Cargo compatibility and reactivity for ships carrying

dangerous chemicals in bulk

Transporting of dangerous and noxious liquid chemicals in bulk

involved various risk factors. Chemical cargoes can be very dangerous,
most of them being flammable and/or toxic, some of them extremely
so. Between some chemicals violent reactions may occur if the
chemicals are mixed in certain proportions. The result may possibly be
an eruption and tank rupture. Such an occurrance must be prevented.
Water may also have to be considered in this respect.

Fig: Chemical carrying at sea

Leakages through bulkheads occur at times in any tanker. Normally,

however, such leakages are only minor seep ages. They will not cause
any violent reaction due to the great disproportion in mixture from
dangerous proportions. But legislation as expressed in the IMO
Chemicals Bulk Code ref (25), and in the US Coast Guard Rules ref
(18) and Appendix 3 expressly prohibits the placement of inter-
reactive cargoes on both sides of a bulkhead. There must be an empty
tank, a cofferdam or a tank with a cargo neutral to both products in
between. This requirement causes some headaches in cargo planning.
"Diagonal contact'' between tanks is normally considered as sufficient
separation between reactive cargoes.

More important, however, is the complete separation of piping systems

so that one product cannot inadvertently be pumped into another. To
this effect strategic pipe bends may have to be removed and blind
flanges fitted on each pipe end. Modern chemical tankers will have
blind flange valves fitted . Such a blind flange valve must have a
double separation between the products with a drain in the interspace.
A single blind flange is not acceptable. Remember also to separate
drain lines or slop connections to avoid the possibility of cargo mixing.

The cargo inter- reactions may be of type:

a) Chemical reaction: Strong ( inorganic) acid plus alikali (or water)

causes heat, e g sulphuric acid plus caustic soda or water. Therefore
sulphuric acid may not be carried in tanks bordering the side shell or
filled ballast tanks. Similarly sulphuric acid may react with a number of
hydrocarbons except parraffines (petroleum oils). Amines ( aniline,
diethylamine) may react with esters ( butyl, acetate, ethyl acetate).
Caustic soda will react violently with acrolein, acrylonitrile and allyl
alcohol.

b) Oxidation : An Oxygen-rich compound like propylene oxide may

react with an amine (e g diethylamine) or an aldehyde (e g
acetaldehyde). An ether (e g ethyl ether) may react with oxygen and
from a peroxide which is an explosive hazard. The ether should be
inhibited and carried in an inerted (N 2 ) tank.

c) Auto- reaction : Certain hydrocarbons compounds have a tendency

to polymerize with time, accelerated by heat, light, sometimes air or
other matter such as rust. Polymerization means that several
molecules of the same kind binding together to bigger molecules. The
compound tends to become more viscous or eventually solidify. Heat is
liberated , which accelerates further polymerization.

Chemically most cargoes are monomers, which means that they,

before any polymerization, consist of single molecules.

Toxic vs edible products

Toxic products must never get mixed into edible products for human or
cattle feed! In this case minor seepages between tanks might prove
disastrous.
IMPORTANT: Edible products should never be loaded with bulkhead to
bulkhead contact with toxic cargoes! The piping systerns should be
entirely segregated or provided with double blind flanges.