Co-ordinated Phosphate treatment program and its control towards boiler

water chemistry

Need for Phosphate treatment - Deposition control

Deposition is a major problem in the operation of stream generating equipment. Deposition is
accumulation of material on boiler surfaces that can cause overheating as well as circulating restrictions.
Both conditions frequently result in unscheduled outages. Many solids, soluble in boiler feedwater,
precipitate in boiler water. This happens for one or both of two reasons. Change in water chemistry when
going from feedwater to boiler water conditions, and retrograde solubility characteristics of some salts.
Calcium, Magnesium, iron, copper, aluminum, silica and to a lesser extent silt and oil are common
contaminants in boiler feed water that can form deposits. Exact combinations in which they exist are
different from boiler to boiler and even location to location. The precipitation is however, usually
somewhat selective for any given boiler water chemistry. In one boiler, Scale may form as calcium silicate,
in another as sodium iron silicate. Salts are not totally insoluble in boiler water, But the lose solubility as
solution temperature increases, often precipitate directly on tube surfaces.
There are two basic methods of applying internal boiler water treatment for the control of
deposition. Chelent/dispersant and Phosphate/dispersant .One is a solubilising program and other is a
precipitation program.
Calcium sulfate scaling was major recognized problem in internal treatment of boiler water.
Sodium carbonate was the std precipitating agent used in internal treatment in past. Calcium carbonate is
less soluble than calcium sulfate and the objective was to precipitate calcium as calcium carbonate rather
than as calcium sulfate.
The driving force for the reaction is maintenance of the high concentration of carbonate ion in the
boiler water. As boiler pressure increases slowly around 200 psi, it becomes very difficult to maintain the
high concentration of carbonate ion in the boiler water due to the decomposition of carbonate ion at higher
boiler water temperature. Sodium carbonate decomposes in the boiler forming sodium hydroxide and
carbon dioxide. The CO2 leaves the boiler with the steam increasing the corrosivity of steam condensate.

Phosphate Control.
Phosphate ion does not decompose as does carbonate ion at higher boiler water
temperatures. This obvious advantage favors phosphate over carbonate, together with the fact that calcium
phosphate is more insoluble than calcium carbonate.
Calcium phosphate is virtually insoluble in boiler water. Maintaining even small levels of
phosphate will ensure the precipitation of calcium phosphate in mid-stream away from heating surfaces.
The introduction of phosphate treatment eliminated calcium carbonate scale.
When calcium phosphate is formed in boiler water of sufficient alkalinity (pH 11.0 to 12.0), a
particle of relatively non-adherent surface charge is produced. This is not to say that over a period of time
deposit accumulations do not develop, they do, but they can be reasonably well controlled with blowdown.
The introduction of phosphate-based boiler-water alkalinity control brought a major improvement
to the development of programs with pH control based upon free NaOH. The application of phosphate
either by itself, or in conjunction with caustic soda, could provide the elevated pH necessary to minimize
the corrosion of carbon steel. At the same time, the phosphate also provided sufficient chemical buffering
capacity to cope with small system upsets, e.g., a small condenser leak. Phosphate was also economical and
easy to use. While phosphate had the ability to significantly curtail incidents of caustic embrittlement and
caustic gouging damage, it could not totally remove the fear of having free hydroxide in excess of that
associated with Tri sodium phosphate. There was a need to get tighter control.

Coordinated Phosphate Treatment

Steam generating unit, supplied with deminerlised or evaporated makes up water, or pure
condensate may be protected from caustic centered damage by using general term Coordinated
pH/Phosphate control. Phosphate is a buffer in this program and limits the localized concentration of
caustic. Excess caustic combines with disodium phosphate and forms Trisodium phosphate. For the
program to work, It is esstional to have sufficient disodium phosphate available to combine with free
caustic to form tri sodium phosphate.
The hydrolysis of TSP is often used to explain the mechanism of a coordinated pH/phosphate program.
When TSP is dissolved in water, it dissociates, forming sodium hydroxide and disodium phosphate:

Na3PO4 + H2O = NaOH + Na2HPO4

Trisodium water sodium disodium
Phosphate hydroxide phosphate

Consequently, when an equal molar mixture of caustic soda and disodium phosphate is evaporated to
dryness, only Trisodium phosphate remains - not sodium hydroxide and disodium phosphate. Trisodium
phosphate is the least soluble of this trio and precipitates first.
The restriction imposed is that the sodium hydroxide molar ratio must be equal to less than the
disodium phosphate molar ratio. In boiler water having a high concentration of bicarbonate alkalinity
(NaHCO3) in the feed water, it may be necessary to control a coordinated pH/phosphate program on a
sodium to phosphate molar ratio. In this case, the sodium concentration is measured and controlled equal to
or less than three times the phosphate molar concentration.
The sodium carbonate concentration is important because beneath the iron oxide deposit build up,
of any area of over-concentration, further decomposition of carbonate can occur than occurs in a bulk boiler
water. This will cause the formation of additional sodium hydroxide and carbon dioxide will pass out of the
concentrated site with the steam.
Coordinated pH/phosphate programs are normally set up to take this into account, and are
maintained between 2.8 to 2.6 molar ratio of sodium to phosphate.

For HP boilers,all the points should be within the Red color boundary limits.
For MP boilers,all the points should be within the Blue color boundary limits.
For LP boilers,all the points should be within the Green color boundary limits.

NaOH

TSP

DSP

Blowdown
3molar ratio line
Phosphate & pH limits for Process Boilers
(Coordinated Phosphate/pH Chart)
10.8
10.7
10.6
10.5
10.4
pH of BD

10.3
10.2 MP LP
10.1 HP
10.0
9.9
9.8
9.7
25 30 35 40 45 50 55 60 65
PO4 conc in BD
Action of TSP towards Boiler water.

Boiler feed water systems using D.M makeup or pure condensate may be protected from NaOH
attack throu' CPT PO4 buffers the boiler water reducing the chance of large pH changes due to
development of high caustic concentrations.Excess caustic combines with DSP and Trisoduim phosphate
sufficient DSP must be available to combine with all free caustic in order to form TSP. Moreover the action
of TSP in the process boilers is given by following reactions.

Na3PO4 + H2O Na2PO4 + NaOH

(TSP) (Water) (DSP) (Caustic)

The added Maxtreat-3223 S first reacts with the boiler water forms Di sodium phosphate and sodium
hydroxide .The DSP formed with be taking care of the Phosphate content in the boiler water where as the
NaOH formed will care of pH of the boiler water.

Phosphate hide-out

"Phosphate hideout" and "chemical hideout" are terms used to describe the loss of boiler water phosphate
residual that accompanies this solid phase formation problem. Typically, phosphate tends to "disappear" as
load (steaming rate load) is increased towards maximum. The pH will also vary, usually in an upward
direction, although one would expect that the change 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 that is also known to exist. Just as phosphate disappears with increasing load, so does it reappear
with decreasing load, with concurrent impact on the system pH. Dissolution of the solid phase occurs as
load is reduced.

The phosphate hideout phenomenon can pose a significant chemistry control problem in high pressure
boilers that experience load variations.

Essentially all reported cases of boiler tubes experiencing phosphate-induced corrosion have been
associated with phosphate hideout. In spite of hideout being a localized phenomenon, it may become
visible in the bulk sample when the boiler changes load. As the boiler pressure is brought up to full load,
hide-out will appear as a loss of phosphate from solution accompanied by an increase in pH and alkalinity.
Typically, the phosphate concentration may drop below the levels specified for coordinated or congruent
treatments while the pH goes above 9.7. Following a load reduction or shutdown, the phosphate may start
to reappear with the pH dropping, possibly below 9.0.
Effect of low pH and high pH values in the boiler: -

Maintenance pH proper pH throughout the boiler feedwater, boiler and condensate systems is esstional for
corrosion control. Most of the low Pr boiler systems operators monitor boiler water alkalinity because it
correlates very closely with pH, while most of the feed water. Condensate and high pr boiler requires direct
monitoring of pH. Control of pH is important for the following reasons.

 Corrosion rates of metals used in boilers systems are sensitive to variation to pH.
 Low pH or insufficient alkalinity can result in corrosive acidic attack
 High pH or excess alkalinity can result in caustic gouging/cracking and foaming, with resultant
carryover.
 Speed of the oxygen scavenging reactions is highly dependent on pH levels.
 The distribution ratio of silica between steam and boiler water depends upon two major factors. One of
major factor is pH of the boiler water. Higher pH of the boiler water decreases the silica carryover. The
effect of boiler water pH on silica ratio becomes greater at higher pH values where an increase of pH
from 11.3-12.1 reduces the silica ratio by 50%,while an increase of pH from 7.8-9.0 shows no
measurable effect .

pH and alkalinity level maintained in a boiler system depends on many factors, such as systems
pressure, system metals, feed water quality, and type of chemical treatment applied.
The corrosion rate of carbon steel at feed water temp Approaches a min. value in pH range of 9.2-9.6.It
is important to monitor the feed water system for corrosion by means of iron and copper testing.

Effect of high PO4 and Low PO4 content in the boiler

The mechanism for the reaction of phosphate with metal oxides has been found that the reaction of
phosphate with magnetite results in the formation of two products. One has the composition
Na4FeOH(PO4)2·1/3NaOH. If the Na/PO4 ratio was less than 2.5 (as can be expected from trying to keep
within the bounds of CPT by blending in disodium or monosodium salts) and the temperature was in the
320-360°C region, the other product was NaFePO4 or maricite, formed as a result of these acidic phosphate
salts attacking both the magnetite and the base metal..

2Na2HPO4 + Fe3O4—> NaFePO4 + Na3PO4 + Fe2O3 + H2O

2Na2HPO4 + Fe + ½O2—> NaFePO4 + Na3PO4 +H2O

3NaH2PO4 + Fe3O4—> 3NaFePO4 + ½O2 + 3H2O

When the Na/PO4 ratio was above 2.5 and the temperature 320°C, the other product was Na2.6Fe0.2PO4
rather than maricite. If the Na/PO4 ratio went above 2.7 and the temperature was raised to 360°C, H2 was
formed as a result of a high local concentration of NaOH first dissolving the magnetite and then base metal.
The presence of the hydrogen gas can be an indication that caustic gouging is occurring.

4NaOH + Fe3O4—> 2NaFeO2 + Na2FeO2 + 2H2O

2NaOH + Fe —> Na2FeO2 + H2

If the concentration of phosphate is in equilibrium with the system, then the phosphate should remain in
solution with blowdown as the only mechanism by which it will be changed. If the phosphate addition is
continuous, the bulk sample, will then represent the steady-state average from balancing what is fed into
the boiler with what is being removed by blowdown. If the addition pump can be isolated and no more
phosphate added, the phosphate concentration should fall at a rate dependent upon the blowdown flow. If
there is no blowdown, then the phosphate concentration should remain constant. The PO4, pH and Na/PO4
ratio should also remain fairly constant in spite of load changes.
If phosphate is present at a concentration in excess of the equilibrium value, the excess will deposit within
the system. This deposition process provides a second removal mechanism in addition to blowdown. The
phosphate concentration within the bulk fluid will drop at a rate dependent upon the sum of the rates of
blowdown and deposition until such time as the equilibrium concentration is reached. At that point, the
deposition will cease and the concentration will fall only in proportion to the blowdown rate. While the PO 4
is above the equilibrium value, the PO4, pH and Na/PO4 ratio are likely to show movement in response to
load changes.

If the phosphate is present at a concentration below the equilibrium value, deposits from tube surfaces
within the system will redissolve. The redissolution would be seen as a sudden increase in phosphate when
a unit trips. It may also, if given enough time, provide a mechanism to at least partially remove old
deposits. It also provides the necessary alkalinity to maintain the system during a shutdown state.

Based on vector control diagram following actions to be taken when specified upset occurs:

In boiler water when pH values are low and PO4 values are maintaining, then add caustic lye to dosing tank
to increase the molar ratio of the solution. This is shown by green color arrow in the vectors.

If PO4 content is low, but pH values are maintaining then add DSP to the dosing tank solution to maintain
the higher PO4 content in the Boiler water. Which is indicated by blue color.

If both pH and PO4 content are low, then add TSP solution to boiler water to increase the same.

If both pH and PO4 values were high then give blowdown to the system to reduce the same. Indicated by
red color.

Trouble shooting: -

Problems type:- Possible reasons Action to be taken

Acute problems
1.Sudden pH and PO4 soot-up 1.More PO4 dosing. Reduce the Pump dosing.
2.Sudden reduction in loads. Calculated amount of Blowdown.

2.Reduction in pH and PO4 1.Extra unwanted Blowdown Increase the dosing rate.
values. 2.Sudden increase in load. Controlling Blowdown.

3.Low PO4 problems. Dosing pump Mal-functioning. Proper operation of pump

Excess blowdown. Optimization of Blowdown flowrate

Some of the perennial problems are due Mal-functioning of dosing pump, low/high molar-ratio and
concentration of the dosing solution.
Calculation: -

Amount of dosing solution to be dosed to attain required amount of PO4 content in boiler water, at absence
of blowdown.

Consider: -

Capacity of pump is 5 lit/min

Volume of water present in the steam drum including the circulating water 5 tons

Initial PO4 content of the boiler water is 25 ppm

Required PO4 content is 50 ppm

PO4 concentration of dosing tank solution 5000 ppm as PO4

Then,

Amount of dosing solution to be dosed = Vol. water * (required PO4 content - Available PO4 content)
Concentration of dosing tank solution.

= 5000*(50-25)/5000
= 25 liters

As per the pump capacity we have dose at 100% stoke for 5hrs OR at 50% stoke for 10hrs.

Blow down Calculation: -

Consider the boiler water present PO4 content as 80ppm

Required amount of Boiler water PO4 content is 40ppm
Volume of water present in the boiler drum 5Tons.

Then,

Vol. Of water to be drained = Vol. of water present in the steam drum * required PO4 concentration

Present PO4 concentration of the boiler water.

= 5000*40/80
= 2500 liters.

Then,
2500 Liters of water to be drained to maintain the PO4 content as 40ppm.
 Molar ratio of the dosing solution: -

Trisodium Phosphate (Na3 PO4): -

Consists of 3 moles of Sodium and one mole of Phosphate. Pure TSP Always has 3:1 Na to PO4
ratio. In manuf. Of TSP the purity is always based on the PO4 concentration in the material. Normally
100% pure TSP consists of 55% of PO4 content. The sodium concentration is not considered in terms of
purity of the TSP.

The molar ratio of the solution can be calculated by

Concentration of sodium/moli.wt of sodium

Molar ratio =
Concentration of Phosphate/moli.wt of Phosphate

Molecular weight of Sodium = 23

Molecular weight of Phosphate = 97

On application, The equation becomes as

(Conc. of sodium / Conc. of Phosphate) * 4.2 = molar ratio of Phosphate solution.

Significance of molar ratio: -

Low molar ratio of the dosing solution causes low pH and high PO4 problem. Because amount of
sodium dosing is less compared to amount of Phosphate dosed in the system. If it is found molar ratio of
the solution is low and Caustic lye can be added to increase the sodium content of the solution as well as
molar ratio of the solution.

High molar ratio of the dosing solution causes high pH and low phosphate problems in boiler
water. Allows free caustic to exist in boiler water and causes caustic embrittlement.

Significance of P& M alkalinity: -

Phenolphthalein - alkalinity
Methyl - alkalinity

In boiler water, If we observe 2P-M is less then or equal to zero then we can ensure that that no free
Caustic is present in the boiler water. Hence chances of Caustic embrittlement is negligible.