
Combustion, 45, pp 4547 (1964).
3. Economy, G. et al., Sodium phosphate solutions at
boiler conditions: Solubility, phase equilibria and
interactions with magnetite, Proceeding of 35th
International water Conference, pp 161173,
Pittsburgh (1975)
4. Jonas, O. and Layton, K.F., Phosphate boiler water
treatment for high pressure boilers, Proceeding of
Second Fossil Plant Cycle Chemistry Conference,
Seattle, GS-6166, Aug(1988).
5. Layton, K.F., Water side corrosion in the water wall
tubes of hunter unit 3, Proceeding of EPRI
Conference on Boiler Tube Failures in Fossil Plants,
EPRI – 1890, pp2-272 to 2-286, Nov.(1987).
6. Principles of industrial water treatment, second
edition, Pub. Drew Chemical Corporate, USA, p
221(1978).
7. Tremaine, P.R., et al., Phosphate interactions with
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metal oxides under high pressure conditions,
Proceeding of 54th International Conference,
pp.186- 196, Pittsburgh(1993).
Written by:
Muhammad Zeeshan Ahmad
Chemical (WT) Engineer
www.linkedin.com/in/muhammad-zeeshan-ahmad-
82507750
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