DRY CHLORINE

AND
CORROSION BEHAVIOUR

BY
H.S.SEHGAL
 TECHNICAL SUMMARY
• Control of moisture in chlorine is essential .
• DRY LIQUID chlorine is defined as chlorine with its water
content dissolved in solution.
• If a condition is reached anywhere in the system that will
allow the water to exceed its solubility and form a second
aqueous liquid phase, the chlorine is defined as WET
LIQUID chlorine.
• WET chlorine form corrosive conditions affecting safety
and integrity of the system.
• Present definition of moisture in chlorine is inadequate .
• Water separation in chlorine occurs under a range of
conditions,
• Each system considered for the proper determination of
acceptable chlorine moisture content.
Conti...
• The temperature conditions throughout the entire system must first be
defined.
• Apply each set of conditions to the charts in Figures 1A and
1B,Solubility of Water in Liquid Chlorine, to determine if the water will
separate from the chlorine.
• The two representations of the same data are made for ease of
interpretation over a wide range.
• Below about 10 C, the second phase will be chlorine hydrate (chlorine
"ice") which is not immediately corrosive.
• However, when the cold system containing this material is warmed,
large amounts of free water will be liberated with attendant accelerated
corrosion.
• a. If the chlorine supply has 30 ppm moisture content and one of the
system temperatures is 10oC, the chlorine meets the DRY chlorine
definition. If the same chlorine encounters a system temperature of (-
20oC), then the chlorine would be considered WET.
• b. A system operating at (10oC) is tolerant to moisture levels of 110
ppm moisture content in chlorine.
Conti...
• The moisture level in chlorine will redistribute when the chlorine is
either partially vaporized or condensed.
• Moisture preferentially distributes to the vapor phase, with a
distribution ratio of about 4:1.
• DRY CHLORINE GAS contains moisture exerting a vapor pressure of
no more than 2.0millimeters of mercury. Chlorine gas that meets this
criteria can be processed in steel systems without appreciable
corrosion.
• This maximum moisture level is shown graphically for gaseous
chlorine at its saturation temperature in Figure 2.
• Steel in chlorine service is protected from corrosion by a layer of ferric
chloride. Depending on the temperature and moisture level in the
system, the ferric chloride will exist as a hydrate. The degree of
hydration varies.
• The water content can be between16 and 52 percent (W/W). The
hydrates exert water vapor pressures.
Conti...
• If moisture in excess of the hydrate vapor pressure, the hydrate will melt,
yielding a highly corrosive solution and exposing bare steel to further
corrosion.
• Temperature range of(–20oC to +100oC), the water vapor pressures exerted by
the hydrates of ferric chloride can be as low as 2.0 millimeters of mercury
• 2.0 millimeter of mercury water vapor pressure limit in chlorine was derived
from limiting vapor pressures.

• Recommendation considered a high limit, as drying to a moisture content one

tenth of this limit .

• Moisture content of the gas is considerably higher than the liquid with which it
is in equilibrium (usually a factor of 4).

• Gas in equilibrium with the liquid will contain much higher levels of moisture
than is allowed by the 2 MM criteria discussed above, especially at elevated
pressures.
 CORROSION CONSIDERATIONS IN ADDITION TO MOISTURE

Elevated Temperatures
• At elevated temperatures below the ignition temperature,
ferric chloride will sublime and deteriorate the protective
layer, increasing corrosion rates.
• High Velocities in combination with elevated moisture
levels can increase erosion damage to piping.
• High temperature liquid chlorine will increase the solubility
of ferric chloride, thereby removing the protective layer.
Cooling liquid chlorine can precipitate ferric chloride.
• Combinations of these mechanisms can result in more
rapid deterioration than can be attributed to any single
mechanism.
Attainable moisture content as a function of concentration
and temperature of the acid
THANK YOU