Detergents:

Enable water and oil to be held in solution as an emulsion, thus enhancing the use
of water to remove oil based residues. Detergents are water-soluble and are
usually utilised to remove traces of oil based contaminants. Although most
detergents are very similar and. claim to do the same function, chemically they are
not the same. Many are caustic soda/potash based and are therefore not suitable
for zinc coated tanks. Define the function of the detergent and it will usually be
possible to find a specific product to do that job, for example, general hydrocarbon
remover, inert gas residue remover, etc. Always get approval from the coating
manufacturer that the product is safe to use at the proposed working conditions.
The use of de-emulsiriers can speed up the separation of the oil / water emulsion,
which enables the cleaning residues to be treated or disposed of in a much shorter
time frame. This may be important if there is limited slop stowage on board.
The use of wetting agents enables a cleaning material to cover a tank surface far
more efficiently, which should speed up the cleaning process.
Saponification:
Oil based products (mainly, but not exclusively animal and vegetable based) react
directly with caustic soda or caustic potash to form a "soap", which is water soluble
and can be readily removed from the tank. Caustic solutions are of course highly
alkaline and this technique only applies to epoxy or stainless steel coatings. But this
chemistry is the basis for the majority of detergents, which are fundamentally caustic
solutions with other materials added to make them multi-purpose, for example deodorizers
or buffers to make them "zinc" safe, etc.
Solvent based:
If there is a measurable quantity of oil based previous cargo to remove, then solvent based
cleaners are usually the most efficient way of doing this. These materials contain
petroleum solvents which readily re-dissolve oil based residues, but they also contain
emulsifiers to enable them to be carried with water. However in practice it is found that
these materials are far more efficient when used undiluted, which involves manual
spraying. In practice a thorough water pre-wash (see section 6.5.1) is usually sufficient to
remove enough of the previous cargo residues to be able to avoid using this type of
cleaning material.
Bufferclean:
Specific cleaning material that is based on a detergent but which contains a mixture of
caustic soda and citric acid, carefully buffered to produce a working pH of around 5.5 - 6.0.
This material is specially designed to clean the surface of zinc coated tanks, by chemically
stripping the top layer away. Its main purpose is therefore to remove surface contamination
like dried on residues, leaded cargo residues or excess zinc salts (see section 6.4.5) which
are produced throughout the active life of the coating.
Metal brightener:
Specific cleaning material that is based on a detergent but which contains an inhibited acid
solution usually based on phosphoric acid. This material is very effective at cleaning stains
on the surface of stainless steel and epoxy coated tanks. It should never be used on zinc
coated tanks.
Inhibitor Killer:
Alternatively called Acrylate Neutraliser. Specific cleaning material that contains a variety
of active ingredients that neutralise strong odours and break down many inhibitors that are
used to stabalise products that are known to polymerise, for example, styrene monomer,
acrylonitrile etc.
Dye out:
Specific cleaning material that contains sodium hypochlorite. This material is an oxidising
agent and is very effective at removing dried on surface contamination, particularly from
dyed petroleum products.

6.4.1.3 Raw Materials - pure chemicals

Methanol:
Probably the most important raw material cleaning agent when the vessel is subject to a
wall washes inspection. Methanol is widely considered to be the most universal solvent
because it is quite aggressive towards hydrocarbons and other products that are not
soluble in water, whilst being completely soluble in water itself Importantly methanol does
not currently have the long-term health effects as other similar type solvents, which also
makes it comparatively less hazardous to use. Fundamentally if a wall wash sample shows
signs of contamination, then it is apparent that the cause of the contamination is being
washed off the bulkhead by the methanol during the wall wash sampling procedure. It
therefore follows that washing the tank with methanol will have a similar cleaning effect. It
is usual to manually spray methanol through a lance attachment fitted to a barrel pump (or
similar) through chemically resistant hosing. The extent of the spraying is then limited to
the length of the lance, although it is widely accepted that most contamination inside a
cargo tank accumulates in the lower 5 metres, due to the washing and rinsing effect of the
cleaning machines and the static pressure of the cargo whilst the tank is fully laden.
However, there is nothing to stop methanol being re-circulated inside a tank, if suitable
precautions are taken. Clearly this will use a much larger volume of methanol, but in terms
of saving time, re-circulating is far more efficient in a much shorter space of time. Methanol
is very volatile and the vapour can be readily distributed through a tank by steaming after
spraying (see section 6.5.5.2.).
Methanol is aggressive to many materials, so if it has to be transferred from a drum for any
reason apart from spraying, then it should only be done so through chemically resistant
hosing. As a rule, methanol should not be transferred unless it is absolutely essential.
Chlorinated solvents:
For example, perchloroethylene, trichloroethane, Genklene, etc. These materials are
generally insoluble in water, so their cleaning effect is limited to removing hydrocarbons
and other contamination that is insoluble in water. Their effect on hydrocarbons is more
aggressive than methanol, so this point should be considered. In general these materials
are more hazardous to health than methanol, so suitable precautions should be taken
when cleaning with these materials. One of the most common, bulk shipped, chlorinated
solvents is ethylene dichloride, which is not usually subject to a wall wash inspection prior
to loading. Carrying this cargo can certainly have a good cleaning effect on the coating and
should be considered if the vessel is being upgraded to a methanol wall wash standard.
Acetone:
Similar to methanol in that it is soluble in water and oils. Probably more aggressive towards
hydrocarbons than methanol, but as it is more widely available, then methanol is usually
preferred. Acetone is also called DMK (di methyl ketone), but in the same family there is
MIBK (methyl iso butyl ketone) and MEK (methyl ethyl ketone), which show less solubility
in water (< 10%).
Toluene:
Organic aromatic solvent, usually used in conjunction with steaming to remove heavier
hydrocarbon contamination derived from a similar source, namely CPP (see section
6.5.5.1.).
Hydrocarbon solvent eg gas oil / kerosene:
These solvents usually form the basis of solvent based detergent cleaners, although there
is no reason why the pure solvents cannot be used on their own. Probably the most well
known hydrocarbon solvent cleaner is gas oil, because it is relatively cheap and widely
available. The most important use of gas oil as a cleaning agent is in the removal of heavy
non-volatile residues for example fuel and crude oil. Cleaning with gas oil will therefore
usually be the first step of a cleaning schedule and will be followed by a more thorough
cleaning programme using more traditional methods.
Caustic Soda/Caustic potash:
As for the hydrocarbon solvent cleaners, caustic soda or caustic potash form the bases of
many detergent type hydrocarbon removers. The saponification reaction is mentioned in
section 6.4.1.2 and it is quite feasible to use the caustic solution on its own as a very
effective cleaning material.