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CH 23-Pyrophoric Iron Sulphide

This chapter discusses the formation and dangers of pyrophoric iron sulphide in cargo tanks. Pyrophoric iron sulphide can form when iron oxide is exposed to hydrogen sulphide in an oxygen-free environment, and can autoignite when reexposed to oxygen due to rapid exothermic oxidation. While rarely cited as an ignition source on ships previously, the increased use of inert gas systems may increase the possibility of forming pyrophoric deposits that could ignite if oxygen is reintroduced. Strict preventative measures like diligent inert gas plant maintenance and never discharging cargo without atmosphere control are necessary to prevent potential ignition from pyrophoric deposits.

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385 views3 pages

CH 23-Pyrophoric Iron Sulphide

This chapter discusses the formation and dangers of pyrophoric iron sulphide in cargo tanks. Pyrophoric iron sulphide can form when iron oxide is exposed to hydrogen sulphide in an oxygen-free environment, and can autoignite when reexposed to oxygen due to rapid exothermic oxidation. While rarely cited as an ignition source on ships previously, the increased use of inert gas systems may increase the possibility of forming pyrophoric deposits that could ignite if oxygen is reintroduced. Strict preventative measures like diligent inert gas plant maintenance and never discharging cargo without atmosphere control are necessary to prevent potential ignition from pyrophoric deposits.

Uploaded by

Antonio Antonio
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© © All Rights Reserved
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Chapter 23

Pyrophoric Iron Sulphide


This Chapter deals with the formation of pyrophoric iron sulphides in cargo tanks
and the dangers to safe tanker operation from pyrophoric oxidation.

23.1 PYROPHORIC OXIDATION

In an oxygen-free atmosphere where hydrogen sulphide gas is present (or


specifically where the concentration of hydrogen sulphide exceeds that of the
oxygen), iron oxide is converted to iron sulphide. When the iron sulphide is
subsequently exposed to air, it is oxidized back to iron oxide and either free sulphur
or sulphur dioxide gas is formed. This oxidation can be accompanied by the
generation of considerable heat so that individual particles may become
incandescent. Rapid exothermic oxidation with incandescence, is termed pyrophoric
oxidation. Pyrophodc iron sulphide i.e. -iron sulphide capable of pyrophoric
oxidation in air, can ignite flammable hydrocarbon gas/air mixtures.

23.2 FORMATION OF PYROPHORS

23.2.1 General

It can be seen from the above that the formation of pyrophors is therefore dependent
on three factors:

 Presence of iron oxide (rust).

 Presence of hydrogen sulphide gas.

 Lack of oxygen.

However, it also depends on the comparative influence of these factors. The


presence of oxygen will inhibit the conversion of iron oxide to iron sdiphide. Also,
while the concentration of hydrogen sulphide gas has a direct influence on the
formation of pyrophors, the degree of porosity of the iron oxide and the rate of flow
of the gas over its surface will influence the rate of sulphidation. Experiments have
supported the view that there is no safe level of hydrogen sulphide below which a
pyrophor cannot be generated.

23.2.2 In Terminal Operations.

In terminal operations, pyrophohc iron sulphide is well recognised as a potential


source of ignition. Pyrophoric deposits are apt to accumulate in storage tanks in sour
crude service and in process equipment handling sour streams. When such tanks or
equipment are taken out of service, it is normal practice to keep all internal surfaces
thoroughly wet during ventilation so that there can be no pyrophohc reaction before
the equipment is made hydrocarbon gas free. Deposits and sludge must be kept wet
until removed to a safe area where subsequent ignition will cause no damage.
Numerous fires have occurred when deposits have dried out prematurely.

23.2.3 In Marine Operations

While pyrophoric iron sulphide is a widely recognized ignition source in shore-based


operations, it has rarely been cited as the cause of a marine ignition and in those few
cases the hydrogen sulphide levels were very high. Presumably marine operations
have been free of this hazard because the cargo tanks of non-inerted ships normally
contain some oxygen in the vapor space as a result of tank breathing.

23.2.4 In Inerted Cargo Tanks

The use of inert gas on crude carriers may, by decreasing the initial oxygen level as
well as that of subsequent replenishments, increase the possibility of forming
pyrophoric deposits. Although tanker flue gas normally contains from one to five
percent oxygen, this level can be further reduced by absorption into the crude cargo.
Furthermore, as the cargo tanks are kept pressurized with inert gas with a low
oxygen content no air will enter the ullage space. If the pressure needs to be
increased it will again be done with inert, gas having a low oxygen content.

23.3 PREVENTION OF PYROPHORIC IGNITION IN CARGO TANKS

The industry-wide conversion to the use of inert gas systems on crude carriers has
probably increased the possibility of forming pyrophoric deposits, but as long as the
cargo tanks remain inerted there is no danger of ignition from a pyrophoric
exothermic reaction. However, it is imperative that the atmosphere in the tank is not
allowed to become flammable. Flammable atmospheres would inevitably arise if the
tanks are discharged while the inert gas plant is inoperable.
This does not mean that the probability of ignition is high if discharge without
atmospheric control takes place. Various factors may inhibit pyrophor formation or
a pyrophoric reaction. These factors include:

 Lack of sufficiently thick deposits of iron oxide.

 Inclusion of elemental sulphur and crude oil in tank deposits.

 Introduction of oxygen by re-pressurizing.

These inhibiting factors are not, however, predictable nor can one be confident that
they will always be effective. Hence the degree of risk is judged to be high enough
to require that atmosphere control is always maintained during and after discharge.
To ensure that atmosphere control can be maintained the following practices should
be observed:

 Diligent maintenance of inert gas plants.

 Spares should be kept on hand for critical parts which cannot be obtained
quickly or which can fail abruptly (e.g. the fans).

 In the event of an inert gas plant failure prior to or during cargo or ballast
discharge, discharge should not commence or continue until the inert gas
plant operation is restored, or an alternative source of inert gas is
provided.

There is evidence that any pyrophoric deposit formed during the loaded
passage will not necessarily be de-activated during the subsequent ballast
passage. Therefore the atmosphere in the tanks should be maintained in an
inert or non-flammable condition both throughout the voyage and during the
discharge of ballast. The correct use of inert gas and gas-freeing procedures
given in Chapters 9 and 10 should ensure that a flammable atmosphere is
avoided.

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