SM

QUESTIONS
AND ANSWERS

Phosphate Hideout
What is phosphate hideout?
Phosphate hideout is a phenom-
enon that causes boiler water
control difficulties. It is defined as
the disappearance, by precipita-
tion or absorption, of the ionic
phosphate (PO4) species, in the
boiler water under high heat
transfer or high load conditions.
When the high heat flux or high
load condition is reduced, the
species (phosphate) returns from Figure 1 — Normal congruent
phosphate-pH boiler chemistry.
hideout, creating even more Figure 2 — Phosphate hideout caused
control difficulties. The magnitude by lower combustion zone.
of phosphate hideout and the
variation in load required to cause During phosphate hideout, little
the phenomenon vary from one or no change in phosphate and/or The best way to recognize phos-
pH values occurs when chemical phate hideout is to graph load
boiler to another.
charges are added to the system changes, pH, and phosphate over
Phosphate hideout is primarily a since fresh phosphate may precipi- a period of time. The variations of
result of a temperature-dependent tate along with that which has the graphs will clearly indicate
interaction of sodium phosphate already occurred. The readings for that the phosphate increases with
compounds with iron oxide, pH and phosphate are typically decreasing load, and that the pH
which creates a low solubility out of control during hideout decreases with decreasing load
reaction product that precipitates when the load is increased, and (see Figures 1 and 2).
in high heat flux areas or under then again when it is decreased. Load pH Phosphate
high load conditions. At lower While it seems that the phosphate Increasing Increases Decreases
loads and lower heat fluxes, the has mysteriously disappeared, and Decreasing Decreases Increases
precipitates return to solution. that additional charges are unsuc-
cessful in increasing the phosphate
reading, the actual phosphate What causes phosphate hideout?
How do I recognize it? inventory in the boiler has not Events which may lead to phos-
Phosphate hideout becomes decreased. It has combined with phate hideout include:
evident in load swings or start-ups oxide deposits to form a slightly
with changing heat input. As the lower Na/PO4 ratio solid (approxi- • Start-up after a chemical cleaning
load is increased, the pH increases mately 2.1:1), causing an increase
with the decreasing phosphate. in alkalinity in the liquid phase • Changes in unit load
When the load is reduced, the pH (bulk water) — hence the boiler • Changes in burner configuration
decreases and the phosphate water pH increases. When the load
increases, without chemical is decreased again, these combina- • Metal oxide ingress and
additions to the boiler. tions return to the soluble form deposition on heat transfer
and the phosphate returns to the surfaces
bulk water, causing higher phos-
phate readings and lowered pH.
Does the hideout vary? What are the consequences of
Recently, a utility boiler
Each boiler, due to design and experienced severe furnace tube phosphate hideout?
cleanliness factors, will exhibit Phosphate hideout causes confu-
corrosion on the hot side of the
somewhat different magnitudes sion, frustration over uncontrol-
of hideout. The cleaner the boiler, tubes. The corrosion was trans-
granular in nature and quite
lable water chemistry, and corro-
the less likely hideout will be for sion. Some phosphate-related
operating units. For units that extensive. Along the corroded corrosion may be severe.
have just been cleaned, the hide- areas, large quantities of sodium
out phenomenon may temporarily iron phosphate were found,
The frustration resulting from
appear severe as phosphate is uncontrollable water chemistry
indicating that sodium phos- may be quite high. As lab techni-
consumed to re-establish the
equilibrium between the boiler phate from the boiler water had cians try to maintain the Na/PO4
water and the iron oxide or heat participated in the corrosion ratio while hideout occurs, the
transfer surfaces, since phosphate- mechanism. resultant situation is often non-
based passivation solutions are productive. Significant amounts of
not typically used for post-clean- time and money may be spent to
ing passivation. try to regain control. Those whose
phosphate hideout problems are
Acidic forms of phosphate should severe will undoubtedly be out of
How do I treat it? not be used in an attempt to control more than they are in
increase the phosphate reading. control as the unit cycles. Adding
To treat phosphate hideout effec- The most acidic form of phosphate
tively, you must first recognize it. more phosphate to the boiler only
is monosodium phosphate. makes the problem worse. The
The situation will be greatly
increased if there is not consistent During start-ups, use mainly tri- frustration of being out of control,
recordkeeping and graphing being sodium phosphate. wondering if corrosion is occur-
done. Once the phosphate hideout ring, and choosing the best solu-
Do not go to heavy blowdown. tion can be very irritating and lead
is recognized, treatment steps may This will further reduce the
be implemented. to expensive mistakes.
sodium:phosphate ratio. It will
The impulsive reaction to hideout also make the condition which The consequences of corrosion,
is to add more phosphate to try to causes the hideout to worsen by frustration, and confusion lead to
correct the low readings. This is allowing acidic conditions to one final conclusion: phosphate
inadvisable, however, since occur. hideout costs money.
adding more chemical will only Keep the phosphate at the lowest
worsen the situation when the end of the allowable range. This How do I prevent hideout?
load is reduced (see Figure 3). will vary from boiler to boiler and
may have to be determined over a Based on work done by J. Stodola
period of time. of Ontario Hydro, equilibrium
phosphate treatment is recom-
Since this equilibrium level of mended for units experiencing
phosphate might be quite low, <1 phosphate hideout to alleviate
ppm for a high pressure boiler, be corrosion risks and to reduce
alert for conditions that may boiler cleaning requirements.
indicate a condenser tube leak. As Figures 4, 5, 6 and 7 depict,
High sodium, silica, and cation reducing the phosphate level in
conductivity are all indicators of a the boiler water greatly reduces
condenser tube leak. variability with load changes, and
may eliminate the hideout phe-
Figure 3 — Changes in concentrations nomenon in many boilers.
of phosphate with load in unit that is
experiencing chemical hideout.
Figure 4 — 5.0 ppm PO4 @ approximately full load. Figure 6 — 1.5 ppm PO4 @ approximately full load.

Figure 7 — 1.1 ppm PO4 @ approximately full load.

Figure 5 — 1.8 ppm PO4 @ approximately full load.

Since phosphate hideout is a Table 1 — Equilibrium phosphate Figures 1 and 2, Table 1 — ©1991. Electric Power
Research Institute. EPRI TR-100195. Proceedings:
phenomenon associated with treatment chemistry control limits* International Conference on Fossil Plant Cycle
precipitation of phosphate/metal at 2600 psig [179 barg] Chemistry. Reprinted with permission by EPRI and
solids in areas of deposits on heat Control
J. Stodola, Ontario Hydro, Toronto, Ontario,
Canada.
transfer surfaces, it follows that Parameter Limit
adequate oxygen control and Figure 3 — Originally presented at the 47th Annual
passivation of metal surfaces is pH 9.0–9.6 International Water Conference, October 27–29,
important in the prevention of PO4 (ppb) 0–2400 1986, Pittsburgh, PA. Reprinted with permission
Cation Conductivity (µS/cm) ≤6.0 by Engineers' Society of Western Pennsylvania
phosphate hideout. Oxygen and J. Stodola.
Cl (ppb) ≤300
control efforts must be maintained SO4 (ppb) ≤300 Figures 4–7 — Reprinted with permission by
for many reasons, but in the case Silica (ppb) ≤160 American Power Conference, from 1991
of hideout, it is important to Proceedings.
control oxygen in the condensate *Pressure dependent
system so that corrosion products
are not deposited in the boiler.
The deposits can then interact
Phosphate hideout in high pres-
with phosphate during high heat
sure boilers can be recognized,
flux conditions to form sodium
and prevented by changing to an
iron phosphates.
equilibrium phosphate treatment
In units where phosphate hideout program. The savings will be seen
led to corrosion damage, Stodola in reduced operator frustration
notes that removing the minimum and a cleaner, less corroded boiler.
phosphate concentration limit and
allowing 1 to 2 ppm free caustic
alkalinity prevented further
corrosion. Table 1 shows equilib-
rium treatment control limits
(at 2600 psig [179 barg]).

NALCO CHEMICAL COMPANY ONE NALCO CENTER NAPERVILLE, ILLINOIS 60563-1198

SUBSIDIARIES AND AFFILIATES IN PRINCIPAL LOCATIONS AROUND THE WORLD

Registered Trademarks of Nalco Chemical Company ©1994,1996 Nalco Chemical Company

All Rights Reserved Printed in U.S.A. 8-96 Bulletin 268