Why is TSP (Tri Sodium Phosphate) dose in EE-103 and EE-105

1. To Prevent scale formation in the boiler caused by feed water contaminants such as
hardness, silica and metals.

Trisodium phosphate reacts with scale forming salts like calcium/magnesium chlorides,
calcium/magnesium sulphates and converts them into sludge.

3CaCl2 + 2Na3PO4 -> Ca3PO4 + NaCl

3MgCl2 + 2Na3PO4 -> Mg3PO4 + NaCl

3CaSO4 + NA3PO4 -> Ca3(PO4)2 + NA2SO4

2. To controls the alkalinity or PH to prevent corrosion as well as avoid silica carry over by
steam.

A common recommendation is to maintain boiler water pH at 8.5-9.5. If the pH is lower than

that, the water will start eating the pipes. Boiler surfaces are coated with a thin protective
magnetite (Iron oxide) film. A low boiler water pH is usually caused by contamination of the
boiler feed water, from sources such as hydrochloric or sulfuric acid from leaks in
demineralizers and condenser leaks of cooling tower water. When Iron reacts with water in
alkaline phase Magnetite (Fe3o4) is formed, that acts as a protective layer and when Iron
reacts with water in acidic phase hematite (Fe2O3) is formed that in presence of NaOH lead
to loss of Iron from the boiler surface. For Information NaOH is normally formed when TSP
reacts with Water along with Disodium phosphate.

Sample analysis of EE103 and EE105 bottom condensate

1. Phosphate Test
To assure that the Ca\Mg + phosphate reaction goes to completion, there must be at least
2-5 mg\l excess phosphate in the boiler. If phosphate rises much over 10-15 mg\l, it can
contribute to boiler carryover. To a small extent, phosphate also helps prevent boiler
corrosion by forming a protective iron phosphate coating on the boiler metal. Also excess
dosing of TSP can lead to formation of high amount of NaOH that can change Magnesium
chloride in presence of NaOH and SiO2 to Magnesium silicate. This silica scales have
high resistance to heater transfer.

Na3PO4 + H2O → Na2HPO4 + NaOH

Na2HPO4 → NaOH + H+ + PO4+
2. Conductivity Test
The conductivity test can be used as a simple and accurate method of blowdown control.
Measure of the total amount of dissolved solids (T.D.S) including the treatment chemicals.
High conductivity can be controlled by Continuous Blowdown (CBD) otherwise dissolved
solids can cause scaling.

3. pH Test
pH should be in the range of 8.5 – 9.5.
If pH drops below it, it can cause Acid Attack. A low boiler water pH is usually caused by
contamination of the boiler feed water, from sources such as hydrochloric or sulfuric acid
from leaks in demineralizers and condenser leaks of cooling tower water. It is recommended
to take fresh DM water.
Also, if pH increases above the range can cause Caustic Attack. The corrosion action is a
result of the formation of caustic-ferritic compounds through the dissolving of the
protective magnetite film. In this case it is recommended to reduce dosing and
intermittently blowdown (IBD) is required. Once the process begins, the iron in contact
with the boiler water will attempt to restore the protective magnetite film.
Fe3O(Magnetite) + NaOH (Caustic) → NaFeO2(Caustic Ferrite) + Na2FeO2 + H2O
This reaction explains the loss of metal in highly alkaline.

4. Silica (SiO2)

Silica is not so appreciated and is considered one of the major impurities to cause boiler
scale. As the scale builds up over time, it reduces heat transfer rates. This leads to local hot
spots which cause the boiler tubes to overheat and rupture, resulting in costly boiler
outages. In addition, untreated boiler scale lowers the boiler efficiency by heat retardation
and increases running costs by unscheduled and more frequent boiler blowdowns. It is
recommended to immediately blowdown if found in the condensate sample.
Na3PO4 (TSP) + H2O → Na2HPO4 + NaOH
MgCl2 (hardness) + SiO2 + NaOH → MgSiO3 (Silica scale)

Regards
Harshit Sharma

Subject: Purpose of Wash Water and Ammonium Polysulphide

What is the purpose of Wash Water and Why Ammonium Polysulphide is
added at the 1st Stage and 2nd Stage discharge of WGC?

In refinery Cynide causes considerable corrosions, Hydrogen Blistering and waste water
disposal problems. Free cyanide destabilize the iron sulphide layer causing it to flake off as
free iron sulphide hence causing metal loss , the phenomenon is called as leaching of metal.
Also, Hydrogen ion produced can penetrate into the metal tube and cause brittleness. The
activity of Cynide corrosion increases at high pressure.

What Wash Water does?

An effective water wash dilutes and scrubs corrosive species-such as hydrogen sulfide,
ammonia, chlorides. Corrosive gases are more soluble in water at high process pressures.
Therefore, the best location for a water wash is downstream of each stage of gas
compression, ahead of the coolers. A water wash alone does not always protect completely.
It is often necessary to supplement the water wash with chemical additives, such as
ammonium or sodium polysulfide and filming inhibitors. Ammonia is more soluble in water
than Hydrogen Sulphide hence its PH is above 8. Also if PH drops below 7.5 reduce wash
water to throw out more acids also if PH crosses 9 either by the presence of N2
or HC increase wash water to maintain PH.

How APS works?

Polysulfide is injected into a water wash to react with Hydrogen Cyanide, producing
Ammonium Thiocyanate. Thiocyanates thus produced do not react with the protective
sulfide film on metal surfaces, as cyanide does, Hydrogen penetration is also reduced.
Thiocyanate is thermally stable in water and does not decompose.

HCN + (NH4) 2S → NH4SCN + H2S + NH3

Ammonium Thiocyanate

Precautions to be taken while handling APS:

1. Ammonium polysulphide is soluble in alkaline water. If PH drops below 8 ammonium

polysulphide will decompose into ammonia, hydrogen sulfide, and sulphur. The formation of
sulphur fouls the equipment. Hence the Wash Water PH is maintained above 7.5.
2. Ammonium polysulphide exposure to air oxidizes polysulfide to thiosulfate and sulphate,
neither of which forms the desired thiocyanate. A change from red or yellow to colourless
suggests oxidation of the polysulfide. Hence APS storage vessel is blanketed with nitrogen.