4 MATERIALS

4. 01 Iron, steel

Mild steel and high tensile steel is, and will continue to be the most important material in the building of
chemical tankers and their cargo tanks.

Steel is attacked by only a few products, mainly acids and, of course ballast and washing water. Steel itself
contaminates very few products, one of them being high purity caustic soda. Rust, however, creates many
problems with cargo contamination. Rust may contaminate a product in the form of minute particles staying
suspended in viscous heavy liquids such as glycols and caustic soda. Rust may accelerate polymerization in
polymerizable products. Rust will be soaked in with remains of previous cargoes, mainly from heavy oils,
which will contaminate the next cargo. Rust will, above all, render tank cleaning much more difficult, cause
delays and perhaps cargo claims.

Due to the above reasons steel is practically never used in chemical tankers without a protective coating, see 4.
05. Coating techniques have advanced greatly in latter years. Still, however, one does not dare to use coatings
for products, which are really aggressive to steel, e g acids (such as phosphoric acid). One has to reckon with
coating defects where corrosion will start. One exception to this is rubber linings, which have been in use a long
time with corrosive cargoes.

For information on a particular product’s sensitivity to steel steel and rust see ref (1), Appendix I and 5.
Generally speaking, steel is resistant to alkalies, even in high concentrations (caustic soda, ammonia).

4.02 Stainless steel

Stainless steel has increased greatly in use as tank material in later years. The motif is not only a better chemical
resistance but primarily it provides for a greater ease in tank cleaning and inspection. Thus cargo contamination
hazards can be reduced.

The stainless properties are due to the formation of a very thin, passive layer of chromium oxide on the surface. The care
of stainless steel tanks aims at maintaining this protective film intact.

Stainless steels possess a number of advantageous properties, rustproofness, however, is not guaranteed. It depends on the
correct treatment of the tanks and on what products carried. A short review may be of interest.

The commonly used stainless steels have the following typical compositions:
Low carbon contents are required to make the steel corrosion resistant near the welds. Carbon tends to bind chromium to
form chromium carbide in the heat affected zone near the welds, thus reducing the corrosion resistance locally. The
addition of titanium has a neutralizing effect on this process and therefore slightly higher carbon contents can be tolerated.
The addition of small amounts of nitrogen increases the tensile strength of the steel considerably. Such steels are often
used in more highly stressed parts such as corrugated bulkheads subjected to corrosion from both sides, where
weight reduction is at a premium.

General corrosion of stainless steels from corrosive cargoes such as phosphoric acid is of a low intensity and
can therefore be disregarded.

Pitting corrosion might cause severe damage. To avoid this happening it is important to choose the correct type
of stainless steel. Generally speaking high molybdenium contents is beneficial in this respect. Pittings may take
the shape of small holes, 1-2 mm in depth and diameter to begin with. At times they are almost hidden below
the surface of the steel with an "entrance hole" of only a few tenths of a mm. with a cavity of 1-2 mm below.
They are therefore sometimes very difficult to detect. So called dye-penetrant tests are useful for detection
when one knows approximately where to look for defects. Pitting may develop in a generally corrosive
surrounding, especially when the surface is disturbed or when some extra chemical aggressive age.nt is present
such as:

- chlorides (seawater, "salt"). Contents above some 100-200 ppm are generally dangerous when together with
some other corrosive agent such as phosphoric acid. Fluorides have a similar effect.
- particles of iron-or other materials on the surface
- craters or pores in weld deposits
- weld slag or slag from rolling mill
- surface defects, micro cracks, rough surfaces
- lack of oxygen renders formation of chromium oxide difficult
- high temperatures (above ca 400C corrosion rates in crease rapidly)

Crevice corrosion may occur in narrow spaces where the corrosive agent can enter but without circulation, with
a lack of oxygen as consequence.
Typical locations:
- under bolted connections
- under cargo sediments
- under paint on a stainless steel surface.

The following rules for maintenance of stainless steel apply:

1. Keep chlorides away. Avoid seawater in the tanks and rinse with freshwater carefully after seawater washing.
Seawater must never be permitted to dry up and leave salt crusts on the surface. Keep the hatch covers closed
and the airpipes protected to prevent seawater or a saline atmosphere entering the tanks. Preferably change
footwear before entering a tank when at sea.

2. Remove any particles or sediments such as rust, particles from grinding operations, cargo sediments
(phosphoric acid), "scale". Cargo remains to be removed as soon as possible after discharge.

3. Surface finish. Tank surfaces to be kept bright and free from scratches. This means-that possible corrosion or
other mechanical defects should be ground and polished to the original finish. Normally grinding disc "grain
80" can be used, followed by a final operation with "grain 120". Local pittings of substantial depth can be
welded, minor pittings ground away.

4. Inspect for corrosion after each cargo, especially tank bottoms and under deck. In order to avoid salt crystals
forming on the tank bottom 10-20 cm fresh water is sometimes kept in the tanks on the ballast voyage.

5. Cleaning can normally be carried out with all common cleaning agent's such as "emulsifiers", "solvent
cleaners" and alkaline cleaners as well as caustic soda.

6. Stainless steel tanks are sometimes passivated by application of 12- 15 % nitric acid (HNO 3) . This acid is
strongly oxidizing. The procedure assists in building up the passive chromium layer on the steel, thus increasing
its chemical resistance. Passivation is normally carried out after tank surface repairs in order to assist the
normal passivation in air. If aggressive cargoes are to be loaded within 24 hours all repairs must be passivated.
In practice "passivation" with nitric acid is often used for the removal of discolorations and particle
contaminations on the surface. In factlit is being more used as a thorough cleaning agent than a passivating
chemical. Passivation is normally carried out with a brush or, for a whole tank, by spraying, After 10-20 min
the acid should be washed off with large amounts of fresh water. IMPORTANT: Nitric acid gives off nitrous
gases which are very toxic (with delayed effects). Ventilate completely and use breathing masks for larger areas
in confined spaces! The atmosphere can be tested for nitrous gases by means of test tubes, see 3. 10. Use
protective clothing and goggles. Nitric acid is usually available in 60 1/o concentration. Be careful: spills may
cause self-ignition of organic matter. See also ref ~i) for safety precautions with nitric acid.

7. Pickling is the toughest way of cleaning stainless steel. This method is used for the removal of welding slag,
oxides and discolorations from welding or discoloration from cargoes. Pickling paste, consisting of, among
other components, nitric acid and hydrofluoric acid shall be applied with the same precautions as nitric acid
above. Pickling should be followed by passivation with nitric acid. Pickling involves a lot of work and can only
be used on relatively small areas, unless carried out by specialists.

4.03 Cuprous alloys

Copper and its alloys corrode in many cargoes and may contaminate them, e g styrene, phenol, vinyl chloride,
aniline, ammonia solutions etc. Check your cargo against information given in e g the ICS-Guide ref (1), (4)
and (5) or Appendix 1 and 5. Particularly aggressive are the ammonia compounds; they cause inter -crystalline
corrosion of cuprous alloys very rapidly. The object in question disintergrates very soon.

Heating coils of cuprous alloys are attacked by caustic soda (NaOH) after being used a long time. But for a
limited number of voyages no serious problems seem to arise. As a general rule in chemical tankers one tries to
replace cuprous alloys with stainless steel (AISI 316 or 317). One must remember, however, that stainless steel
easily scores against stainless steel in sliding contact (in valves etc) and design accordingly, using also other
materials.

4.04 Magnesium and aluminium, alloys

Alloys of magnesium and aluminium should never be used in the cargo tank area, due to their poor corrosion
resistance in such environments.

As sacrificial anodes these alloys are frequently used. They are severely attacked by caustic soda. Methanol will
be severely contaminated by magnesium. Any anodes should be removed before loading these cargoes. Check
cargoes against ref.,(1) or other information.

There seems to be a belief that Al/Mg alloys are spark-proof materials, suitable for tank cleaning equipment etc.
The truth is the opposite: "light alloys" are considerably more prone to cause incendive sparks than steel
objects. When an object fall-s down into a tank light alloys oxidize at the point of contact, thus adding a
reactive energy to the kinetic energy released. "Hot" sparks are created instead of "cold" sparks, which are
created by steel objects falling down. As a flammable mixture requires a certain minimum amount of energy to
trigger off an explosion it follows that "light alloys" are considerably more dangerous. Therefore: do away with
tank cleaning gear of light alloys!

In this connection it can be mentioned that so-called spark free tools are no longer particularly recommended.
Tests have shown that steel tools are equally safe, see ref (9).

4.05 Tank coatings

A modern chemical tanker has all her cargo tanks coated unless they are made of stainless steel. The main
reasons for coating are: easier cleaning and less risk for cargo contamination. The durability of properly applied
and maintained coatings may be ten years or more. On the other hand one mistake in cargo selection may totally
ruin a coating. It is a matter of knowing the limitations and possibilities of each type,or even of each make, of
coating. Here the chemical build up of coatings shall not be elaborated, only the physical properties as regards
resistance and application. Every paint manufacturer has his own resistance list stating approved cargoes,
temperature and time limitations etc. Contact the maker if in the slightest doubt; mistakes may turn out to be
very costly. Many coating manufacturers give some sort of guarantee for the first two years after application.

Epoxy coatings generally possess a good resistance against alkalies, seawater, wine, vegetable oils, crude oils,
gas oils, lub oils, jet fuels, gasoline and also weak acids (as in free fatty acids in vegetable oils, but acid value
should not exceed 20-40). Epoxy ha s limited resistance against aromatic hydrocarbons ("solvents" such as
benzene, toluene), certain alcohols (e g methanol), ketones (acetone) and some esters. Epoxy is sometimes
indicated as resistant also to stronger acids. This may be correct, but as an applied coating one must count on
"holidays" in the film, thus making epoxy unsuitable for really corrosive liquids.

Epoxy coatings which have been stressed beyond their chemical resistance with strong solvents tend to soften;
test with your nails. In such a case the coating must be given ample time to "weather out" trapped solvents and
recover its hardness before being subjected to cargo or water again. Do not try to speed up the recovery by
application of heat! The top skin of the coating may then first harden, leaving trapped solvent underneath, with
flaking as a consequence. Ventilate with a good turbulence in all corners of the tank. Hardness of epoxy
coatings can be established by means of a standardized test using pencils of different hardness as a reference
(Sw standard SIS 184 187).

Adhesion of a coating to the steel is also reduced if it is overstressed by a cargo of strong solvents. There are
standard test methods for the determination of adhesion by means of glued-on tablets, which are then pulled off
with a recording of the necessary force.

Epoxy coatings should normally not be heated above 60 -(80) degr.C during tank washing, steaming etc, During
the loaded voyage lower temperatures should be kept.

Epoxy tar coatings. are made up from epoxy with an addition of coal tar. They are excellent against seawater
and crude oils but should never be used in chemical tankers, Light hydrocarbons of moderate solubility such as
jet fuels, gas oils, gasoline may cause the tar to leak out, which may contaminate the cargo.

Zinc silicate coatings particularly those of inorganic type, are very resistant against strong solvents and
normally tolerate higher temperatures than epoxies. Typical products are: aromatic hydrocarbons (benzene,
xylene etc), alcohols, ketones. Jet fuels may suffer zinc "pick up" from the coating to an extent which is
considered a contamination. Therefore: check with shippers requirements. Zinc silicates are not resistant against
acids or alkalies. The pH value of the cargo should be within the range 5, 5 -10, 5 (neutral pH 7, 0). This means
that some molasses (slightly fermented - low pH) may attack zinc silicates, as well as high contents of free fatty
acids in vegetable or animal oils: Zinc silicate coatings may under such circumstances cause zinc pick up into
the cargo. They are therefore not normally suitable for edible oils for human or animal consumption. Remember
that the contents of free fatty acids, and thus also the aggressivity and zinc pick up, may increase during
transport. Certain coatings have Governmental approval for edible oils, check for pH-limitations in such cases.
Zinc silicates are not suitable for long time exposure to seawater, the life span will be unduly reduced.

After carriage of molasses in zinc silicate coated tanks a thorough cleaning should be carried out as soon as
possible. Sour cargo remains on the tank bottom may damage the coating.

Zinc silicates are only partly resistant to chlorinated compounds (e g carbon tetrachloride, ethylene dichloride,
trichlorethylene). If the water content is high hydrochloric acid may develop, which will attack the coating. In a
similar way hydrolyzable hydrocarbons such as esters, acetates and halogenated compounds may .attack the
cargo. If, however, the product is guaranteed dry and the cargo tanks and piping are completely drained and
dried these products can be carried.

Alkaline tank cleaning agents (caustic) should never be used in zinc silicate coated tanks. Considerable damage
can be done~in one single cleaning operation. Zinc silicates stand well up against other cleaning agents such as
"solvent cleaners" and "emulsifiers" unless they have alkaline additives: Check first with the maker of the
cleaning product!
If a zinc silicate coating has been attacked one can often observe a thin layer of white dust on the surface, or the
coating gives a porous appearance. Inform the Owners at once; it may be that the last cargo was off
specification and caused the damage.

Phenolic resins are a recent addition to the family of tank coatings. They have a wide resistance list including
strong solvents which the epoxies do not tolerate- At the same time the phenolics accept about all of the
products that zinc silicates tolerate. This type of coating is likely to gain further application on board.
Polyester coatings have poor resistance to solvents but are fairly resistant to weak acids and alkalies. They are
not used on board in chemical tankers to any extent.

Maintenance of tank coatings means, above all, not to subject the coatings to non-permissible cargoes. Check
with maker's recommendations. Limitations as regard pH-values, max temperatures and max permissible
storage time on board must be followed. Let epoxies regain their hardness if softened. Generally it is not worth
while to recoat an epoxy coated tank on top of an old coating, the risk for a poor bond is too great. Minor
damaged areas can, with a certain degree of success be recoated. The area must first be degreased well. The
area should then be ground to a bright steel finish with a rotating grinder, grain 80 to 120, with an even
transition to the coating. 1 - 2 coats of primer plus 3 - 4 finishing coats may be necessary in order to build up
the proper film thickness (200-300 microns). The tank wall may have to be warmed up (preferably from behind)
in order to insure that there is no risk for condensation on the surface. If possible the, tank wall should be
warmer than the tank atmosphere. For application of coating on a whole tank the steel bulkheads must be
properly sandblasted (non marine origin sand), normally to the internationally known standard Sa 2 1/?.

4.06 Rubber lining

In recent years a number of ships have been fitted with rubber lined tanks, for the transport of phosphoric acid,
waste acids and hydrochloric acid.

The mild steel surfaces to be lined should be prepared by grinding away rough weld beads, surface defects,
weld splatter etc. Then comes sandblasting to "bright metal" (Sa 2 1/2 - 3), priming with a rubber glue and an
application of a contact rubber glue. Thereafter the uncured rubber is applied in wide sheets and pressed on by
means of hand rollers. The rubber is usually 4-6 mm thick with reinforcements where mechanical wear may
occur, such as hatches etc. The rubber is vulcanized by heating with steam or hot water for a period of 15-30
hours. Synthetic rubbers may have a curing accelerator added and will vulcanize at normal ambient temperature
(20-30 degr. C) in a few weeks.

Natural rubber has been used in ships for phosphoric acid. But chloroprene (neoprene) synthetic rubber is a
more usual choice on board. It has a much better resistance to sun radiation, oils and ozon, Chloroprene is,
however, more expensive and is somewhat more difficult to apply. Chloroprene is resistant to strong acids (not
sulphuric acid) and strong alkalies such as caustic soda. In some cases chloroprene lined tanks have been used
for backhauls with fuel oils. This rubber will, however, not tolerate light hydrocarbons. Butyl rubber has a very
good chemical resistance but is stiff and hard to apply.

Great caution must be exercised so that the rubber will not be subjected to mechanical damage due to falling
objects, tools etc, Rubber lined tanks should have a minimum of fittings such as brackets, ladders, internal
piping etc which can create weak spots.

Steel piping, including bends, can be rubber lined. The pipe diametres should be chosen somewhat liberally in
order to keep liquid velocities relatively low. Membrane types of valves as well as pumps can be lined with
hard rubber. As heavy wear may occur on these parts the use of stainless steel is, however, recommended. The
advantage of having a pure rubber lined system with regard to a possible high contents of chlorides in the
product will then, however, be lost, see 4.02.

Rubber linings are tested for pores and defects by means of a high voltage tester at 10 000 V (chloroprene) and
20 000 V (natural rubber). To check the progress of curing or aging a Shore Durometer is used.

Shore tanks are sometimes lined with PVC (poly vinyl chloride) sheets glued into place. But this technique does
not seem to be sufficiently developed for use on board ships.

4.07 Gaskets and packing

When PTFE (polytetrafluor ethylene, trade names: Teflon, Fluon, Hostaflon TF) came on to the market a few
Years ago it solved many gasket problems. This material is resistant to all likely chemical cargoes and all
common temperatures on board. The PTFE has some very typical properties: it is expensive, has a low frictional
resistance and a low thermal conductivity, does not adhere to other materials and yields or "creeps" when under
pressure.

PTFE as a gasket in flange connections should either be reinforced (asbestos or glass fibres), contained in a
grove (male/female) or used as a relatively thin envelope around a core of more conventional gasket material.
"Creep" can then be controlled. "Blue" asbestos generally gives better chemical resistance against acids (pH
1-4) than "white" asbestos. In "envelope" gaskets the cargo comes into contact with PTFE only, which is an
advantage.

It is an advantage to use PTFE packings in pump and valve spindle gland boxes. But remember that the bottom
clearance between spindle and housing may have to be less than usual as the packing will have a tendency to
creep out this way.

Although PTFE will solve most problems one must remember that common, and cheaper, materials will often
suffice. If an existing oil tanker is to carry strong solvents (e g aromatics, ketones etc) flange gaskets of
asbestos- reinforced synthetic rubber will usually be acceptable. Flange gaskets of synthetic rubber-asbestos
will normally stand up against strong solvents, alcohols, strong alkalies (caustic) and acids. If in doubt, check
with the maker. Expansion glands in cargo piping and valve spindle glands, however, should be repacked
with PTFE-asbestos packings.

Rubber gaskets are not suitable for oils or solvents. Rubber is suitable for phosphoric acid. Chloroprene rubber
(Neoprene) is resistant to caustic soda and ammonia solutions.

Carbon fibre spindle packings are sometimes used in high speed pump glands. They are expensive but have the
advantage of low friction, chemical inertness and high thermal conductivity.

Nitril and fluor (Viton) rubber have a very good chemical resistance, see 3. 02, to strong solvents as well and
are used particularly in O-rings for stem seals in valves.

See also resistance table in Chapter 3. 02.

5 FIRE PROTECTION
Fire prevention is one of the most essential safety measures on board a chemical tanker. Discipline is needed in
the daily routines. Watch out for obvious things such as:
- look out for all leaking flanges, valve and pump glands
- keep pump room bilges free from cargo spills
- see to it that steam pipe insulation does not get soaked with oil or cargo
- check cargo tank and pump room atmosphere for cargo vapours before starting any work there
- do not steam a cargo tank simultaneously with washing
- use flame-proof lights in cargo tanks and pump rooms
- check pump glands and bearings regularly for heating
- cigarette lighters in the cargo tank area to be forbidden
- observe cargo vapour release during loading and take action if vapours reach accomodation areas
- check cargo pump glands for heating
- take active part in safety-drills and get acquainted with all the safety equipment
- instruct newcomers on board on safety procedures
- get to know your ship, cargo handling gear etc.

The formal responsibility for surveillance of the fire fighting equipment normally rests with the respective
National Authority, but is in some cases delegated to the Classification Society. It rests with the Owner and the
Master to keep all equipment in order and to provide additional means for any cargo not covered by the intent
of the Rules of the National Authority. The IMCO "Bulk Chemicals Code" ref (25), Chapter III, see Appendix
6, gives some general guidance on necessary equipment on board and indicates the best means for extinguishing
fires for a number of cargoes. Similarly the ICS Tanker Safety Guide ref (t) gives more detailed information on
the choice of extinguishing method to be used for the individual cargoes
Several methods of extinguishing fire can be used. Without going into more complicated details let us list the most
important aspects of the matter of fire fighting in the cargo area on chemical tankers:

5.01 Water extinguishing

All ships are fitted with means for fire fighting with water. Although not ideal, water can be used on fires in a
majority of chemical cargoes, the advantage of course lying in its abundant supply. Water is, however, not very
effective in extinguishing fires in very gassing cargoes such as naphta, gasolines or liquified gases; it may, however,
then be used as a cooling medium in connection with dry powder or other methods of fire fighting in order to avoid
dangerous "back flash", see 5. 03.

Water should be applied to the base of the fire by means of water fog jets, water pressure preferably not lower than
9 kp/cm 2. The fog serves as an excellent heat radiation shield in front of the. operator. Never direct a solid jet of
water on to a burning liquid surface, the effect will only be that burning liquid is splashed around, thereby making
the fire bigger. 'Water fog shall be applied with a strategy of chasing the fire succesively away from the operator.
The fog may be swung from side to side to cover a wide front of attack. Do not apply water fog on top of foam; it
will cause the foam to disintergrate and may possibly in so doing expose the surface of the flammable cargo to the
risk of a back flash.

It is a good practice to have water hoses with fog jets connected to the fire main on deck during cargo handling.

The IMCO Code ref (25) advices against water for most products in the relevant "Summary of minimum
requirements". This list, however, is meant to emphasize that other extinguishing media are a first choice and are to
be provided on board.

Do not hose water into conc sulphuric acid, an eruption of liquid may occur!

5.02 Foam extinguishing

Foam extinguishing is provided on many chemical tankers and on a majority of modern large crude oil carriers. Of
all the extinguishing methods in the IMCO Code foam is preferred, but the use of dry powder is generally accepted
as an equivalent method.

Water soluble chemicals, e g acetone, alcohols, have a tendency to break down conventional foams and render them
in effective. Chemical tankers should therefore be provided with alcohol- resistant foam ( "alcohol foam"). On the
data sheets in the ICS-Tanker Safety Guide, Chemicals, ref (1) it is especially stated for every product if alcohol-
resistant foam is a "must".
Heavy foam (water/air ratio abt 1:15) is in modern tankers distributed by means of several foam guns which can
cover the entire deck area, by means of portable jets or by means of long portable pipes. The latter are intended to be
used for the introduction of foam into a tank on fire without risk for the foam to dip underneath the liquid surface.
Foam has a limited extinguishing effect on very gassing cargoes: the gases penetrate the foam and burn on top of it.
Foam is a good method for fire prevention: a deck area or a free cargo liquid surface can be protectively foam
covered if there is a danger of fire. If a liquid surface is to be foam covered: direct the foam onto a bulkhead or other
vertical surface and let it spread from there and float out to cover the entire liquid surface. The foam operator may
have to be shielded against heat radiation by means of a water spray.

Medium density foam (water/air ratio abt 1:200) is used in enclosed spaces such as pump rooms. Medium density
foam can be produced very simply in fixed distribution jets under deck, in e g a pump room, by using the ejector
power of the water stream to draw air into the water foam mixture. Medium density foams are intended to cover the
bottom part of a compartment. The installation is very simple and relies on starting the fire-pump only.

Light foam (water/air ratio 1:200 - 1:1000) is only used in enclosed spaces such as engine and pump rooms. It is usu-
ally produced by means of a water driven fan which blows up the foam mixture. The foam is intended more or less
to completely fill up the compartment in question.

Light foam is sometimes used as a preventive blanketing medium when "hot work" (e g welding) has to be carried
out in a cargo tank, which may not have been possible to clean perfectly. The whole tank bottom is then foam
covered, leaving only the work location free. Of course the tank has to be guaranteed gas free before starting hot
work. Similarly neighbouring tanks can be protected before welding is started on bulkheads.

5.03 Dry powder extinguishing

Many new chemical tankers use dry powder extinguishing Dry powdersystem as the main fire fighting method in the
cargo tank extinguishing area.

There are to be found centralized powder systems with possibilities of discharging several thousand kgs of powder.
Release boxes and hose f eels are strategically located on deck so that any point can be reached by two hoses, each
being usually max 25 m length. On smaller vessels self-contained powder containers of 1000-3000 kgs are located in
small deckhouses.

As mentioned above the IMCO-Code accepts dry powder as equivalent to foam. Dry powder has decided limitations,
which are explained below.

The extinguishing effect of dry powder originates mainly from an inhibiting effect on the combustion. The smother-
ing and cooling effects are small.

Dry powder has a particularly good extinguishing effect on larger volumes of burning gases and strongly
vapourizing liquids, as compared with other means of fire fighting. But it has virtually no cooling effect on any steel,
cargo liquid or other matter that has become heated from the fire. Once the flames have been thrashed out with dry
powder there is a great risk for a fire back flash which can be more violent than the original fire. At a major fire
therefore, the fire area should be cooled down with water fog as much as possible prior to application of powder.
Water cooling must be continued after the flames have been extinguished If a fire can be fought immediately after its
outbreak and only little heating has occurred one should of course immediately start with dry powder, not awaiting
water fog assistance.

Common types of dry powder have a tendency to break down a foam layer. Therefore the two methods should be
avoided being used together. Some new powders are claimed not to have this deteriorating effect on foam.

Always place two dry powder extinguishers at hand on deck aft of the cargo manifold, when loading /unloading.

5.04 "Total flooding" system for pump rooms. Inert gas for fire protection
II

Many tankers have a-CO2. “total flooding" system for the cargo pump rooms. This is a most effective method for
extinguishing a fire in a closed compartment. Certain dangers, however, are involved
- make sure the room has been evacuated before admission of CO 2' No one will have a chance of escaping
once the gas has been admitted.
- the released CO 2 may assume a strong electrostatic charge which may cause incendive sparks. This is of no
consequence if the room is already on fire, but if the room is to be inerted with CO 2 as a preventive,
measure this should only be done knowing that the room is gas free.

Lately halogen gas total flooding systems have been installed on a trial basis. This gas does not possess the above
disadvantages and is easier to install.
Inert gas in the cargo tanks, see 3. 05, is to be considered a preventive safety measure only. The delivery capacity of
inert gas generators etc is far below the requirements for active fire fighting.
6 TOXICOLOGY.,
SAFE PRACTICES ON BOARD,
PERSONAL PROTECTION
To ensure safety on board one must adhere to the following points: Knowledge, training and strict routine.
Knowledge of the cargo to be loaded, knowledge of your ship and her equipment; training in the use of safety
equipment on board; strict routines in cargo handling, tank cleaning, strict routine in command and reporting,
strict routine in using protective clothing etc.

6.01 Poisoning and other risk with cargo contact

Different chemicals affect the human body in many different ways. The subject is comprehensive and a deeper
insight in to this is beyond the scope of this book. A general information and some practical advice will be
given, however. Reference is given to Appendix,7, being an extract of "Medi cal first aid guide for use in
accidents involving dangerous goods" published by IMCO, WHO and ILO ref (36).

The definition of "poisonous" and classification of poisons is not uniform throughout the world. We can define
a poison as a substance which is harmful to human beings (or environment). In the IMCO Code ref (25) a
substance is classified as a poison if there is a risk of death or serious bodily harm after oral intake, inhalation
or skin contact.
The "poisonousness" of a substance is usually expressed in terms of LD 50- values, Lethal Dose (sometimes LC
509 Lethal Concentration). These values are determined by tests with animals and give the dose, expressed in
mg/kg body weight, which kills 50 % of the animals in a test series. This figure gives a rough indication of the
degree of toxity of a substance. Various species of animals have different sensitivity, which gives some
problems in applying the results to human beings. Examples of LD 50 values (pesticides of three categories):
Class LD 50 Substance
1 125 mg/ kg body weight paration (pesticide)
2 125-1500 - //- malation - // -
3 1500-2000 - // - bromofos - // -

In industry the effect of long time exposure of low concentration to a substance is of prime concern. The
expression used is TLV (.1hreshold Limit Value), previously called MAC (Max Allowable Concentration). The
TLV-value expresses the concentration of a substance in air, in ppm (parts per 3 million) or mg/cm , which
must not be exceeded if a daily 8-hour exposure over a long period of time shall be harmless.

TLV-values are published by National Authorities and various organizations. The most recognized list of
TLV-values is probably the one published by ACGH (American Conference of Governmental Hygienists
ref (15). The ICS-Guide ref(1) also gives TLV-values. The gas concentration can be measured by means of a
portable apparatus described in 3. 10 (Drager, Auer). The scale of reference for gas exposure on board is
normally TLV -values. Human beings can, however, tolerate a significantly higher concentration in a short time
exposure:

Substance Danger of serious TLV

poisoning after (Swedish 1978)
less than one hour
inhalation

Acrylonitrile 100 ppm 2 ppm

Trichlorethylene 250 pprn 20 ppm
Carbontetrachloride 2000 ppm 2 ppm
Methanol 2000 ppm 200ppm
Benzene 10000 ppm 5 ppm

A person who is tired or ill is more sensitive than others and should not be asked to work with cargo handling.

It is a good safety practice to use a breathing apparatus whenever the TLV-value in the atmosphere is exceeded
Poisoning

The poison may enter the human body orally, by inhalation, or by skin contact. After being absorbed by the
body it may affect certain organs or give a general poisonous effect. Lately the cancerogene effects of some
industrial chemicals have been noticed. This has led to significant reductions of hereto accepted TLV- values in
many countries. Certain substances affect the tissues locally as an irritant (cashew nut shell oil) or cause grave
damage to the eyes, skin or mucous membranes (e g strong acids and caustic). Other substances may be ab-
sorbed by contact to the skin without local effects (e g nitrobenzene, aniline). Gases, in themselves
non-poisonous, may be dangerous by their displacement of air (e g nitrogen as an inert gas in cargo tanks). The
effect of a substance also depends on the temperature, its solubility in water or (skin) fat, its volatility etc.

Chlorinated hydrocarbons (e g tetrachloride and chloroform) may cause damage to kidneys and liver after
prolonged exposures.

Symptoms of poisoning may appear many hours after contact with the substance. Typical examples are
poisoning from nitrous gases, see 3:05, and methanol ( oral intake). The reason for the delay being that the
decomposition products rather than the original product are toxic. Common symptoms of poisoning are: nausea,
headache, dizziness, difficult breathing, unconsciousness.

The human body often reacts very differently to acute and chronical poisoning. (Acute poisoning - one contact
with the poison, usually high dose or strong concentration. Chronical poisoning - small doses or low
concentrations over a long time). E g benzene causes reduced conscoiusness in acute poisoning but causes
blood and bone marrow damage in chronical poisoning.

Certain chemicals may cause sensitizing upon first contact. Later contacts with the same chemical, even at
lower concentrations, may cause much stronger poisonous effects. Typical in this respect are isocyanates ( e g
toluene diisocyanates) where astmathic -affects on sensitized persons may occur below TLV- value.

6.02 First aid

All cases of poisoning, regardless of which kind of poison, require certain basic common methods of treatment.
Additionally, a few particular cases of poisonous substances may require antidotes. See Appendix 7 for detailed
information on first aid for the various products!

After a severe acute case of poisoning involving unconsciousness: Bring the patient as soon as possible out into
the fresh air. Rescue personnel must not take undue risks themselves, don't therefore rush down into tanks or
pumprooms where vapour may be present- Too many fatalities have occurred with people who have not
realised that a breathing apparatus was needed. First, keep the breathing passages free (prevent the tongue from
falling back). An unconscious person should be laid on his side, face down, with one arm and one leg bent to
prevent him from rolling over. Loosen the clothes around the neck and waist and remove false teeth, see fig 39.
Mouth to mouth artificial breathing may be necessary (avoid mouth to mouth contact with severely poisoned or
contaminated patients as the rescuer may then be at risk). Heart massage may be necessary. See Appendix 7 for
detailed advice.

If the patient's condition does not apparently involve immediate risk for his life the following measures are
applicable:

After inhalation: The patient to be brought into fresh air with as little effort and strain to himself as possible,
Undue strain on the patient may affect him adversely later. Even if the patient is free of all symptoms he should
be kept quiet and rest as some gases have delayed effects (nitrogen oxides in combustion inert gas, nitrous
gases). Keep the patient in a comfortable inclined sitting position (if unconsciousness does not prevent it).

After splash in the eyes: Immediately wash the eyes in gently flowing water, in a washbasin, in a jug or a
special plastic eye bath with a bottle of water, see fig 40. The eyelids may have to be forced open and the
patient told to move the eyes in order that all parts will be thoroughly rinsed out. Washing out the eyes may be
very painful and pain-relief eye drops can be used. Continue to wash for another 10-15 minutes. In case of acids
or alkalies (caustic) the washing must be repeated for a couple of minutes every 15-30 min for the next 4-5
hours, preferably with a NaCl (table) salt solution (0, 7 - 0, 9 %). A sterilising eye ointment should be applied
several times during the day. In case of acids and alkalies: obtain medical advice!

After skin contact: Regardless of product the area should be rinsed liberally with water, clean sea water can be
used.Soiled clothes, rings, watches, shoes etc must be taken off. Wash the area thoroughly with soap and water.
Also products which do not disolve in water will be partly removed by washing in soapwater. (Poison dissolved
in the skin fat will then be washed off).
After swallowing: If the patient is unaffected give him a couple of glasses of liquid to drink for dilution of the
poison, preferably water (never any alcoholic drink). After intake of alkalies (caustic) a drink of lemon juice
can be given, or a 1 '76 solution of acetic acid. If available give medicine coal which absorbes a number of
poisons and which in itself is harmless (30-60 crushed coal tablets or coal granulate in some water). Make the
patient vomit, NOT, however, in the case of corroding (acids or caustic) products or oil products like kerosenes,
gasoline, jet fuels, when vomiting may be life-threatening. Dilution of the stomach contents, however, is
important. In case of doubt: do not cause the patient to vomit.

Vomiting can be caused by giving warm salt water (one table spoon of salt to one glass of water). Then by
putting two fingers down the throat and moving them about gently vomiting usually follows. The procedure is
described in ref (36).
After certain products antidotes should be given, see advice in ref (1) and (36). The most likely cargo for which
an antidote may have to be used is acrylonitrile ("AN") and acetone cyanohydrine. The remedy then is to douse
some clean rag with an ampoule of amyl nitrite from the medicine kit and hold it under the patient's nose 5
times with 15 s interval.

Oxygen should be administered in cases of weak breathing. It is an IMCO Code ref (25) requirement to have
oxygen resuscitation equipment on board.

In cases of poisoning medical advice should be sought as soon as possible, e.g through the various
radiomedical" services. While at sea also contact the shipper, who usually possesses a good knowledge of the
product and its after effects.

6.03 Cargo information to ship’s personnel

The following advice is more or less obvious but is listed for the sake of completing the above information.
It is a clear responsibility for the Owner, the master and the officers to inform their personnel about the cargoes
to be carried, safety procedures etc and to arrange for the proper training.

Information should be given partly in the form of written notices combined with informal meetings with the
entire crew present when new cargoes are to be loaded or when unexperienced personnel are to be signed on.
Among other things the following information should be given:

- Cargoes to be loaded; their characteristics as regards handling, pumping, toxity, corrosiveness, first aid etc

- the cargo loading plan to be posted in places where it will be clearly seen by everyone on board and at the
accomodation ladder, when in port.

- Post cargo information cards for products to be loaded or are contained on board. One suitable type of card
can be found in ref (i), with examples in fig 43. Also ref (4) and (5) show suitable information. For "new"
products ask the shipper for safety brochures and leaflets. See also ref (3), (12), (13), (16), (17) and (28).

- the personal safety equipment to be used by those involved in cargo handling, pumping, sampling etc.
CHEMICALS - YOUR SAFETY ON BOARD!

Make sure that you:

- use goggles, gloves, oilskin or apron and rubber boots when operating cargo gear.

- use more extensive personal protection when needed or when ordered to do so. See separate instructions for various
products.

- know what products are carried on board and that you are familiar with their respective safety measures. Study safety
instructions and ask the Chief Officer!

- know where eye flushing bottles are located (pump-rooms and on deck midships).

- now and practise how to flush your eyes with water IMMEDIATELY in case of accident. Eyelids may have t6 be forced open to
permit proper flushing!

- know where safety showers and water rinsing hoses are located, in pumprooms and on deck.

- use breathing apparatus in tanks/pumprooms which have not been declared safe or when ordered by officer on duty.
Breathing apparatus shall be available for immediate use on deck when loading/discharging.

- never enter dangerous compartments unless ordered by officer on duty. Proper personal protection should be used and
personnel should stand by.

- know where the oxygen resuscitation apparatus is located.

- take part in the monthly safety drills.

Fig 42 Examaple of a safety poster

- Have available on board litterature on chemical cargoes, medical advice etc,

- Inform in particular if the cargo to be loaded has an odour threshold which is higher than the TLV-value,
see 6. Of, and that danger cannot always be sensed in advance ( e g allyl alcohol, carbon tetra chloride,
etylene dichloride).
- Give information that most vapours are heavier than air and have a tendency to accumulate in low spaces.
Therefore work below gratings in pump rooms, cofferdams, pipe tunnels etc is extra dangerous.
- Never take work clothes into your cabin! Soiled clothes must be washed before being used again or in the
case of toxic products, destroyed.
- Wash your hands before meals!
- Give information about fire fighting methods for each type of cargo on board.
- Give information if the cargo is water-reactive or reactive to other cargoes on board. Give information on
segregation required.
- For some very toxic cargoes mouth to mouth artificial breathing might be dangerous to the rescuer (e g
acrylonitrile, acetone cyanohydrine).
- Information must be given particularly if the cargo danger lies primarily in vapour inhalation (e g
acrylonitrile, trichlorethylene) or skin contact (e g phenol, caustic soda, sulphuric acid).
- State where eye washing bottles are located (deck office, at cargo manifolds on deck, in pump rooms, on fore
deck etc).
- Insist on that nobody should work with cargo gear without anyone standing by. Have people report when
going to and returning from pump rooms!
- Give information if any cargo is so toxic that an escape breathing mask must be used in an emergency.
6.04 Ship information to ship’s personnel
It is essential on chemical tankers that everyone knows his ship's safety precautions thoroughly. Also the
master/chief officer must assume responsibility for this. Newly signed on members of the crew should be informed
about the following items and be shown around the ship to get detailed knowledge:

- Get to know pump rooms, cofferdams, pipe tunnels, emergency exits.

- The manouvering and emergency stops for cargo pumps and cargo valves.
- Bilging of pump rooms.
- Pump room ventilation incl information on necessary pre-ventilation before entry and emergency stop of fans in
case of fire.
- Safety showers-(in pump rooms, fore and aft on deck),
- Gas warning equipment incl the sounding of alarms (fixed and portable).
- Lifting gear incl stretcher to get an unconscious person out of a Pump room.
- Cargo tank vapour vents, incl opening, prior to cargo filling/discharge.
- Cargo sounding equipment.
- Location of fire fighting equipment incl detailed instructions for operating them.
- Portable fire (powder) extinguishers placed at hose manifold.
- Water hoses to be connected amidships ready for washing off cargo spills (if considered proper under the
circumstances)
- Cargo tank arrangement.
- Cargo piping system incl means of segregation.

In fig 42 a set of safety instructions for a particular vessel are shown as an example. Make one which suits your ship!

For the sake of record it may be noted in the deck log when cargo/ship information has been given.

6.05 Safe practices when handling cargo

Most of the items listed below have been briefly mentioned in the previous text. The list can be used, however, as a
check list for some general practices and common safety routines:

Before loading /unloading:

- Have cargo tanks to be loaded well ventilated and checked for any toxic vapours so that tank inspection can
commence without any danger or undue delay.
- Portable (dry powder) fire extinguishers to be placed on deck ready for use. Take off covers etc and make other fire
fighting equipment on deck ready.
- Check cargo hoses to see that they have not deteriorated, that flange connections are intact, that there is an
electrical bond between hose flanges and that the working pressure for the hose is marked on it. If there is any
doubt about the hose's condition, find out when the hose was last pressure tested, see 3. 02. After connection of the
hose to the ship's manifold the. flange should be pressure tested for tightness with air at 6-10kp/cm 2 (shore valve
closed). With corrosive and toxic cargoes a protective cover should be placed over-the hose flange connection. A
drip pan should also be there.
- Establish communication routines with the terminal operators regarding flow rates, emergency stops, topping up,
general alarm etc.
- Keep unauthorized people away from the cargo deck and hoses. Check that vapour release/admittance to the cargo
tanks is unobstructed (P/V valves moveable, lids opened, flame screens unclogged etc).
- Keep hatch lids closed except when taking ullages, sampling etc.
- See to it that everyone engaged in cargo handling is wearing the correct protective clothing (depending on whether
there is danger to the skin on contact or inhalation of vapour.
- Avoid getting the blast of vapour in your face when taking ullages during loading. Do not stand "upwind" or
"downwind" of an ullage hole but stand beside it with the wind across your face.
- Keep pump rooms ventilated with fans running during cargo transfers.
- Keep moderate loading rate during the first phase of cargo transfer to an empty tank (not necessary with
inerted tanks), particularly with petroleum products of the type kerosene, jet fuel. The liquid velocity should
be kept well below I m/s in the cargo piping until the liquid covers bottom framing or about 0, 5 m above
bottom. (Risk for static electric charges and incendive sparks. See ref (9)).

1 m/s means for a 4” pipe 30 m.3/h

- // - - // - 8” - // - 114 - // -
- // - - // - 12” - // - 258 - // -

- The final ullages should not be taken before 30 min after loading is finished if conductive tape is used (when
possible static electric charges are likely to have been dissipated). Non-conductive tapes to be preferred.
- Never go down into a pump room without reporting to someone on duty when leaving and on returning.
- Never work alone in confined spaces!
- Have breathing apparatuses on deck ready and available when handling toxic cargoes.
- Remember that an explosimeter only indicates the risk for explosive conditions - toxic conditions may arise
at far lower concentrations than detectable by an explosimeter instrument. Use also a toxiometer for health
readings. See 3.10 and 6.01.
- Never wash and steam a tank simultaneously. Many explosions have proved this to be a dangerous
combination, electric charges are a likely reason. It might be dangerous to enter a tank containing oxidizing
vegetable oils (e g castor seed oil, cotton seed oil, ground nut oil, linseed oil) during the last phases of
discharge. There are indications that conditions with lack of oxygen in the tank atmosphere may develop. Use
a breathing mask with fresh air supply or forced ventilation.

One "half-mask" and one emergency mouthpiece with nose clamp is shown in fig 48. The maker will be able to
advice on types of filters for the cargoes in question. For escape purposes a better equipment is handy air
bottles with masks for short time use.

- Air compressor for recharging of breathing air bottles (200-300 atm) should be standard equipment on
chemical tankers.

Below is listed suitable equipment for operational personnel for various typical cargoes and operations on
board:

a) Products involving little or no danger upon skin contact, moderate vapour toxity and relatively high volatility
(low boiling point) as e g: petroleum products, petroleum naphta, toluene, benzene, xylenes, methanol, acetone,
methyl ethyl ketone, gasoline, styrene,
Use: Rubber boots, gloves.
Have in your pocket for use : (when taking ullages, sampling etc) Plastic goggles
A breathing apparatus (compressed air type 200 atm) should be kept ready for immediate use if sudden entry
into a gas-filled pum-proom should become necessary. Eye washing bottles available on deck and in pump
rooms. Explosimeter and toximeter available.

b) Products with a strong corrosive effect on human tissue, moderate or low vapour toxity as: sulphuric acid,
caustic soda, phosphoric acid (eye danger primarily), acetic acid. Use : Goggles or face shield, oilskin or apron,
rubber boots (trousers outside), long cuffed rubber gloves, helmet. Eye washing bottles available on deck and in
pump rooms
c) Products which involve great danger upon skin contact (poisoning) and high vapour toxity as e g: phenol,
acrylonitrile, acetone cyanohydrine, allyl alcohol, aniline, chlorosulfonic acid. Use on open deck (as a
minimum): skintight fitting goggles or face shield, oilskin, rubber boots (trousers outside), long cuffed rubber
gloves (tucked inside jacket sleeves), helmet.
Have in your pocket for immediate use: Gas mask (full mask or emergency mouthpiece with nose clamp). Eye
washing bottles available on deck and in pump room . At least two breathing apparatuses (compressed air types)
should be kept available on deck for immediate use. Toximeters available on deck. When handling hoses or entering
contaminated areas: use full protective suit, preferably of pressurized type with hood and permanently attached
rubber boots.

The IMCO Bulk Chemicals Code ref (25) gives some general information on the amount of and the type of personal
protecti6n to be provided on board. For the purpose of being a check list is given below what might be considered
the minimum amount of equipment on board a chemical tanker of 30 000 tdw. Indicated, in brackets, is the
IMCO-Code minimum requirement (where given). An "x" means "sufficient":

Number of

6 (3) Breathing apparatus, compressed air type, with air bottles ( in addition to SOLAS fire fighting
equipment) min. 20 minutes action time.
1 Compressor with fittings etc. for charging of air bottles for breathing masks.
12 Air bottles to above (7 l at 200 atm or 4 1 at 300 atm), as reserves.
3 Breathing hood with filters and 2 x 30 m hose.
3 (3) Protective suit, chemical resistant, overpressure type with hose connection. Rubber boots attached
with chemicals resistance list.
6 (3) Protective suit, chemical resistant, rubber boots (attached with chemicals resistance list)

30 (x) “Oilskin”, chemical resistant.

20p (3) Long rubber boots.

10 (3) Apron
30 p (3) Gloves, long sleved.
50 p (3) Goggles, plastic, tight fitting.
10 p (3) Face shields.
3 (3) Steel cored rescue line with belt and hook.

12 (3) Safety lamp.

2 (2) Gas indicator for flammable gases (double scale), with calibration unit.
2 (2) Oxygen indicator.
2 (2) Gas indicator for toxic vapours (with liberal supply of detection ampoules for likely cargoes).
10 (x) Eye washing bottles.
1 (1) Oxygen resuscitation equipment.
(all on (all on Gas mask for emergency use, with filters for cargo vapours (if very toxic and volatile cargoes are to be
board) board) carried).

(x) (x) Antidotes. See 6.02 and ref (36) re cargoes.

(i) (1) Stretcher suitable for use in pump rooms etc (Japanese type)

(x) (x) Shower (on deck and in pump rooms)

(x) (x) Cargo and medical information (e.g ref (1), (2), (4), (5), (16), (17), (22), (25), (36)).
NB: Nitrile rubber (gloves) is not resistant to acrylonitrile and should not be used with this product.
7 TANK CLEANING
Cleaning of tanks is usually the responsibilty of the ship. See paragraphs 8 and 9 in "BIMCHEMVOY" in
Appendix 8.

Tank cleaning and the cleanliness involved have different standards depending upon the previous cargo and the
cargo to be loaded. But the matter can be still more complicated, as cleanliness for one and the same product
may vary, depending on who the receiver is and for what purpose the cargo is finally intended. Examples:
glycol intended for cosmetics or pharmaceutical purposes requires cleaner and completely odourless tanks than
does glycol intended for antifreezes; caustic soda for making paper is more sensitive to iron contamination than
caustic soda for the aluminium industry.

It must be mentioned first that the majority of cleaning op -rations on board chemical tankers are being carried
out by means of water washing only. Further chemical cleaning is required for only a limited number of
cargoes, but these cases may be very important.

One must take into consideration the nature of the previous cargo and the cargo to be loaded, time factor,
available equipment and cleaning chemicals etc. In Appendix 5 it is stated the necessary degree of cleanliness
for a number of products, in line with what cargo surveyors normally require.

Generally speaking one should use mechanical tank cleaning methods, that is usually washing with water,
before applying more expensive methods involving chemical cleaning agents. The most expensive, and least
safe, method is manual cleaning, which should be kept to a minimum. Manual work should preferably be
reduced to inspection and possibly to a final drying up of washing water only.

It is important to drain the tanks as much as possible in order to deliver all cargo and to reduce pollution of the
seas to an absolute minimum. This will now be even more important with the anti-pollution Convention of 1973
(see 10.01).

Examples on measures on how to obtain the best possible cargo stripping:

- Due regard to ship's trim and heel.

- Viscous cargoes may first be stripped from the various tanks to one tank near the pump room and from there
be pumped ashore.
- Keep the cargo temperature sufficiently high so that the cargo drains also from remote corners of the tanks,
especially in cold climates.
- Waxy deposits under the heating coils can sometimes be melted out be means of filling with water and then
applying heat to the coils.
- Sometimes steaming is allowed during discharge of molasses, which facilitates draining of molasses from
the bulkheads.
- Vegetable oil tanks may in the last phase of discharge be recirculated and hosed down with vegetable oil
taken from the cargo pump delivery side (see warning under 6. 05). Similarly phosphoric acid can be
recirculated to loosen sediments on the tank bottom.
- Drain cargo piping to shore. It is useful to have a small stripping pump with 50 mm delivery line to the hose
connection for delivery of contents in the cargo piping to shore.
- Before loading sensitive cargoes: mudboxes, valve bodies and pump housings must be drained by opening the
drain plugs (with due regard to personal safety).
The following text is intended as a general guide and will give some practical examples on problems and
methods. Reference is given to "Tank cleaning Guide", ref (10), excerpts of which are given in Appendix 4. See
also ref (11). The information given should not substitute your own or others' good and proven methods! Also
consult shippers and tank inspectors coming on board.
Analyze the properties of the previous cargo and take advantage of its "weak points", e.g as follows:

- Water soluble? If the cargo is reasonably soluble in water then chemical cleaning agents are unnecessary in most
cases.
- Will an increased cleaning temperature cause a beneficial reduction of cargo viscosity and lower surface tension or
could it cause the opposite: that cargo residues polymerize or oxidize ("dry"). Polymerization and drying must be
avoided, therefore the first cleaning operation must be carried out cold.
- Is it possible to emulgate the cargo in water or in water with emulgators added? Make a test on board.
- Will the product be affected by alkalies? Caustic soda is a relatively cheap and easily available alkaline chemical.
- Will the product dissolve in other easily available products by which the tank walls can be treated? (Succesively
"upgrading" or "floatation" methods).
- Will cargo residues vaporize without leaving any traces?
- Can cargo remains be safely mixed with the cargo to be loaded? In many cases it is not known what the next cargo
will be but sometimes this method can be applied.

7. 01 Pre- cleaning ( washing)

Practically all cases of tank cleaning start by washing with water. This is mechanical removal of cargo residues.
This method has a slight emulgating effect (forming minute droplets of cargo suspended in the washing water).

The water pressure should preferably be 12 - 14 kp cm 2 with a capacity corresponding to 4 washing machines (80-
10o m 3 /h). The washing water heater should have a capacity of yielding 80 degr. C washing water with 2 - 3
washing machines working.

While washing one should simultaneously drain the tank at the same rate in order to assist the cargo residues in their
flow towards the tank suctions. If not, the residues will have a-tendency to come to rest anywhere on the tank
bottom.
a) Products with good solubility in water (data on solubility in ref (1), (3), (5), (16): Pre-cleaning can normally be
carried out with cold water. Examples are: mineral acids (sulphuric acid, phosphoric acid), alkalies (caustic soda,
ammonia/potash solutions), alcohols (ethanol, methanol, butanol), acetone. The more viscous water-soluble products
may have to be pre-cleaned with hot water, examples: glycols, glycerine, molasses. Note: sulphuric acid must be
washed with copious amounts of water to guarantee rapid dilution and reduce risk of heavy corrosion.
b) Products which are volatile and vaporise without any traces frequently need no tank washin , only ventilation and
possibly steaming of the tank. Examples: acetone, methyl ethyl ketone, hexane, methanol, butanol, propanol, toluol,
trichlor ethylene. If water flushing is not carried out: remember to drain all cargo lines, pumps etc. Draining out
cargo may be a difficult process to carry out safely and therefore water flushing and subsequent draining of the
piping may be an advantage. Thereafter draining of water from the piping system can be carried out.
c) Some vegetable oils and animal oils (fatty acids) oxidize and "dry" upon application- of air and heat. Examples
are: castorseed oil, cottonseed oil, groundnut oil, linseed oil, spermoil, talloil. Pre-cleaning must then be carried out
with cold water. Otherwise the residues will dry up and harden and may be very difficult to remove. Final washing,
however, can be carried out hot, see 7. 02.
d) Vegetable oils and animal oils of non-drying type should preferably be pre-washed directly with hot water
(800C). Examples: coconut oil, palmkernel oil, palm oil, tallow, whale oil.
e) Polymerizing products should be. pre-washed with cold water or the tanks should be flooded with water. Hot
water may cause deposits of polymerized material, sometimes very difficult to remove. Examples on such products:
styrene monomer, vinyl acetate, acrylonitrile, vinyl chloride.
f) Heavy oils, lubrication oils, lubrication oil additives, gas oil are normally pre-washed with hot seawater (800C)
although cold water can also be used.
g) (Crude oil is mentioned as a reference. Crude oil with a relatively high percentage of light fractions such as
Arabian crudes are often pre-washed cold and then hot. If hot water is used the light fractions are liberated first and
then the residue tends to be tougher and more difficult to remove. Heavy crudes, however, e.g Boscan crude with
little or light fractions can be washed directly with hot water. )

7.02 Final cleaning

Method of cleaning to be used depends on both previous cargo and cargo to be loaded. Check with Appendix 4
and 5 regarding cleanliness requirements for cargo to be loaded.

As a general rule the tanks and piping shall be completely drained of water or residues before loading. The bottom of
the tanks may have to be dried up with rags.

Some cargoes are very sensitive to chloride contamination. The tanks to be loaded with these products have to be
washed out thoroughly with fresh water. Examples on such products are first of all glycols and alcohols (methanol)
but also aromatics and acetates. Vegetable and animal oils, gasoline, heavier oils, caustic soda do not normally
require a fresh water rinse of the tanks to be loaded.
,a) Products with good solubility in water: The final cleaning is a direct continuation of the pre-cleaning with water,
possibly with hot water for viscous products. If sensitive cargoes are to be loaded any odours that remain must be
ventilated and/or steamed away.
b) Volatile products , as mentioned above, do not often require cleaning after discharge.
c) and d) Vegetable oils (drying and non drying) and animal oils are best cleaned by using an alkaline chemical,
usually caustic soda, added to the hot washing water. The oil residues will then be converted into soap, which is a
water soluble product and which will be rinsed off the bulkheads. The cleaning chemical is consumed quite rapidly if
there are un necessary amounts of cargo left. About 100 kgs of caustic soda are required, counted as a 50 % solution,
to saponify 50 kgs of oil. Usually the cleaning chemical is added to the washing water in a 2-3 % concentration of
caustic soda (max 5 %. Warning: alkaline washing solutions are dangerous to eyes, use goggles! IMPORTANT:
Zinc silicate tank coatings are adversively affected by alkaline cleaning chemicals. Never use caustic soda or
alkaline cleaning agents in zinc silicate coated tanks !

Mineral oils and waxes cannot be saponified. It is possible to remove vegetable and animal oil residues by the use of
detergent cleaning chemicals. Detergents reduce the surface tension of the washing water, thus "lifting off" the
residues. Cleaning with detergents usually works out more expensive than cleaning with alkaline chemicals but it
might be the only solution with zinc silicate coated tanks.
e) Polymerizing products can, after a cold prewash, usually be cleaned off using cold or moderately warm water with
a cleaning chemical of a detergent type, emulsifier or with synthetic soap added
f) Heavy oils, lubrication oils, lubrication oil additives, gas oils and similar often account for the most difficult
cleaning problems, particularly if demanding products like methanol and aromatics are to be loaded. After the
pre-wash: hot washing with cleaning chemicals of a detergent type, solvent cleaner, emulsifier or synthetic soap.

Emulsifiers assist in forming minute droplets of the product suspended in the water. The emulsifiers are usually of a
type where one end of its molecules attract water and the other end oil. Soap from an alkaline treatment acts also as
an emulsifier. A dosage of 1-2% to the washing water is usually recommended. Certain emulsifiers are so effective
that the emulsion will not break up (water and product separate) after a long time, even if heated. If such a washing
solution is to be discharged to a slop-receiving facility ashore difficulties may arise. Check with the supplier of the
cleaning chemical and the slop-receiver before making your purchase of cleaning chemicals!

"Solvent cleaners" contain water-soluble and hydrocarbon dissolving agents (ketones, aromatics, alcohols), usually
in addition to other cleaning effects (alkaline etc). Solvent cleaners often have relatively low flash points: treat them
with care, as flammable products.

Detergents contain wetting agents (tensides) which reduce the surface tension of the water, thus "lifting off" impuri-
ties from the tank wall.

When several cleaning chemicals are used their sequence of application should be: (water), detergent/alkaline
(caustic), synthetic soap, emulsifier, solvent cleaner, solvent.

Leaded gasoline leaves posionous lead compounds on the tank walls which is unacceptable if edible products are to
be loaded next. In Appendix 4 a method is described where the tank is washed with 10 % acetic acid to remove lead
remains. This method does not, however, guarantee that the tank will pass a chemist's test and be accepted for edible
products. Wine has a particular tendency to absorb lead compounds from the tank walls. Edible products should not
be carried until after several other intermediate cargoes.

It is becoming more and more common to apply the cleaning chemical in undiluted form, see 7. 043.

7. 03 Odour
Some products are very sensitive to foreign odours, usually stemming from previous cargoes in the same tank.
Examples of sensitive cargoes are: glycols, glycerine, vegetable and animal oils, molasses.

Odours remaining after a thorough tank cleaning are usually best removed by steaming and/or ventilation of the tank.
Steaming "sweats out" cargo from pores etc. Cargo piping may also have to be steamed out. Epoxy coatings should
not be heated above 60 - (80) degr.C, zinc silicates tolerate somewhat higher temperatures. So called deodorant fresh
air sprays have an effect only on the atmosphere in the tank. Usually the odours stem from cargo residues on the
actual tank walls and will therefore soon come back. The spray method is more of a symbolic value with regard to
the care of the cargo.

7.04 Practical cleaning methods

7.041 Cleaning agent added directly to the washing water.

The cleaning chemical is injected into the washing water by means of a dosage pump, usually air-driven, through a
fitting attached to the washing pipe on deck. Sometimes the cleaning chemical is added to the suction side of the
washing water pump, thus eliminating the need for a dosage pump. But the dosage becomes less accurate and the
method is more cumbersome in the latter case.

A direct addition of cleaning chemical to the washing water is quite common, but chemical consumption tends to be
high and its full cleaning effect is not always utilised. 1-2 hours of washing is usually to be recommended. The final
rinsing being sea or fresh water, depending on the product to be loaded.

7.042 Recirculation of the washing water

Gives a better utilisation of the cleaning chemical. A mixture of 5 - 50 tons of hot water with the recommended
amount of cleaning chemical is made in a cargo tank, a slop tank, a cofferdam or a special tank for the purpose.
The water may be further heated by means of heating coils. A cargo pump may serve as a washing pump with
delivery to the washing line on deck, and then to the washing machines. Another cargo pump or stripping pump
drains the water back to the containment tank where the cargo residues can be removed by carefully drawing out the
washing water from the bottom.

Washing should only be carried out on condition that the tank atmosphere is well below LEL (lower explosive limit).
Check during washing! Washing should be carried out under inert gas atmosphere if cargo vapour concentration is
above LEL. There are indications that contaminated washing water may cause incendive static electricity sparks.
This refers in particular to recirculation washing.
The recirculation method can be used with all types of cleaning chemicals. One advantage is that one can easily
incorporate major parts of the piping system in the cleaning circuit. Remember cross-overs and risers to deck!

Finally rinsing with sea or fresh water.

7.043 The cleaning chemical can be applied undiluted directly onto the tank walls.
This method is becoming quite common. The cleaning chemical is sprayed directly onto the tank bulkheads by
means of a high-pressure (portable) pump and a long lance, which the operator can direct all round the tank. The
operator must use protective oilskins, goggles and preferably a breathing mask too. The cleaning chemical is left on
the tank walls for 20 - 40 minutes. The tank is then washed by hot water. The process is repeated where necessary
until the tank is clean. This method is very effective.

In a similar operation the cleaning chemical is added to an ejector, which draws it into the steam when steaming the
tank. The tank should first have been steamed thoroughly. After steaming with a cleaning chemical, steaming is con-
tinued for a while. Finally rinsing with sea or fresh water. Remember to keep the hatch lid slightly open to eliminate
excess pressure during steaming or sub-pressure after steaming is finished!

7.043 A floatation method is sometimes used

For the final cleaning to achieve a high degree of cleanliness after heavier hydrocarbons such as lubrication oils,
lubrication oil additives and before loading hydrocarbon- sensitive products such as methanol. (Normally a tank is
"upgraded" to methanol standard via two-three intermediate cargoes of aromatics ). The floatation method should
only be used after first washing with cleaning chemicals. The method is then very effective, but it is less effective if
cargo residues on the tank walls are of any appreciable thickness.

The tank is first filled to a level of 0, 4 - 0, 8 m from the bottom with a strong non water-soluble solvent, which is
also reasonably cheap. Toluene is usually used. Then the tank is slowly filled with water, thereby lifting the toluene
on top of it. After filling, the water is slowly drained again until the tank is empty. The top layer of toluene is then
transferred to the next tank and the process repeated (with the same water used again to minimize solvent losses).
The filling and draining can be done with a level change of, say 0, 5 - 2, 0 m/h depending on the degree of
contaminants on the tank walls.

There have been advanced warnings that this floatation method, although frequently used, might involve hazards as
regards static electricity charges in the interface between the two liquids. It is wise to pump slowly in order not to
exceed I m/s in the filling pipe, see also 6. 05. The process should preferably be carried out with the tank inerted,
see 3. 05.

7.045 Steaming with a solvent

Can also be done as a final cleaning process, after washing with a cleaning chemical. The method will only be
effective for removal of the very last traces of a previous cargo.
Fill the tank with water to just above the heating coils and add a non water-soluble solvent, usually toluene or
xylene. The water is then heated by means of the heating coils and the solvent vaporises. The solvent condenses to a
certain extent on the tank walls and dissolves minute amounts of cargo residues, which after draining of the tank can
be washed off using water with/without cleaning agents added.

The amount of solvent should be of such small quantities that the forming of explosive mixtures in the tank is
avoided. Choosing 2/3 of LEL as a guide one arrives at the following maximum amounts of toluene:

Tank size 200 m 3 abt 10 l of toluen

500 m 3 -//- 25 -//-
1000 m 3 -//- 50 -//-
For other solvents the corresponding amounts can be calculated based on the fact that one grammolecule (=as many
grams as the molecular weight) occupies 22,2 litres of volume at normal atmospheric pressure and temperature.

7.046 Rinsing with water is normally the final cleaning process,

Unless the cargo remains can be completely vaporised away. Remember that certain cargoes to be loaded may
require fresh water rinsing (risk for chloride contamination), e g methanol, ethanol and glycols. Stainless steel tanks
shall always be finally rinsed with fresh water, otherwise there is a risk for tank pitting corrosion, see 4.02.

Finally the tanks should be ventilated dry and any water left be dried up with rags prior to loading.

7.05 Cleaning of stainless steel

Stainless steel can be cleaned with all the methods mentioned above. Regarding removal of tank wall
discolourations see 4. 02.
1

7.06 Rust “descaling”

In the trade of chemicals loose rust will never be accepted upon loading. The rust itself may be harmless for many
products, e g gasoline, but the rust may contain residues from previous cargoes, which may contaminate the next
cargo. Gas freeing may also become more difficult if large amounts of rust collect on the bottom of the tank.

It is sometimes possible to scrape off loose layers of rust. Another method, sometimes used but relatively expensive,
is "electrochemical descaling". A provisional, but very strong, anodic protection system consisting of Al/Mg strips
is tack welded to the tank interior. The tank is then filled with (salt) seawater for a couple of days. The anodic
alkaline process breaks off rust from the bulkheads and the rust can be washed down. "Only" rust-removal remains.
This method is intended for uncoated tanks only.
8 TESTING OF TANKS AND CARGOES
The following pages describe and discuss some of the most common tests and checks that are made on oil and
chemical cargoes including testing tank walls for cleanliness.

Testing is normally carried out by independent surveyors who, according to local practice or a written agreement in
the charter party, are accepted by shipper, receiver and owner.

If possible one of the ship's deck officers should take part in the cargo sampling, cargo testing, tank cleanliness exa-
mination etc. He should make notes and observations on the work of the surveyor with a view of protecting his
party's interests. It is therefore necessary to have a general knowledge of the various procedures, without necessarily
being able to carry them out himself. In the following text, however, there will be-mentioned tests which are easily
carried out by the ship's staff by relatively simple means. A small laboratory with a stainless steel sink, a rack for 10
- 20 bottles of chemical reagents, test tubes (Nessler tubes) and a supply of distilled water are an advantage to have
on board.

In some remote ports independent surveyors may not be available. This gives the chief officer added responsibility
in following the shipper's or receiver's instructions, particularly if he is requested to sign their protocols etc.

Described below are a number of tests, which are commonly used by surveyors. Most of the tests are of a physical
nature and are relatively easy to carry out on board. Normally the test results do not give any exact answers as to
contaminations etc but have to be judged in relation to commonly accepted standards in industry or agreed values be-
tween the parties. Furthermore, the answers are often only indices of contaminations. In case of any disagreement
full laboratory examinations may have to be carried out. It is then of the outmost importance that the ship secures
samples, sealed by an independent surveyor or by both parties, of the cargo parcel in question for further analysis.

The text below often refers to ASTM-standards (American Society for Testing and Materials). The standards are
contained in a series of updated books, obtainable through good bookstores or from: American Society for Testing
and Materials, 1916 Race Street, Philadelphia, PA 19103, USA.

Similarly API (American Petroleum Institute) issues various standards, which are generally applied.

All measurements and tests have their tolerances, usually rather widespread and with correspondingly great
economic consequencies. It is good practice to take all readings twice, repeat important tests twice etc!

With ships engaged in special trades it might be useful to be able to carry out the more common tests on board and to
train personnel correspondingly. This refers in particular to the testing of tank walls for cleanliness. Many delays can
be avoided if the ship's officers can satisfy themselves that the tanks are properly cleaned before entering port, using
the same methods as the surveyor coming on board does.

8.01 Sampling of cargo

Cargo samples are taken for the purpose of checking whether the cargo satisfies a given specification or not.
Samples are also taken to establish if contamination has occurred during the voyage, during loading or unloading or
prior to loading.

After examination of the tanks, mudboxes, piping etc (as far as possible) for cleanliness it is usual to load sensitive
chemicals into the ship's tanks to a level of approximately 0, 3 m and then take samples from the tanks, presuming
that any previous residues in the piping are by then dissolved into the new cargo (''soak test"). Similarly samples are
taken from an initial discharge into container tanks or similar located on the shore before commencing unloading at
full rate to the shore storage tanks.

If a "soak test" upon loading is turned down by the surveyor or the shipper and loading stopped, the chief officer
should then request sealed and identified samples of the cargo lot in question, from the ship's tanks as well as from
the shore tanks. By these means the shipowner may be able to protect his interests in case of any dispute.

Sometimes drip-samples are taken from the loading manifold during loading. This method is simple, but not always
fully representative. The pumping rate may vary during the transfer, whilst the sampling rate is more or less
constant. Furthermore it is difficult to guarantee the proper identity of a sample taken over a long period of time.
This is not meant to discourage the ship’s officers from taking a drip-sample during loading, but only to mention the
weak points of the method. In fact, drip-sample during loading may be the only way to establish whether a cargo was
contaminated during the pumping on board or ashore.

Before unloading cargo samples are normally taken from the ship's tanks.

The cargo samples should be sealed and marked on board, particularly if no independent surveyor is present. The
ship should keep one sample for future reference in case of any disputes arising. The samples should be stored in a
dark and cool room especially put aside for this purpose. The room should have steel bulkheads and be open to the
weather deck.

Samples of products which deteriorate or change with, time (e g styrene, vegetable oils) have a limited purposeful
storage time on board. With e g phosphoric acid the samples may remain representative as regards chemical
composition, but may not be so as regards contents of sediments, However, normally the samples are stored one
year, which is the normal respite for making any claim.
Sampling at deep levels is carried out with containers which are lowered upside down or have valves or other means
of filling themselves up at the deeper level. Sampling at various different levels is necessary for products which have
a tendency to stratify, viz phosphoric acid which may contain a higher percentage of solids near the tank bottom than
at top level.

8.02 Cargo temperature determination

The temperature difference between the top and bottom of a tank may be considerable. This applies particularly to
shore tanks, where the ship’s officers are sometimes requested to attend when readings are being taken. ASTM
standard D 1085-65 (API 2545) rules that temperature readings are to be taken at three levels when the tank depth
exceeds 4, 5 m. Ordinary thermometers should be kept immersed at least 5 minutes at each level. The most common
type of thermometer is shown in fig 50.

As regards skin-contact dangerous products such as phenol, acrylonitrile etc one should, if possible, avoid handling
contaminated thermometers. Readings are much better taken by means of thermometers pocketed in the discharge
manifold.
Glycerine or other suitable contact medium should be filled in the pocket in order to give a good thermal contact.

Simple, portable, remote reading thermometers which can be lowered into the tank would be a welcome
development.

8.03 Specific gravity, density

Specific gravity expresses the weight of a unit volume of a matter compared with the weight of the same volume of
water, both at a defined (but sometimes different) temperature. Expressions such as SG 20/200C are used in the
petroleum industry. The first figure denotes the temperature of the product and the latter the temperature of the water
used as a comparison. Specific gravity includes the effect of air displacement.
The specific gravity of water varies as follows:
4 degr. C 1,0000
15 degr. C 0,9982
20 degr. C 0,9913

If a specific gravity SG 20/200C is to be converted to SG 20/40C (40C is a common reference temperature) multiply
as follows:

SG 20/4 = SG 20/20 x 0,9913

1,0000
Other examples:

SG 15/4 = SG 15/20 x 0, 9913

1,0000

SG 15/15 = SG 15/20 x 0,9913

0,9082

The tendency is now to use metric units in cargo calculations. The expression specific gravity is then substituted by
density and weight with mass. Density is expressed in absolute figures, viz kg/m 3 at a defined temperature.

A recalculation from specific weight to density involves a correction for the displacement in air by means of a
"vacuum factor":

Density = Specific gravity

Vacuum factor

The vacuum factor varies slightly with density (specific gravity):

Density 1,0 0,9 0,8 0,7
Vacuum factor 1,00108 1,00122 1,00139 1,00161

The difference between density and specific gravity is, as can be seen, small. An error in application gives a dis-
crepancy of abt 12 m *3 for a cargo of 10 000 m* 3 (at SG 0, 9).

Density (and specific gravity) is measured by means of an areometer (hydrometer) or pycnometer.

The areometer consists of a displacement body with a graduated scale, see fig 51. The accuracy in reading gives
a maximum of three correct figures, the fourth figure being doubtful. This means an accuracy of 0, 1-0, 2 %.
This accuracy is generally insufficient for cargo quantity determination. The areometer is, however, well suited
as an instrument for a general check of cargo density on board. See also ASTM standard D 1298-67 (API 2547).
A set of areometers for density ranges 0, 7 to 1, 0 and 1, 3 to 1, 8 (alkalies and acids) should be on board.
The pycnometer consists of a small glass retort with an accurately determined volume (certified pycnometers
available). The specific gravity is determined by weighing the pycnometer empty and filled with liquid. The
result is obtained with five correct figures which is much better than the areometer principle. The determination
is generally made at 20 0 C. The use of pycnometers on board is not practicable due to the need for a very
sensitive weight scale.

Specific weight/density is part of all product specifications as a check on concentration, mixture etc. The
SG/density falls with the rising temperature. Volume correction factors are used for recalculation (per degr. C or
degr. F) or tables (for petroleum products) available from, e.g American Petroleum Industry (API).

A warning: It sometimes happens that cargo density and thus the quantity is determined at both the loading end
and the discharge end by means of areometers. Obviously therefore there will be discrepancies in the two
quantity determinations simply due to the relatively poor accuracy in the density readings. As a result questions
regarding cargo claims may arise. The answer is to use the "as loaded density" (whether completely correct or
not) and correct it for the change in temperature at the discharge end. This “calculated” density is then used in
the quantity determination upon discharge. Thereby it can be established with good accuracy whether cargo has
been lost or not.
There are also other specific gravity scales. Conversion can be carried out thus:

a) API-scale, commonly used for petroleum products:

API-gravity (at 600F) = 141,5 - 131,5

SG at 60/60n degr. F

b) Baume-scale, used for liquids heavier than water, e g sulphuric acid:

SG = 145
(145 – degr.Baume)

There is also a Baume-scale for liquids lighter than water.

8.04 Colour determition

Most products shipped in chemical tankers are pure and well defined. The colour is known and any deviations
indicate the presence of contaminants.

Most chemicals, furthermore, are clear and translucent. A milky or turbid Appearance indicates that contaminants
may be present.

A sample is best studied in a test tube against a black or white background in good daylight.

Empirically a number of colour scales have been established. They are each particularly suited for certain kinds of
products.

A method called APHA (Hazen) is often used for very light products, defined in ASTM D-1209, viz aromatics,
ketones. This colour scale is defined with an origin in 100 cc distilled water (value 0) to succesively higher values
(max 500) by adding APHA-solution (a platinum-cobolt salt solution). The number of cc APHA-solution (min 5 cc)
added to the distilled water gives the APHA-colour shade number. A comparison is made against a white
background with a product sample in one test tube and a matching APHA-solution in another. This method can
easily be carried out on board. APHA-solutions are best bought from a laboratory, already premixed for a
number of shades.

The Saybolt colour scale uses coloured glasses against which the sample is compared in a defined apparatus.
The colour scale goes from plus 30 (lightest) to minus 16 (darkest). The Saybolt scale is widely used in the
petroleum industry. The method is defined in ASTM D156-64. The Saybolt method requires a special
apparatus, is somewhat complicated and not particularly suited for use on board ships.

The Gardner-scale uses sealed reference tubes for comparison with samples in a tube of the same diameter.
(The FAC-method resembles the Gardner method but has a different graduation). The Gardner scale goes from
1 - 18 and is defined in ASTM 1544- 63T.

The Lovibond-scale has several different colours (yellow, blue, red) and uses a test cell with a variable depth.
This method is used for e.g vegetable oils.
ASTM D 1500, previously called NPA defines colour scale and an apparatus suitable for field work and
application on board. A test sample is compared with coloured glasses in a revolving magazine . The scale goes
from i (water) to 8 (extra dark red). The name "NPA grade . . . . " is still often used in shipping when a
prospected cargo is circulated or when a vessel's cleanliness is described. A cargo may be accepted at NPA 2,
with discharge permitted at NPA 2 1/2. A certain amount of degradation in such a case can be permitted.

With a colorimeter on board one can take samples and by experience get an idea of how much of the previous
cargo residues can be left unattended without risk for cargo claims (refers to petroleum cargoes rather than to
chemical products)
8.05 "Acid wash"
This method is used to determine if petroleum hydrocarbons are present in aromatic compounds. Aromatics (e.g
toluene, xylene, benzene) are unaffected by sulphuric acid, but oils and most other contaminants are affected,
causing a discolouration. The method is suited for application on board and can be used as a check that proper tank
cleaning has been accomplished. The method is defined in ASTM D 848-62.
A test tube is filled with 7 cc conc (96 %) sulphuric acid, on top of which is filled 21 cc of the product sample. The
tube is then shaken 40 - 50 seconds (150 times) and is then left to settle for a period of time. The colour of the acid in
the bottom of the tube is then compared with the standard shades where 0 corresponds to water and 14 to a dark
yellow colour.

The acid wash method is used if there is any suspicion that a cargo of aromatics may have been contaminated by a
previous oil cargo.

The method is also used as a check that a tank is sufficiently cleaned before loading aromatics. A surface of about
one m 2 is carefully cleaned with clean cotton and an aromatic, e g toluene, and the liquid wrung out and tested as
the cargo sample mentioned above. One can also take rust sediments (uncoated tanks) and dissolve any oil
contaminants by means of toluene, which is then tested by this method.

Finally a difficult question arises: how much of cargo contaminants can be tolerated on the tank wall? Make tests
and train your own judgement!

8.06 Dissolving contaminats from rust

As a rough check if cargo residues hidden in rust may discolour a cargo to be loadedthe following check can be
made:
Break the rust into pieces, 0, 5 - 1, 0 cm in size, and place them in a clean bottle. Add some of the product to be
loaded (or other similar available product) and leave for 5 min. If no discolouration has occurred by then, shake the
bottle vigorously and leave for another 15 min. If still no discolouration appears the tank could be cleared for
loading. If there is a discolouration: filter the contents through double filter papers in order to remove any possible
suspended rust particles. A non-discoloured liquid after filtering should also clear the tank for loading. A
discolouration means that the tank requires further cleaning.

Observe: this simple test does not necessarily clear a tank for loading of e g aromatics, but it may prevent you from
trying.

8.07 Hydrocarbons in methanol - "water miscibility test"

8.08 Chlorides
Methanol is very sensitive to oil contaminants. The following test method uses methanol as a testing medium. The
methanol must therefore be guaranteed free from any hydrocarbon contaminants.

About one m 2 of the tank wall is carefully washed with cotton and about 40 cc methanol. The methanol is wrung
out and put into a test tube. Then 60 cc distilled water is added. The mixture is well shaken and left to settle for 20
min. If the solution remains a clear liquid the tank wall can be considered to be clean, but if the solution has turned
milky or only slightly milky it is an indication that the tank should be cleaned again before loading methanol or any
other oil-sensitive cargo.

This method should be a standard practice to be carried out by the ship's personnel. The method can, of course, also
be used as a check on the cargo upon loading and discharging.

8.08 Chlorides
Certain cargoes are very senstive to chloride contamination, in particular glycols, methanol, ethanol (see
Appendix 5). As mentioned before the tanks should be finally washed with fresh water. However, chlorides (salt)
may still be present and a check might be useful. The greatest risk for salt deposits is on horizontal surfaces.
The following method utilises the well known principle that chlorides form a milky solution when silver nitrate is
added (as commonly used when checking the boiler feed water).

About one m*2 of a suspected tank wall is cleaned by means of cotton wool and distilled water. The water is filtered
through a funnel into a test tube. The tube is then filled to a total volume of 100 cc with distilled water and well
mixed. Another reference test tube is filled with 100 cc of distilled water. To both tubes are then added 5 drops of
silver nitrate solution and the tubes well shaken. If chlorides are present the sample tube will show a milky
appearance. To the reference tube is then added a standard (known) chloride solution in small amounts by means of a
pipette until turbidity is the same in both test tubes. With a known chloride contents in the standard solution and a
known added amount one can calculate how many grams of chlorides were present on the one m 2 of the tank wall.
The total amount of chlorides in the tank can thus be evaluated. This amount divided with the tank tonnage gives an
idea of increase of chloride contents (if no other sources of contamination occur during the voyage). If the test tube
turns out to be too milky for comparison (which means a concentration of above some 100 ppm) its contents can be
diluted with a known amount of distilled water and the calculation corrected correspondingly.

ASTM D 512 describes in detail a standard chloride determination.

As an example it can be noted that some specifications allow 0, 3 ppm of total chlorides contamination (ethanol).
This corresponds to 0, 3 kg in 1000 tons of product. The permitted increase during transportation is only a fraction
thereof. A similar method is used for the determination of chlorides in clear water-soluble products, such as alcohols.
To 50 cc of distilled water is added a few drops of nitric acid (HNO 3 ) and 2 cc of saturated silver nitrate solution,
then mixed with 50 cc of the product to be tested, e g methanol. A milky appearance indicates that chlorides are
present. Reference tests have to be carried out with the same product with known contents of chlorides if exact
values of contamination are needed.

8.09 Water contamination

Presence of free water in non water-soluble products can, very roughly be determined on board by the following
simple methods.
- Warm a sample of the product in a test tube or in a bottle.Water will then collect at the bottom of the tube and
can be seen after some time.
- Drop a little of the product on to an electric hot plate. A crackling sound indicates that water is present. Can be
used on lubrication oils etc.

Other methods for non water-soluble products are:

- The product is kept at a temperature slightly above 100 degr. C for a period of time and is accurately weighed
before and after heating (for products with a boiling point above about 125 degr. C).
- Use a centrifuge and see if there is any water at the bottom of the test tube.
- A distillation met-hod according to ASTM D 95-62 (Dean Stark) is often used for oil products with
relatively high boiling points (fuel oils, gas oil, asphalt, creosote). A sample is dissolved in xylene and the
solution boiled in a glass retort. The vapours pass through a condensor. The water condenses and can be
measured in a graduated tube.

An accurate determination of water contents can be made with a "Karl- Fischer" - reagent. This method is suited
for laboratory work only.

Very small amounts of water in some products can be observed as a turbidity in a clear liquid when a sample is
cooled down to a low temperature (cloud point). As a reference calibrated samples are used with known water
contents at defined temperatures. The method is used primarily for chlorinated hydrocarbons such as carbon
tetrachloride and trichlorethylene where water might be a severe contaminant also in minute concentrations
(example: for trichlor ethylene a max water contents of e g 0, 006 %). (Remark: "cloud point'' also means the
temperature at which wax needles may form in certain oils, e g in gas oil, upon cooling. See ASTM
D 2500-66).

8. 10 Odour
For methyl ethyl ketone (MEK) the presence of water. can be proven by adding a drop of oil. If the sample turns a
brownish colour there is water in it.

An unusual smell is an indication of cargo contamination and should be reported when it is noticed upon loading.
For normally odour-free products such as glycol, odour may be a severe contamination in itself.

In order to check products which have a strong "natural" odour one can moisten a filter paper with the product and
let the liquid evaporate. If a strange odour should then arise from the filter paper it is an indication of a
contamination (by a product with a higher boiling point than the cargo in question).

8. 11 Sulphur contamination (sulphides)

Certain products, in particular "virgin naphta feedstock'' (petroleum naphta) are severely contaminated by minor
amounts of sulphides (and also lead compounds), which poison catalysts in further processing. Previous heavy
oils or dirty harbour ballast water may have left traces of sulphides in the cargo tanks.

Usually sulphides are detected by means of a "copper strip test", according to ASTM D 130-65. A polished copper
strip is immersed in the product during a period of 2 – 3 hours at 100 0 C resp 50 0 C. If sulphides are present the
copper will become darkened and can be compared with ASTM standard shades where 0 means no discolouration,
I - 3 increasing discolouration and 4 corrosion. Usually, however, the test is use d as a "yes or no"-test without
mentioning figures. The method is easily applicable on board.
Another less frequently used method uses mercury. A small amount of the product is mixed together with mercury in
a test tube. If sulphides are present the mercury will become dull in appearance and the product sample turn a
brownish colour. The use of mercury should, however, be avoided.

8. 12 Flash point

The flash point is a measure to show at what temperature flammable vapours are released in appreciable
amounts, The flash point refers to a defined test equipment and is only a relative measure: the fact that a cargo
is below its flash point does not necessarily mean that the tank is safe against ignition

The flash point for a certain product is defined in its specification. A lowering of the flash point means that the
product has been contaminated with a more volatile product, which is a severe contamination. A redistillation of
the parcel may become necessary. Flash point lowering is of particular concern with cargoes of type jet fuel, gas
oil, marine diesel oil.

Flash point determination is carried out by means of the Pensky-Martens apparatus described in ASTM
D 93-66 and well known in all petro-chemical laboratories. A product sample is succesively heated and in the
vapour space above the liquid a standard ignition flame is introduced at regular intervals until an ignition
occurs. Two methods are used: open cup (o c) respectively closed cup (c c). The latter gives a lower flash point
with a difference of 5 - 7 degr.C. Closed cup is the most commonly used method.

8.13 Distillation range

Any pure liquid has a defined boiling point. Commercial products often consist of mixtures with also other
compounds in accepted amounts. Boiling of a commercial product therefore means that the more volatile
components will boil off first and the heavier components later and at a higher temperature. This results in a
range in temperature between commencement of boiling and finished boiling (dry retort), called "distillation
range". The distillation range is defined in the specification for a certain product parcel. Deviations indicate that
the product has been contaminated.

The test equipment is defined in ASTM D 1078, D 1437 and E 133-58. 100 cc of the product is heated to
boiling in a retort and the vapours condensed in a water-cooled condensor, see fig. 56. A thermometer is inserted
in the vapour stream.
The initial boiling point (IBP) is defined as the temperature at which the first drop is condensed in the condensor.
The final boiling point is read when the retort just becomes dry, dry point (DP). (For certain products, particularly
gasolines, the final boiling point is read when the last drop leaves the condensor, end point (EP).)
The distillation range then becomes: t = IBP - DP (in general) degr.C or degr.F
t = IBP - EP (gasolines)
This test is used on all hydrocarbons: alcohols, aromatics, esters, ketones, glycols etc. The method is best suited for
laboratories ashore.
 8. 14 Refractive index
This method is based on the property of light to be refracted at different angles-when it passes a prism into different
liquids. This test is realized in an instrument called a refractometer where only a drop of the liquid to be tested is
needed to cover the surface of the prism. The refractive angle can be, me4Lsured with good accuracy.

The angle of refraction is a typical property for every pure product. The method is sensitive to temperature. Usually
a standard temperature of 20 0 C is used, but temperature corrections can also be made.

Standards are defined in ASTM D 1747-62. Refractometers are available in laboratory and portable models. The
latter can easily be used on board.
There are tables available against which refractometer readings can be interpreted in terms of concentrations.

The refractive index of a mixture of two products is proportional to the relative contents of the products. Therefore
the instrument is suitable to determine strength of solutions, e g sugar in water (molasses), glycol in water. It is also
used for the determination of hydrocarbon mixtures (aromatics) and vegetable oils (See British Standard BS 628-32,
650-56, 1950)

8. 15 Solidifying point
The solidifying point (freezing point) is well defined for pure products. Deviations indicate that contaminants are
present.

The solidifying Point is measured by placing a test tube with a thermometer in a cooling bath. The product is kept
stirred and the temperature is read at short intervals. It will fall to a minimum and afterwards rise slightly and remain
constant for a while. This temperature is defined as the solidifying point.

Examples on solidifying points:

Benzene + 5,4 degr. C

Cyclohexane + 4,6 degr. C
Soyabean oil + 22,2 degr.C
Sulphur + 117,0 degr.C
Phenol + 40-41 degr.C
Paraxylene + 13,2 degr. C

Observe the high solidifying point of benzene and paraxylene.

8. 16 Permanganate-time test
This is a test to determine contaminants in alcohols and ketones (e g in acetone). The method is described in ASTM
D 1363-67.

2 cc potassium permanganate solution (conc: 0,2 g KMnO dissolved in 1 litre of distilled water) is added to a 50 cc
sample in a test tube. Contaminants in the sample chemically reduce the potassium permanganate which changes
colour from red to yellowish. The time is noted for the sample to assume the same shade as a standard reference
solution of coboltchloride-uranylnitrate. A shorter time for this colour change means a greater amount of
contaminants. Acetone is tested at 25 0 C, methanol at 15 0 C. The test tube should be kept dark during the test.

After some practice this method can be carried out on board, and is in fact already in use in some ships.

8. 17 Gas chromatography
In a gas cbromatograph a small product sample is injected and made to pass througn a pipe filled with a very fine
mineral powder by means of a carrier gas stream (N., H 2$ He, argon). Temperature is kept constant. The lighter
components will pass through the tube easily but the heavier ones will take more time. In this way the components
are separated at the outlet where an ion-cell picks up an electric signal which is recorded. Each product has a typical
"print". Deviations indicate contaminants.

The method is only suitable for laboratory work ashore.

A gas chromatograph test from product samples taken prior to loading and upon discharge can tell if contamination
has occurred while the cargo was on board. This method is some times used taking "fingerprints" from an oil spill
and from a suspected source-in order to establish the origin of a pollution.

8.18 pH value (acidity)

A neutral solution is defined as pH=7. Acidous solutions have pH lower than 7 and alkaline solutions higher than 7
(max 14).

Water soluble products are readily tested by means of litmus paper where a colour change directly indicates the
pH-value roughly. There are also electrode -meters available where the pH-value can be read directly from a scale.

The pH-value can also be established by means of neutralisation with a sodium hydroxide (caustic soda) solution
from which the acidity can be calculated from the amount of alkaline matter added. A colour reagent shows when the
solution changes from acidous to alkaline.

Vegetable and animal oils require the determination of pH value, which indicates the contents of free fatty acids.
This is, in turn, a measure of the quality of the oil, or the degradation of the oil during transport. The oil is first
dissolved in alcohol and afterwards neutralized with sodium hydroxide as indicated above. The method is described
in British Standard BS 628-32, 650-56:1950.

8. 19 Viscosity
Viscosity is measured by means of capillary tubes (ASTM D 445-IP and ASTM D 2515) or by an apparatus measuring
the friction of liquid between two cylinders of which one is revolving. Measurements on board will rarely be needed.

Viscosity is interesting as regards the pumpability of a product. Usually the upper limit for centrifugal pumps is
considered to lie around 400 centistoke (cSt), corresponding to about 1500 Seconds Redwood (sec R) or about 50 degrees
Engler ( degr.E). Screw pumps may pump liquids with viscosities as high as 10. 000-20. 000 cSt. See conversion table.

8. 20 Spectro-photometry
A spectro photometer is used to trace minute contaminants (1 - 2 ppm). One common application is the
determination of degree of polymerisation in styrene monomer.

The principle of the instrument is that a product sample is transluced with a light of a known wave length (ultra
violet, visible or infra red light). A certain part of the light is absorbed and does not reach a detector cell. The amount
of absorption is known for pure products. For common contaminants there are calibration curves available for
comparison with readings.
9 CARGO PRODUCT INFORMATION
Throughout this book examples have been given on the properties of various chemical cargoes. Where does the
reader find collected information on all likely cargoes? What about new chemical compounds coming on the market
every day? As mentioned in Chapter I the owner, according to the IMCO Code, has the duty to inform his personnel
about the hazards involved plus, of course, handling instructions.

As regards general product information including, to a certain extent, also trade names, reference is given to ref (1),
(3), (4), (5), (16), (17), (28), (46).

Questions about personal safety, the product's "hazard profile" (whether danger upon skin contact or vapour contact,
reactivity etc) are treated in ref (1), (4), (5), (36).

Tank cleaning questions are treated in ref (10) and (11). Further information can be obtained from the manufacturers
of chemical cleaning agents.

Information on the handling of the cargo including necessary cleanliness, max permitted contaminants etc, is often
hard to get. In the text some suggestions are made, see also Appendix 5 for a selection of common cargoes.

Never load an unknown cargo identified by only a trade name!

In the past it has been difficult to obtain a full product information from the makers and from shippers. They should
have the very best information and should be consulted whenever possible. It is hoped that information will be more
easily available in the future!
10 ANTI- POLLUTION MEASURES,
SPILLS, EMERGENCIES
10. 01 International Convention 1973
At an IMCO conference in London 1973 an "International Convention for the Prevention of Pollution from Ships,
1973” was drawn up. The convention has not yet been ratified by the necessary number of Governments, We shall
only concern ourselves here with Annex Il of the convention: "Regulations for the Control of Pollution by Noxious
Liquid Substances in Bulk".

The convention rules that a Cargo Record Book shall be kept, In certain cases, as detailed below, official National
surveyors are required to make entries regarding tank washing etc. for certain cargoes. For each vessel shall be
drawn up a "Procedures and Arrangements” book.

The convention divides noxious substances into three categories :

a) Category A - Substances which if released into the sea from tank cleaning or deballasting operation would
present a major hazard to either marine resources or human health or cause serious harm to amenities or other
legitimate uses of the sea and therefore justify the application of special measures to prevent their escape into the
marine environment.

Substances of Category A are bioaccumulated and liable to produce a hazard to aquatic life or human health; or
are highly toxic to aquatic life.

Examples of Category A substances: acetone cyanohydrine, acrolein, carbon disulphide, creosote, cresols,
dichlorbenzene, sodium pentachlorophenate, tetramethyl lead.

b) Category B - Substances which when released into the sea from tank cleaning or deballasting operations may
present a hazard to either marine resources or human health or cause harm to amenities or other legitimate uses
of the sea and therefore justify the application of special antipollution measures.

Substances of Category B are bio-accumulated with a short retention of the order of one week or less; or are
liable to produce tainting of sea food; or are moderately toxic to aquatic life.

Examples of Category B substances: acrylonitrile, allyl alcohol, carbon tetrachloride, chlorobenzene, ethylene
dibromide, phenol, trichlor ethylene.

c) Category C - Substances which when released into the sea from tank washing and deballasting operations
may present a minor hazard to either marine resources or human health or cause minor harm to amenities or
other uses of the sea and therefore require special operational conditions.

Substances of Category C are slightly toxic to aquatic life and include additicrnally certain substances which
are practically non-toxic to aquatic life.

Examples of Category C substances: acetaldehyde, acetic acid, allyl chloride, amyl acetate, benzene,
chlorosulphonic acid, cumene, cyclo hexane, ethylbenzene, ethylene diamine, nonyl phenol, octanol, sodium
hydroxide (caustic soda), styrene monomer, sulphuric acid, vinyl acetate, xylenes. The following substances are
excluded from the Convention requirements as causing negligible harm (Appendix III to

Category A discharges
The convention rules that discharge into the sea of substances of Category A shall be prohibited. Tank washings are
to be pumped to a receiving facility until the washings have a concentration of less than 0, 1 % in the Category A
examples above (0, 01 % for carbon disulphide) and the tank is then empty . Thereafter the tank may be flushed to
min 5 % of tank capacity and the water may then be discharged into the sea if all of the following conditions are
satisfied (Category A):

a) Ship's speed greater than 7 knots

b) "Adequate dilution" in ship's wake to be proven to satisfaction to the Administration (reliable calculations or
references to experiments)
c) Discharge below the waterline, taking into account the location of sea water intakes
d) Discharge not less than 12 NM from the nearest land at a depth of water not less than 25 metres.

Category B discharges
Substances of Category B, contaminated ballast water or tank washings containing these substances shall be
prohibited to be discharged into the sea. However, such mixtures may be discharged when the following conditions
are fullfilled (Category B) :

a) Ship's speed greater than 7 knots

b) Concentration in ship's wake shall be proven by reliable calculations not to exceed 1 part per million
c) The maximum quantity of cargo discharged into the sea from each tank and ass. piping does not exceed 1 m 3 or
1/3000 of tank capacity, whichever is the greater.
d) As c) above
e) As d) above

Category C discharges
Substances of Category C, contaminated ballast water or tank washings containing these substances are prohibited to
discharge into the sea. However, such mixtures may be discharged when the following conditions are all fullfilled
(Category C) :
a) Ship's speed greater than 7 knots
b) Concentration in ships wake shall be proven by reliable calculations not to exceed 10 parts per million
c) The maximum quantity of cargo discharged from each tank and ass. piping not to exceed 3 m *3 or 1/10000
of tank capacity, whichever is the greater
d) As c) for Category A
e) As d) for Category A

The Convention further describes "Measures of Control" saying that each Government shall appoint or
authorize surveyors whose duties shall include surveillance according to this Convention. Other measures of
control:

- Category A substances: The Master shall make entries regarding tank unloading and all cargo operations in
the Cargo Record Book including concentrations of cargo in tank washings to be discharged; the latter also to
be certified by the above surveyor. As further stated in the Convention the surveyor may satisfy himself that for
Category A substances alternative procedures for pre-cleaning and direct calculation of maximum cargo
remaining on board may be acceptable, provided no more pollution occurs other than ruled for Category A
above. All such deviations from the strict Convention rulings to be entered in the Cargo Record Book together
with all relevant calculations etc.

- Category B and C substances: The Master shall enter in the Cargo Record Book when a tank is unloaded,
piping systems drained and when he has ascertained that the amount of cargo left on board after unloading does
not exceed the amounts allowed and necessary dilutions achieved etc (see above). Such observations and entries
may be checked by the surveyor. The Master shall further record internal transfer of cargo, discharge of
washings according to regulations as well as disposition of tank washings if cleaning is carried out in port,
Residues from slop tanks and pump room bilges shall be treated equivalently with cargo from the cargo tanks.

The Cargo Record Book shall be completed on each occasion and for each tank whenever any of the following
operations take place:
- loading of cargo
- transfer of cargo during the voyage
- discharge of cargo
- transfer of cargo, cargo residues, etc to a slop tank
- cleaning of cargo tanks
- discharge of slop tanks
- ballasting of cargo tanks
- discharge of ballast water discharge or escape of cargo or cargo mixtures

The Cargo Record Book shall be signed on each page by a responsible officer and the Master. The book shall be
kept readily available on board.

A chemical tanker shall be surveyed by the relevant Administration with regard to this Convention and after
compliance obtain a ''Certificate of Fitness for the Carriage of Noxious Chemicals in Bulk". The Certificate shall be
endorsed with details of approved washing procedures and approved discharge arrangements for tank washings.

10.02 Spills, emergencies

Ship design and operational routines all aim at reducing the risk for environmental pollution. Nevertheless: accidents
can happen or be caused by improper action by anyone involved on board, ashore or by other ships. Traditional
thinking rules that the vessel and her cargo should be salvaged on the basis of the values they represent. With che-
mical and oil cargoes this is not necessarily true. It is more a matter of containing the cargo on board or by other
means until the situation can be mastered with due regard to weather, shipping etc.

Spills of any size in port, due to over-fillings, hose break age etc, should be reported to the Port Authorities at once.
Keep in mind that water supplies, other water intakes local fishing, public amenities etc can be affected with enormous
human and economical consequencies unless immediate counteractions can be taken.

In order to reduce the danger for minor spillages deck scuppers should be closed, drip pans arranged under hose manifold
and a close watch kept when topping up the cargo tanks.

Within IMCO work is in progress on defining ''danger profile" for various substances with regard to, among other things,
what action is to be taken after spills in shore areas, estuaries etc. For the time being information on how spills are to be
treated must be sought from Port Authorities, who will normally take charge of a spill situation. See also ref (24) where
various chemicals are rated with regard to the effect on marine life and aesthetic effects.

Common cargoes which are particularly damaging to marine life when released to the sea: acetone cyanohydrin, acrolein.
Strongly negative aesthetic effects will be caused by the release of: aniline, creasote, dodecyl benzene, acrolein, acetone
cyanohydrin.

10. 03 Controlled discharge of ( noxious) tank washing

First and foremost the cargo tanks and piping shall be dischargect as completely as possible, taking into account:
- Ship to have beneficial trim and list to assist final stripping.
- Cargo to have correct temperature for easy flow to pump suctious.
- Adjoining tank walls (=cargoes) as far as possible to have a temperature which reduces noxious cargo under discharge
to cling to the walls.
- Possibilities to drain the piping system by blowing ashore with air or inert gas or use stripping line of small diameter
ashore.

Studies and calculations have been made for many individual ships and products to demonstrate that the amount of
cargo remains from the various tanks, using above procedures and other particular methods, will not exceed the
“permissible amounts for B and C" (1 m *3 or 1/3000 arid 3 m *3 or 1/1000 of tank volume).

Similarly, pumping procedures for overboard discharge (pumping speed and discharge pipe arrangement) have been
established for many vessels in order to fullfill requirements of dilution in the ship's wake. In some ships special
"mixing tanks'' are provided. By means of mixing pumps cargo remains are diluted with seawater to permissible
concentrations.
11 - CARGO COMPATIBILITY AND REACTIVITY
11.01 Compatibility
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.

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 IMCO 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, one type of which is shown in fig 13. 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: See 11. 02 -

Information about dangerous cargo combinations can be found in the data sheets in ref (1), in the US Coast Guard
Compatibility Chart (with amenaments and exceptions) reprinted in Appendix 3.

11. 02 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.
Examples on polymerization products commonly shipped in chemical tankers:

acrylic acid
acrylonitrile
butyl acrylate
butyl methacrylate
decyl acrylate
ethyl acrylate
ethylhexyl acrylate
isoprene
methyl acrylate
methyl methacrylate
styrene (monomer)
vinyl acetate
vinyl chloride
vinylidene chloride

In order to prevent or delay polymerization certain inhibitors are added to the product before loading. The inhibitors
are being consumed with time, usually accelerated by increased temperature. It is hardly possible in practice to add
more inhibitor during the voyage. IMPORTANT: check with the shipper -that enough inhibitor has been added and
request a Certificate of Inhibition before loading!

The inhibitor consists of various substances depending on the product. As examples can be mentioned:

Product Inhibitor
acrylonitrile paramethoxy phenol
styrene monomer Paratert butyl catechol
(PTBC),
hydroquinone
vinyl acetate hydroquinone,
diphenylarnine
vinyliciene chloride paramethoxy phenol,
thymol,
Phenol
acetone cyanohydrin Inorganic acid

It is possible to check the contents of inhibitor in the product, usually by relatively simple means. A test for inhibitor
contents in styrene consists of mixing one part of styrene with three parts of methanol. If the mixture remains clear
or slightly bluish the product is intact. A slight whitish turbidity indicates polymerization and that the inhibitor
probably is consumed. Ask the shipper to deliver on board a kit for inhibitor check for the product to be loaded.

In order to take good care of polymerizable products, remember:

- Keep the product as cool as possible. Never place close to heated cargoes!
- Keep hatches closed to avoid unnecessary light.
- Check cargo temperatures regularly. In the event of an unexplicable temperature rise: consult the shipper and
the shipowner and discuss possible action. To jettison might be a last resort.

Acetone cyanohydrin decomposes with time, accelerated by heat. A stabilizer should be added consisting of an
inorganic acid. Other precautions are similar to those for the products above.
11.03 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. Strangely enough the IMCO Chemicals Bulk Code does not rule on this point,
however, in ref (1), chapter 9. 2. 2 the matter is mentioned. 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.
12 CARGO PLANNING ETC
A check list is given below, which might be useful when discussing cargo planning in your ship. The order of the
points is of no importance.

1) Load the vessel so that positive trim is ensured during discharge, preferably without filling ballast in cargo
tanks, particularly not in port. Try to find out the receiver's desired sequence of discharge. Keep an eye on
hogging /sagging!

2) Inter-reactive cargoes must not be placed in neighbouring tanks. Piping systems must be separated by double
blind flanges to prevent erroneous handling of valves. Check the cargoes with data sheets in ref (1) and
Appendix 3 for cargo compatibility.

3) Toxic cargoes must not be placed in neighbouring tanks with edible products (human or cattle).
Separate the piping systems by means of double blind flanges

4) Check with the tank coating manufacturer's list of permissible cargoes for coatings in each tank. The
general rules are: Zinc silicate coatings are resistant to strong solvents (aromatics, alcohols, ketones etc).
Zinc silicates are not resistant to caustic soda or alkaline cleaning chemicals. Epoxy coatings are resistant
to petroleum products, caustic soda, vegetable oils, wine, seawater, fatty acids, limited resistance to
alcohols and aromatics. Coal tar epoxy is resistant to sea water, crude oil and petroleum products in general but
should not be used for jet fuels or light oils as they tend to be contaminated by bleeding tar.
5) In certain cases the tank coating manufacturer gives a limited acceptance for a product (time and/or
temperature). Avoid then placing heated products on the otherside of the bulkhead. Let epoxy weather out
properly after solvent cargoes. Do not fill ballast water immediately after methanol in the same tank.
6) Polymerizable products (e g styrene, vinyl chloride) should never come in bulkhead contact with heated
cargoes. The same refers to drying vegetable oils (e g linseed oil) .
7) Volatile products (aromatics, ketones, alcohols etc) should not be put into bulkhead contact with heated
cargoes in order to avoid unnecessary evaporation losses.
8) The cargo tanks are normally inspected and approved prior to loading. This does not necessarily relieve the
vessel of responsibility for contaminations. The master/ owner carries the responsibility in taking due care of
the cargo. To protect ones own interest the vessel's own inspections should be recorded in the deck log.
9) After cargoes with a strong odour (fish oil, phenol, octanol, tall oil, turpentene, molasses) the tanks should not
be used immediately for odoursensitive cargoes such as glycols, ve getable oils,
10) After leaded gasoline, cargoes for human or animal consumption must not be loaded as the next cargo,
neither "virgin naphta feedstock". Lead compounds may adhere to the bulkheads after several intermediate
cargoes even in coated tanks. Wine cargo may dissolve lead remains, which are many intermediate cargoes
''old".
11) In case of doubt of purity of cargo to be loaded: take cargo samples also from the loading manifold upon
loading and have them sealed and identified for future reference.
12) In tanks which have contained products with a high boiling point and/or low water solubility (e g lubrication
oils) there will be minute amounts of cargo left after washing. These tanks are then not suitable for a
''sensitive" cargo such as methanol.
13) Consult the cargo trim and stability book. There may be restrictions with regard to cargo distribution and
stabllity in hypothetical damaged condition.
14) When one and the same pipe has to be used for several consecutive products: Start with the lighter products,
going on to more viscous ones. The pipe may have to be drained and steamed in between, therefore try to
arrange an open loop. The most sensitive cargoes may have to be loaded "over top" through the hatch.
15) Double valves are usually not considered as a sufficient means of segregation in the chemical trade. Blind
flanging is necessary. Provisional blind flanges can be made of 2 - 3 mm sheets, preferably stainless steel.
Observe: reactive cargoes need a more substantial segregation, see 2) and also 3) above.
16) When two cargo parcels cannot be segregated by means of blinds the liquid level can purposely be kept higher
for one of the products, thereby ensuring that any possible leak will go in the less dangerous direction with
regard to contamination damage.
17) Check cargo valves for tightness prior to loading and take leaking valves into consideration when placing
cargoes.
18) Blow heating coils over deck prior to loading to ensure that no cargo has leaked into them which could cause
danger in the engine room when heating is commenced. Pressure test the coils before loading.

19) Heating coils (steam) should be blind flanged towards the engine room when products are carried which do
not require heating.
20) Before loading water-sensitive cargoes (halogenated compounds, e g trichlor ethylene) or chloride- sensitive
cargoes (alcohols, glycols): hose test the tank hatches for tightness and check valve spindle glands on weather
deck.
21) Inform the Owner if there seems to be a disagreement between B/L product and the product actually loaded
(may affect freight, cleaning costs, safety).
22) Avoid carrying the most toxic products as last cargoes before dry-docking and shipyard work.
REFERENCES
1 Tanker Safety Guide (Chemicals). 3 vol.
International Chamber of Shipping. London 1971.
30-32 St Mary Axe, London, EC3A 8ET.

2 Tanker Safety Guide (Petroleum).

International Chamber of Shipping. London 1970.
30-32 St Mary Axe, London, EC3A 8ET.

3 Handbuch der gefdhrlichen Gtiter. Springer 1970.

4 Chemical Safety Data Sheets.

Manufacturing Chemists Assoc. (MCA) Washington D C.

5 Chemical Data Guide for Bulk Shipment by Water. (USCG CG 388).

US Coast Guard. Governm. Print. Off, 1976, 317 pp.

6 Kemisk Skyddshandbok
SAF, Svenska Arbetsgivarfbreningen, Stockholrn 1958.

7 Safety in industry. Maritime safety data.

US Dept. of Labour. Bull 304.

8 National Fire Protection Association

Hazardous Chemicals Data
NFPA nr 49, NFPA Boston, Mass.

9 Int. Oil Tanker and Terminal Safety Guide (IOTTSG)

Inst. of Petroleum, 61 New Cavendish Street,
London WIM 8AR.

10 Tank-cleaning Guide (2 ed)

Chemical Laboratory Dr A Verwey, Coolhaven,
Rotterdam.
11 Vecom Tankcleaning Vecom International, Antwerp.

12 Bulk shipment of some ICI products. ICI England.

13 Phenol handling and storage. Cerechlor bulk storage and handling.

ICI England.

14 Liste over yrkeshygieniske grenseverdier

Yrkeshygienisk Institutt, Oslo.

15 Threshold Limit Values of Airborne Contaminants and Physical Agents.

Am. Conference of Governm. Industr. Hygienists.
P.O. Box 1937, Cincinnatti, Ohio 45201.

16 Sax, N Irving, Ed. Dangerous Properties of Industrial Materials. 3rd ed..

New York, Reinhold 1968, 1251 pp.

17 Marsden, C. Ed. Solvents Guide.

London, Cleaver-Hume, 633 pp.

18 Code of Federal Regulations, 46 CFR 1-65, 46 CFR, 66-145, 46 CFR 150-199. The Superintendent of
Documents, US Government Printing Office, Washington DC 20402. (Revised edition every year).

19 Fristedt, B, Yrkesmedicin
Studentlitteratur, Lund 1971, 96 pp.

20 Moeschlin S, Klinik und Therapie der Vergiftungen

Georg Thime Verlag, Stuttgart, 750 pp.

21 Wirth N, Hecht G, Gloxhuber M, Fibel, Toxikologie

2 ed, Georg Thime Verlag, Stuttgart, 391 pp.

22 Patty F, Industrial Hygiene and Toxicology

Interscience Publishers Inc, New York (2 vol).

23 Navigation and Vessel Inspection Circular No 5-70 "Guide to Compatibility of Chemicals" (with exceptions).
US Coast Guard, Washington DC 20591 (expected revised late 1974).

24 Evaluation of the Hazard of Bulk Water Transportation of Industrial Chemicals (Tentative guide), National
Academy of Sciences, Washington DC, 1972, 30 pp.

25 Code for the Construction and Equipment of Ships Carrying Dangerous Chemicals in Bulk
( Incl Arnendrnents 1 -9),
Inter -Governmental Maritime Consultative Organization (IMCO), 1-0 1 - 104 Piccadilly, London W 1V OAE.

26 BIMCHEMVOY Voyage Charter Party.

Fr. G Knudtzen Ltd, 55 Toldbodgate, Copenhagen.

27 Anvisningar om behandling av fbrgiftningar uppkomna vid transport av farligt gods, sasom kemiska
bekampningsmedel. Sjbfartsverkets Medd. 1972 A:16
28 International Martime Dangerous Goods Code (IMDG Code)
Inter -Governmental Maritime Consultative Organization (IMCO), iOl-iO4 Piccadilly, London WIV OAE,
1972, 3 vol.

29 Code of Practice for the Safe Carriage of Dangerous Goods in Freight Containers,
The Chamber of Shipping of the UK, 30/32 St Mar
Axe, London EC3A 8ET.

30 Kjemikaliefart Norges Rederforbund- Skip sfartens Arbeidsgiverforening, Oslo 1972

31 Dangerous Goods in Harbours etc.

Notice (1972 A:12) of the Swedish Administration of Shipping and Navigation.

32 European agreement about International transportation of dangerous goods by road (ADR).

33 International regulations about transportation of dangerous goods by railway (RID).

34 The IATA- regulations relating to the carriage of restricted articles by air (RAR).

35 Certain Bulk Dangerous Cargoes, Special Interim Regulations for Issuance of Letters of Compliance US
Department of Transportation, Coast Guard, Federal Register Vol 38, No 115, June 1973.

36 Medical First Aid Guide for Use in Accidents Involving Dangenous Goods
IMCO, WHO, ILO, IMCO sales No 197 3:3(E), London.

37 Symposium om regler og foreskrifter for kjemikalieskip.

Information No 11, June 1973, Det Norske Veritas, Oslo.

38 International Convention for the Prevention of Pollution from Ships, Annex I (Oil), Annex II (Chemicals),
1973, IMCO, 101-104 Piccadilly, London WIV OAE.

39 Stowage and Segregation to IMCO-Code K. 0. Storck & Co Verlag und Druckerei Gmbh, Hamburg 1973.

40 Stainless Steel for Chemical Tankers

Avesta Jernverk AB, 774 01 Avesta, Sweden.

41 Recommended Practice for Descaling and Cleaning Stainless Steel Surfaces.

Sect. III, Bull. E, The Int. Nickel Co Inc, 67 Wall Street, New York 5, N.Y.

42 Rules governing the design of chemical tankers are included in the Rule Books of the Classification
Societies:
American Bureau of Shipping, Bureau Veritas, Det Norske Veritas, Germanischer Lloyd, Lloyds Register
of Shipping.

43 Gas Evolution: Tanker and Terminal Safety.

The Institute of Petroleum, 61 New Cavendish Street,
London WIM 8AR, 1971.

44 Clean Seas Guide for Oil Tankers

Int. Chamber of Shipping, Oil Comp. Int. Forum,
 1973, London.

45 Monitoring of Load-on-Top
Int. Chamber orf Shipping, gil Comp. Int. Forum,
1973, London.

46 Condensed Chemical Dictionary, rev. by Gessner & Hawley

Van Nostrand Reinhold, New York.

47 Handbook of Emergency Toxicology, Kaye.

48 Articles on "Tanker cargo handling" "Skip" No 8, 1965 Oslo.

49 Chemical carriers and their tanks, Les Streeter, Tanker & Bulk Carrier, Aug/Sept 1974.

50 Toxic and Hazardous Industrial Chemicals Safety Manual.

The International Technical Information Institute, Toranomon-TachiKawa Bldg 1-6-5, Nishi-Shimbashi,
Minato-ku, Tokyo 105 Japan.

51 "Chemical Tankers - The Ships and the Market" by M. Corkhill. A Fairplay report. Fairplay Publications Ltd. I
Pudding Lane, London EC3R 8AA.

52 "Safety in Chemical Tankers'' International Chamber of Shipping. 30-32 St. Mary Axe, London EC3A 8ET.

53 Hygieniska gransvdrden (Treshold limits values) Arbetarskyddstyrelsens anvisningar nr 100 (1978) Liber
Forlag, S-162 8,9 Vallingby, Sweden.

54 "Chemlog -79'' Resistance list for stainless steels Uddeholm, Fack, S-693 01 Degerfors, Sweden.

55 Rules and Regulations for Foreign Vessels Operating in the 'Navigable Waters of the United States.
US Coast Guard, I Dec. 1977 Part 153, CG-5f5
Superint. of Documents, US Government Printing Office
Washington DC, 204 02

56 Oilseeds, Oils and Fats (second Ed.

Int Ass. of Seed Crushers Transport and Quality
Sub-Committee.

57 Tdtning och Invallning ( Sealing and Containment of Spills) (Swedish)

Svenska Brandf6rsvarsf6reningen
Kungsholms Hamnplan 3, 112 20 Stockholm
 APPENDICES

APPENDIX I

TABLE OF PROPERTIES OF SOME COMMONLY SHIPPED PRODUCTS

Excerpt from: "The carriage of special liquid cargoes" by Egil Abrahamsen

Det Norske Veritas Publication nr 45

 APPENDIX 2

CHEMICAL DICTIONARY
EXPLAINING SOME COMMON TERMS
Acid number (neutralization number) Number of milligrams of potassium hydroxide required for
neutralization of free fatty acids present in I g of fat or oil, a measure of free acids
present in a substance.
Alcohol Organic compounds containing one or several hydroxyl radicals (OH). Alcohols may
be mono-, di-, tri-, etc according to the number of hydroxyl radicals they contain
and primary, sec. , or tert. according to position of hydroxyl radical.
Aldehydes A group of organic compounds containing the –CHO radical and holding a position
between alcohols and acids. They are produced by the oxidation of hydrocarbons (e
g
alcohols) and can be used for production of alcohols.
Example: acetaldehyde (CH 3 CHO)
Alkyl A non-cyclic saturated hydrocarbon of general formula C n H (2n +1)

Aliphatic Organic compounds in which the carbon atoms are not arranged in a ring structure.
Alkanes (alcynes) Aliphatic saturated hydrocarl-)ons of type CnH(2n + 2) Example: Pentane C 5 H12
Amines Substances derived from ammonia where the hydrogen atoms are replaced by one,
two or three alkyl groups.
Antifreeze Usually glycol derivatives.
Aromatics Aromatic hydrocarbons (benzene hydrocarbons), unsaturated, with the carbon atoms
in rings with a 6 carbon nucleus ring. Examples: aniline, naphtalene, benzene,
toluene, xylene.
Atom The smallest particle of an element which retains the characteristic properties and
behaviour of the element, the smallest particle of an element which can take part
in a chemical reaction.

Brix degree The per cent by weight of soluble solids in a syrup at 68 0 F. X 0 Brix indicates that
the solution to which it refers contains Xgm of sugar in 100 ml at 15, 6 0 C. A
measure of specific gravity SG = 400
1 400 - degrees Brix
Carbinol 1) Synonym for methyl alcohol
2) Compounds of similar structure as 1) obtained by substitution processes.

"Carbitol" Trademark for a group of mono and dialkyl ethers of diethylene glycol.

Carbonyl group The group.CO which is a characteristic of aldehydes and ketones.

Carboxyl group The characteristic part of most organic acids, e g fatty acids. I

Cellosolve Trade mark for mono- and dialkyl ethers of ethylene glycol and their derivatives.
Widely used as industrial solvent.

Chlorination The treatment with or introduction of chlorine into a compound.

Derivative A compound obtained from another compound by a simple chemical reaction; an

organic compound containing a structural radical similar to that from which it is
derived e g benzene derivatives containing the benzene ring.

Detergent Cleaning agent.

Dowanol Trade mark for a series of glycol monoethers used as solvents and making
 plasticizers.

Dutrex Trademark for a series of aromatic hydrocarbon concentrates, generally of low

volatility.
Element Ultimate constituent of matter. There are 103 known elements.

Ester An organic compound (salt) formed from an alcohol (base) and an organic acid.
Many esters occur in nature, e g fats. Many esters are important as solvents.
Ethanol Ethyl alcohol (spirit, spirit of wine, grain alcohol, absolute alcohol).
Fatty acids Organic monobasic aliphatic acids. The three acids occurring most frequently in fats
as glycerol esters: palmitic stearic and oleic acids. Fatty acids are common in animal
and vegetable tissue and are obtained by boiling or extraction; they are used in edible
oils and fats, soap manufacture etc.
Glycerid An ester derived from glycerol. The fats and oils are mainly triglycerides of fatty
acids, e g tripalmitin.
Glycerol (Glycerine) Alcohol which combined with (ester) fatty acids is a constituent in fats. Colourless
sweet syrup used as plasticizer, solvent and reagent in paints, printer's ink,
explosives, cosmetics.
Glycols Aliphatic secondary alcohol compounds containing 2 –OH groups. Ethylene glycol,
colourless liquid, produced from ethylene (oxide). Antifreeze, used in polyesters,
cosmetics.
Halogens The chemically related elements fluorine, chlorine, bromine and iodine. Combined
with hydrogen they form acids (e g HC1) and with metals salts (e g NaCl).
Hydrocarbons Combinations of carbon and hydrogen. The most important:
- Paraffins; saturated aliphatic hydrocarbons incapable of combining further with
hydrogen or halogens and comparatively indifferent to chemical action. Liquid
paraffins soluble in alcohol and ether but not in water.
- Olefin or ethylene series, unsaturated hydrocarbons. Example: propylene (gas).
- Cycloparaffin (naphtene) serie have saturated ring hydrocarbons. Examples:
cyclopentane, cyclohexane.
- Benzene hydrocarbons. Examples: benzene, toluene, xylene.
- Terpenes, unsaturated hydrocarbons. Example: turpentine oils.
Hydrogenate To introduce hydrogen into a molecule, as the saturation of unsaturated compounds.
Hydrolysis A chemical reaction in which water reacts with another substance to form one or
more new substances (e g "hydrolyzable solvents1such as acetates, esters,
halogenated compounds (often chlorinated) may with water form organic or
inorganic acids.
Hydroxyl group The radical OH-group (oxygen and hydrogen). Is a characteristic patt in.alcohols and
phenol.
Inhibitor General term for compounds or materials that have the effect of slowing down or
stopping undesired chemical changes such as corrosion, oxidation or polymerization.
ISO- A prefix indicating a similarity.
Isomer The property of having the same percentage composition as another compound yet
differing in relative position of the atoms within the molecule from which result
different physical and chemical properties.

Ketones A class of organic bodies produced by oxidation of secondary alcohols and

characterized by the carbonyl group (CO). Examples: acetone, methyl ethyl ketone.

Methanol Methyl alcohol

Mineral acid Strong inorganic acids e g sulfuric, hydrochloric, nitric and phosphoric acid.

Mineral oil Mixture of liquid hydrocarbons obtained from petroleum.

Molecule The chemical combination of 2 or more like or unlike atoms.

Mono- A prefix indicating ''one".

Monomer A molecule or compound usually containing carbon which is capable of conversion into
polymers, plastics, synthetic resins by combination with itself.

n- A prefix indicating ''normal", usually a straight chain.

Olefins A class of unsaturated hydrocarbons. They are characterized by relatively great chemical
activity. Examples: propylene, ethylene.

Paraffin oil See mineral oil.

Paraffins See alkanes.

Paranox Trademark, for a series of lubrication oil additives for improved anti-wear, high
temperature detergency etc.
Paratone Trademark, for a. series of lubrication oil additives for improving viscosity index.
Petrolatum (petroleum jelly, Vaseline) Purified mixture of semisolid hydrocarbons.
Plasticizer Ingredient which is added to a plastic to soften increase toughness or otherwise modify the
properties of the binder, e g camphor, trioresyl phosphate.
Polymer A substance c! giant molecules composed by sirnple molecyles (monon-ers) in great
numbers.
Polymerization The formation of a polymer from a monomer. Polymerization is an undesired process in
storing and transportation. Polymerization is accelerated by the presence of heat, light,
some
acids, sometimes rust or other compounds.

Safflower oil A drying vegetable oil,

Saturated compound All valence bonds of the elements are satisfied; incapable of absorbing substances by
addition.
Solvent In chemicals trading usually the name for products used in industry for dissolving other
substances. Examples: acetone, alcohols, glycols, benzene, petrol (gasoline), naphta, carbon
tetrachloride, turpentine, carbon disulphide, cyclohexanol, toluene, xylene.
Solvesso Trademark for a series of hydrogenated naphtas used as solvents.
Stoddard Solvents (safety solvent) A petroleum distillate used mainly in cleaning with limits to max flash point
and boiling point temperatures.

Tall oil Liquid resinous saponifiable oily by-product of the sulfite process.
APPENDIX 5
INFORMATION ON THE HANDLING OF SOME COMMON CARGOES

Listed in this appendix are some of the common products in chemicals trading. Information on necessary tank clean-
liness, cargo handling on board, materials etc are also given.

The information contained in this Appendix, however, does not take into account toxity, reactivity with other
products or safety regulations. This type of information can be found in other literature, in particular in ref (1, 2, 3, 4,
5, 8, 9, 13, 15, 16, 17, 23, 25, 36, 46).

Every opportunity must be taken to obtain additional information from the shipper, terminal operators etc! Discover
for what purpose the cargo in question is intended. One and the same product may have more or less stringent
requirements on cleanliness depending on its future use.

Chemical cargoes in general require that the tanks are completely dry and clean, pumps, valves and piping well
rinsed and drained before loading. In the following pages tank cleaning is commented upon only when particularly
stringent requirements apply or when some unexpected rules apply.

Regarding tank cleaninp in general see Chapter 7.

The necessity of taking properly sealed and identifiable cargo samples is important, see Chapter 8.01

CONTENTS

Acetic acid
Acrylonitrile
Ammonia solutions
Asphalt
Benzene
Butyl acetate
Butyl alcohol
Butyl glycol
Carbon Black Feedstock
Caustic soda
Cerechlor
Cresol
Cyclo-Hexant
Detergents
Ethyl acetate
Ethyl glycol
Ethyl glycol acetate
2-Ethyl Hexoic acid
Glycols (general)
Latex
Methanol
Nonyl phenol
Octanol
Para-xylene
Phenol
Phosphoric acid
Styrene monomer
Sulphuric acid, conc
Toluene, Xylene
Vegetable oils

ACETIC ACID

Toxity: Toxic, see ref (1), (4), (16)

Cargo Handling.: To be kept at min +17 0 C. Heating coils to be of stainless steel (or aluminium).

Materials : Mild steel is normally not acceptable. Coatings of epoxy, zinc silicate or phenolic resins are not
acceptable.

Tanks of stainless steel are normally used.

ACRYLONITRILE ("AN'')

Toxity : Very toxic, see ref (1), (4), (16).

Contamination : Light causes polymerization and darkening of the product and should be avoided. Water should be
avoicieu as it may inactivate the inhibitor added to the product.

Tank condition prior to loading: Tanks and piping must be completely dry and clean.

Cargo handling : Loading of ship's tanks should preferably be arranged with cargo vapour return to shore tanks.
Keep all tank lids closed. Only closed gauging system should be used. Blind flange cargo and vapour piping to other
tanks. Do not place acrylonitrile with bulkhead to bulkhead contact with edible products. Blind flange heating coils.
Heating coils to be blown through over deck prior to being taken in use again. Avoid entering pump rooms as much
as possible during cargo transfer. Keep pump rooms well ventilated.

Tank cleaning.: Wash the tanks thoroughly with cold seawater. Steam and ventilate the tanks well. Check for toxic
vapours prior to entering.

Safety precautions etc: Use oilskin-type protective suit with long rubber boots, gloves, safety goggles and helmet.
Have breathing apparatus available for immediate use when handling cargo gear and when entering pump rooms.

Unauthorised personnel should not be allowed on deck when cargo transfer is in progress. Have an antidote for
poisoning available, see Appendix 7, Chapter 225, ref (36).

Materials : Stainless steel tanks are to be preferred, Zinc silicate coated tanks may be accepted provided the product
is free from water. Epoxy coatings are normally considered non-resistant.

AMMONIA SOLUTIONS, AQUAOUS AMMONIA,NPK SOLUTIONS

Ammonia, phosphates and potassium in various aquaous solutions.

Toxitv: Low toxity, odour warns before danger.

Cargo handling Do not place close to heated cargoes as ammonia in solution has a tendency to ''boil off". Some of
these cargoes, however, are to be heated moderately in order to avoid crystallisation.
Check that vapour lines and pres-vac valves do not get clogged.

Materials : Mild steel, stainless steel, rubber coatings (chloroprene, neoprene) are resistant. Brassware may corrode
very rapidly (inter cristalline corrosion). Bronze may be slightly attacked.

Tank cleaning Tanks can be washed with cold seawater.

ASPHALT, BITUMEN

Heavy petroleum products occuring naturally and as byproducts from refineries.

Melting point 80 degr.- 150 degr C. Loading temperatures 150 degr.-200 degr. C, discharging temperatures
sometimes slightly lower. Certain qualities (blown bitumen) still higher shipping temperatures (230'C).

Contamination : Some remains of heavy oils may be tolerated. Light products should not be permitted.

Tank condition prior to loading: Tanks and cargo piping must be completely dry (if not, eruptions due to the hot
liquid may occur).

Heating coils must be drained or blown free of any water prior to loading.

The tanks should be preheated prior to loading in order to reduce thermal stresses.

Cargo handling on board: Asphalt can only be carried in tanks specially adapted for this product (heated cargo
piping and pumps, extra heating coil area, tank structure arranged to give reduced thermal stresses etc).

There are additives available which can be added to the product, giving it a lower surface tension thus reducing the
effects of eruption due to any entrapped water.

The high cargo temperature causes thermal stresses. Distribute the cargo evenly in order to reduce still water
stresses.

Tank cleaning-: The tank walls can be sprayed with a cold asphalt solution (as used in roadworks) and afterwards the
tanks can be washed out with hot water.

Alternatively the tanks can be successively upgraded by means of heated cargoes.

Materials: Asphalt tanks are normally not painted. Warning: most tank coatings are non-resistant to the tempe-
ratures in question.

BENZENE

Toxity: Toxic after prolonged contact, see ref (1), (4), (16), (36).

Contamination : Discolouration from previous cargoes. Sulphur compounds, see below.

Tank condition prior to loading: Normally only light products such as naphta, aromatics, gasolines are accepted
as last products. If oils (light) were last carried the tanks may have to be cleaned using solvent cleaners added to
the washing water. Cleaning agent sprayed onto the tank wails and with subsequent water washing or the
floatation method using toluene could be used, see Chapter 7.

After completed discharge the tank must be properly ventilated prior to entering. Benzene vapours may be
liberated from sediments, when draining valve bodies etc. Check the atmosphere with toximeters,
see Chapter 6.

Materials : Uncoated steel is usually accepted, but coated tanks are preferable. Zinc silicate coatings are
normally resistant to benzene while epoxy coatings are normally non-resistant. Phenolic coatings are rated as
resistant, check with the coating manufacturer.

Common flange gaskets of asbestos / nitrile rubber are usually acceptable. Expansion glands in cargo piping and
shaft glands conventional in cargo pumps may, after long use with benzene, have to be substituted with PTFE
(teflon) impregnated packings.

BUTYL ACETATE

Toxitv: Moderate, see ref (1), (4), (16).

Tank condition prior to loading : Tanks must be absolutely dry and free from hydrocarbons. Loose rust must be re
moved. The tank must be rinsed with fresh water and dried. e

Cargo handling : Butyl acetate may decompose and form, acetic acid. The product then turns aggresive against steel
and zinc silicate tank coatings (against which it otherwise is neutral). The degree of acidity should be documented
(not below pH 5, 5 for zinc silicate coatings).

Insert blind flanges against other cargoes and keep seawater away.

Materials : Mild steel tanks and epoxy coated tanks are commonly used. Regarding zinc silicate coatings see above.

BUTYL ALCOHOL N- (BUTANOL)

Toxity: Moderate, see ref (1), (4), (16).

Contamination: Sensitive to contamination from other cargoes. Last three cargoes carried should preferably have
been solvent type products (aromatics, naphta, alcohols etc).

Tank condition prior to loading: Tanks must be dry and free from cargo residues. Loose rust to be removed as it may
contain cargo residues.

Tanks to be rinsed with fresh water

Cargo handling : Insert blind flanges against other products on board. Keep seawater out.

Materials : Mild steel tanks, epoxy or zinc silicate coated tanks are acceptable.

BUTYL GLYCOL
Toxity: Moderate, see ref (1), (4), (16).

Contamination - Sensitive to contamination from hydrocarbon products and chlorides (salt).

Tank condition prior to loading: Last three cargoes should preferably have been ''solvents'' (aromatics, alcohols etc)

The tank should be dry and clean and finally rinsed with fresh water.

Loose rust shall be removed (particle contamination)

Cargo handling_: Insert blind flanges against other cargoes and keep seawater away.
Materials : Mild steel, epoxy and zinc silicate coatings are acceptable.

CARBON BLACK FEEDSTOCK (CBFS)

Rawmaterial for the production of carbon black. A heavy oil.

Toxitv: Nil.

Contamination : Sodium (Na) is a contaminant (max 5 – 2 ppm). Sodium is a component in salt (NaCl). 50 - 100 1
seawater mixed into 1 000 tonnes of carbon black feedstok, may give a serious contamination.

Tank condition prior to loading: Tank and piping to be drained free of seawater.

A certain amount of rust and other hydrocarbons are usually accepted.

Cargo handling : Transport temperature 40 - 50 degr C.

Materials : All common tank materials and coatings are acceptable.

CAUSTIC SODA (SODIUM HYDROXIDE)

Toxity : Strongly aggresive to human tissue, see ref (I), (4), (16).

Contamination : Caustic soda intended for paper manufacture is sensitive to iron contamination, particularly rust.
A common limitation is max 10 - 25 ppm iron. For the aluminium, industry the requirements are somewhat less
stringent, but spotlessly clean tanks are required.

Due to its high viscosity and high specific gravity the product is sensitive to particle contamination. Any particles
left will settle very slowly out of the product.

Tank condition prior to loading: Tanks must be kept clean from any hydrocarbon residues and loose rust. Surface
rust may be accepted for the aluminium industry but cellulose industry will require uncoated tanks to be thoroughly
cleaned. Coated tanks are preferred.
Anodes of magnesium, zinc or other light alloys removed or they will be corroded away.

Tank cleaning : Wash ,with cold water, no cleaning agents are, required.

In some cases the cargo may leave drops of mercury behind on the bottom of the tank. These should be removed as
the, tend to initiate local pitting corrosion.

Cargo handling : Caustic soda is strongly aggresive to human tissue and eyesight is at a risk if splashes occur. Use
full protective suit, oilskin type, gloves, rubber boots, protective goggles and a helmet, when handling hoses, taking
ullages, etc.

Caustic soda corrodes copper alloys, however, not stronger than that various bronze fittings in pumps, valves etc can
be accepted. Check the condition of these details after a longer period in service. For single voyages heating. coils of
bronze alloys may be accepted.

Common shipping concentrations are 48 - 50 % Na OH. Corresponding lowest pumping temperatures are about 20 -
22 degr. C. This means that heating must normally be applied. In case of a break down of the heating system the
receiver may accept that the cargo be heated by introduction of live steam at the bottom of the tank.

The specific gravity of caustic soda is high (around 1, 4). This means that cargo tanks have to be strengthened above
''tanker for oil''-standards or special loading conditions discussed with the classification society in question.

Materials : Caustic soda destroys zinc silicate coatings. Epoxy coatings are normally resistent, check with the manu-
facturer. In some cases time limitations for exposure to caustic soda are applicable.

Stainless steel tanks: no restrictions.

Chloroprene (Neoprene) rubber is resistant to caustic soda.

All common types of flange gaskets can be used.

Expansion glands in cargo piping may have a tendency to leak after a period of time in caustic soda service. White
asbestos impregnated with PTFE (Teflon) is suitable for repacking.

CERECHLOR (trade name)

A chlorinated hydrocarbon.

Toxity : Moderate.

Contamination : Cerechlor has a tendency to pick up zinc, tin, copper and also iron from uncoated tank surfaces.
Deteriorates with excess temperature.

Tank condition prior to loading: Normally coated tanks are required. Tanks to be clean and dry. Heating coils of
stainless steel (or possibly coated).

Cargo handling : Product to be kept at 20 - 30 degr. C. Surface temperature of heating coils must not exceed
35-40 degr. C. Heating system should preferably be circulating warm water or warm thermal oil.
Cargo can with advantage be recirculated periodically
Lowest pumping temperature 20 degr. C.

Materials : Epoxy coating preferred. Zinc silicate coating may be acceptable for a product which is water-free and
non-acidous

CRESOL

Toxity: Toxic, see ref (1), (4), (16).

Contamination: Cresol is discoloured by light.

Tank condition prior to loading: Tanks to be clean and dry and free from loose rust

Cargo handling : Heating to 35 - 40 0 C. Avoid over-temperature on the heating coils. Hot water circulation in the
coils is preferred.

Material : Tanks of mild steel are usually accepted. Epoxy tank coatings non-resistant, zinc silicate coatings are
usually acceptable.,

CYCLO-HEXAINE

Contamination : Discolouration due to light. Previous cargo remains.

Tank condition prior to loading : Tanks to be clean and dry and free from rust.

Cargo handling : Cyclo-hexane is particularly sensitive to the build-up of electrostatic charges. Loading rate max
1 m/s until liquid covers filling pipe ends.

Material : Mild steel tanks usually accepted. Epoxy and zinc silicate coatings are usually acceptable.

''DETERGENTS''

Surface-active compounds, pure or mixed with water.

Toxity: Generally low toxity. In some cases alkaline ad6ecl which may give some contact danger similar to caustic
soda solutions.

Contamination: These products are contaminated by the addition of water, salt and hydrocarbons. They may be
damaged (oxidize) if subjected to heat and air for a longer period of time. Avoid temperatures above 60 0 C.

Tank condition prior to loading : Tank to be dry and free from the above contaminants. Proper cleaning is required
as the product will dissolve any cargo remains.

Tank cleaning to finish with a fresh water rinse.

Cargo handling : These products have a tendency to foam during loading. Load at a low rate until the bottom
suctions are well submerged. See to it that air does not enter throught pump shaft glands, valve spindles etc as foam,
problems may then arise.

Heating of the product and seawater contamination rnust be avoided.

Tank cleaning.: The products are water-soluble. In some cases slightly warmed water may be required to avoid gel
formation.

The tanks can be washed with sea-water . Foaming may occur and may be reduced by the addition of some
iso-butanol.

Finally the tanks must be steamed and ventilated.

Materials : Mild steel is usually accepted as tank material for detergents free of water. Products with water contents
are preferably shipped in stainless steel tanks.

Resistance of tank coatings: Check with the maker of coating.

Flange gaskets of rubber-asbestos type are generally resistant.

ETHYL ACETATE

Toxity : Moderate, see ref (1), (4), (16).

Contamination: This product is very sensitive tu nation from other products. As last three cargoes tank aromatics,
alcohols etc (solvents) should preferably have been carried.

Tank condition prior to loading: Tanks having been rinsed with water must then be completely dry and free from
previous cargoes and loose rust.

Cargo handling : Be aware of low: flash point (- 5 degr. C).Insert blind flanges against other cargoes. Keep seawater
out

Materials : Mild steel tanks, epoxy coated , and zinc silicate (water free cargo) coated tanks are acceptable.

ETHYL GLYCOL

Toxity Moderate, see ref (1). (4), (16).

Contamination: The product is very sensitive (: to contamination from previous cargoes. Also sensitive to odours
remaining in the tank. The last three cargoes should preferably have been very light products such as naphta,
aromatics, alcohols etc. Chlorides (salt) is a serious contaminant. Rust and other particles should be carefully re-
moved from the tanks as they cannot be settled out of the product easily.

Tank condition prior to loading : The final rinsing to be done with fresh water. Tanks are to be dry and free from any
previous cargoes, odour, rust and any particles.
Cargo handling : Insert blind flanges against other products. Keep seawater out.

Materials : Mild steel tanks, epoxy coated and zinc silicate coated tanks are usually accepted.

ETHYL GLYCOL ACETATE

Toxity: Mode rate, see ref (1), (4), (16).

r

Contamination: The product is sensitive to contamination from other cargoes. The last three cargoes should pre-
ferably have been very light products such as naphta, aromatics, alcohols etc.(solvents).

Tank condition prior to loading: Final rinsing with fresh water. Tanks to be dry and free from remains of previous
cargoes. Loose rust to be removed.

Cargo handling : Insert blind flanges against other cargoes. Keep seawater away.

Materials : Mild steel tanks are usually accepted. Epoxy coatings are normally accepted but the coating manufacturer
may impose a max time allowed for the product (e g 30 days). Zinc silicate coatings will be attacked if water is
present. Check with the maker of the tank coatings.

2-ETHYL HLXOIC ACID

Contamination: The product is very sensitive to contamination from previous cargo residues.

See also OCTANOL.

GLYCOT S (GENERAL)

Toxity: Moderate to little, see ref (1), (4), (16).

Contamination : Glycols intended for cosmetic and pharmaceutical products are sensitive to odour contamination
(from, previous cargoes such as methanol, molasses, from cleaning agents, from uncured tank coatings etc).

Chlorides are a serious contaminant in certain cases (pharmaceutical grade max 1 ppm).

High viscosity and high specific gravity of many glycols make them sensitive to particle contamination (e g rust).
Particles will be slow in settling out in shore tanks.

Tank condition prior to loading: Tanks to be finally rinsed with fresh water. Tanks to be well swept free of any sand,
rust etc. Tanks and piping to be drained.

Mild steel tanks are usually accepted for water-free glycols but coated tanks (well cured) are to be preferred.
Remaining odours to be removed by steamig , ventilation or repeated washing. Odour-removing aerosols usually
have little effect as the odour originates from minute cargo remains on the tank walls.
A loading inspector may make a chloride test on the tank walls, see Chapter 8. 08. A pre-test can with advantage be
made by the personnel on board to prove that fresh water rinsing has been adequate.

Cargo handling : Keep seawater out and insert blind flanges against other products. Certain glycols require heating, e
g poly-ethylene glycol to max 48 degr. C.

Materials : Epoxy and zinc silicate coatings are acceptable for glycols.

LATEX (GENERAL RULES FOR NATURAL AND SYNTHETIC LATEX)

Toxity: Littie.

Contamination : Latex is damaged (lumps formed) if it freezes below 0 degr. C or is kept above 35 - 40 0 C for any
duration of time.

Rust and unprotected steel may contaminate latex.

Natural latex has added approximately 0, 7 % ammonia to reduce its tendency to coagulate. Therefore galvanized
steel, copper, brass cannot be used as these metals will be readily attacked by ammonia, which may also contaminate
the product.

Tank condition prior to loading : Mild steel tanks (uncoated) must be coated with a paraffin wax (melting point
above 140 degr.C). The tank must be dry during the process.

The tanks must be clean but need not be dry upon loading. It is said that wet tank walls while loading reduces
the tendency for skin adherance after discharge.

Sometimes the tanks are required to be sterilised prior to loading if the state of their cleanliness is held in any
doubt.

Cargo handling : Avoid heating the product from neighbouring tanks.

Natural latex with ammonia added excerts a relatively high vapour pressure. Pres/ vac valves may have to be
set at max permissible value (0,2-0,25 atm = 2 - 2,5 m water col. ). A higher pressure is sometimes demanded
by the shipper (0,3 - 0,35 atm) but the tanks should then have been designed for such a pressure.
Avoid unnecessary access of air to the tanks.

Tank cleaning after discharge: Wash with cold ,water immediately after discharge. Any remaining skin on walls
may then have to be peeled off manually. Be careful not to damage tank coatings
Materials : Stainless steel tanks to be preferred. Mild steel tanks to be treated as, described above. Epoxy
coatings normally considered non-resistant. Zinc silicate and phenolic coatings have limited resistance: check
with the coating manufacturers.
Most gasket materials are acceptable, incl rubber,

Pumps: Ordinary pump shaft glands have a tendency to score in latex service (latex coagulates in contact with
air). Double glands or double mechanical seals are advisable, as the intermediate medium,
METHANOL (METHYL ALCOHOL)

Toxity: Toxic, see ref (1), (4), (16).

Contamination : Methanol is being contaminated by minor amounts of hydrocarbons (also light products) and by
very small amounts of chlorides (salt). Magnesium (a constituent in protective tank anodes) will form magnesium
methylate which is a serious contaminant.

Tank condition prior to loading: Tanks to be dry and absolutely free of any hydrocarbons. Last cargo preferably to
have been a light product.

No anodes in the tank.

Loose rust to be removed as it may contain traces of previous cargoes.

Last rinsing to be done with fresh water.

A tank inspector may make a chloride test, see Chapter 8.08 and a hydrocarbon test, see Chapter 8. 07, on the tank
surfaces.

In certain cases a permanganate time test is required, see, Chapter 8. 16. Remember to conserve loading samples, on
the jetty, for reference. Contamination may have occured before the product was loaded on board.

Cargo handling : Do not locate near heated cargoes (to reduce evaporation losses).

Chlorides contamination has occurred due to seawater ingress during voyage. Keep tank lids carefully closed all
Pres / vac valves protected from the possibility of water entering in bad weather.

Blank off heating coils.

NONYL PHENOL

Contamination: Air may cause a discolouration.

Cargo handling : Inert gas (preferably nitrogen) blanketing during voyage. The cargo tanks to be purged, if possible,
with inert gas prior to loading.

OCTANOL (OCTYL ALCOHOL)

Toxity : Moderate, see ref (1), (4), (16).

Contamination : Sensitive to contamination from previous cargoes. The last three cargoes should preferably have
been aromatics, alcohols etc.
Tank condition prior to loading: Tanks to be finally rinsed with fresh water. Tanks to be clean and dry and loose rust
removed.

Materials: Mild steel tanks, epoxy and zinc silicate coated tanks acceptable.

PARA-XYLENE

Toxity: Moderate, see ref (1), (4), (16).

Contamination : Sensitive to contamination from previous cargoes. Last cargo should have been "solvent'' like a1cc.-
hol, aromatics etc.

Not acceptable last cargoes are vinyl acetate, styrene monomer, vegetable oils or animal oils, gasolines or products
with anti-oxidation additives.

Tank condition prior to loading: Tanks to be clean and dry and free from loose rust. Very careful cleaning necessary,
see Chapter 7.

Cargo handling: Para-xylene has a very high freezing point, +13 degr. C. The cargo should be kept around
20-30 degr. C. Freezing will occur from the sides and bottom of the tanks. The botton, suctions may freeze and get
blocked. With the shipper's consent one may, if difficulties arise, "lift'' the cargo onto a water bed in order to avoid
blocking the tank suctions.

Materials : Zinc silicate coatings are resistant to paraxylene. Epoxy coatings are normally considered non-resistant.
Check with the maker. In any case epoxy coatings have to be very well cured.

Epoxy tar coatings -are not acceptable as they may bleed and discolour the product.

Stainless steel: no restrictions.

Common flange gaskets of asbestos / rubber type are normaily resistant. Common packing in spindle glands and pipe
expansion boxes may after some time have to be repacked with PTFE-impregnated asbestos.

PHEINOL

Toxity : Very toxic, in particular to skin contact, see ref (1), (4), (16).

Contamination : Phenol may become discoloured by the effect of light, excess heating, minor amounts of alkaline
matter, iron, copper, bronze and oxidation.

Tank condition prior to loading: Normally stainless steel tanks are to be preferred. Mild steel tanks can be
accepted if a certain discolouration can be tolerated.

Tanks to be clean and dry and free from any alkaline matter (e g from last tank cleaning operation).

Cargo handling : Phenol shall be kept at a temperature of min 50 degr. C, max 58-60 degr. C. Steam heating
should be avoided: overheating of the coils may result in discolouration and cargo claims. Heating should
preferably be achieved by means of circulating warm water or by a heating oil in the coils thereby obtaining a
better temperature regulation.

Phenol vapours may sublime and form deposits on cold surfaces above the liquid level. Sometimes there are
available special means of heating pres/vac valves and vapour outlets in order to avoid the risk of blocking the
same. However, in most cases of common exterior temperatures such heating may not be necessary.

Keep water away in order to avoid contamination.

Tank gauging should be carried out by means of enclosed sounding devices in order to eliminate the risk of skin
contact.

Tank atmosphere : The free exposure of the product to air should preferably be restricted. Avoid slack tanks.
Sometimes inert gas blanketing is required above the cargo or driers inserted into the vacuum vents.

Safety procedure: Use an oilskin-type protective suit with long rubber boots, gloves, safety goggles and a
helmet. Have a breathing apparatus available and use it when entering the pump room and when handling cargo
gear.

Keep unauthorised persons away!

Tank cleaning_: Wash the tanks with hot water and steam afterwards if necessary to remove any odour. Sometimes
soda is added in the steam in order to achieve a degree of neutralisation.

Materials : Normally stainless steel tanks are required by the shipper. Epoxy and zinc silicate coatings are normally
not guaranteed for use with phenol.

Gaskets preferably of asbestos,/PTFE (Teflon) type or silicone type preferred. Pump shaft seals preferably of a
mechanical seal type.

PHOSPHORIC ACID (ORTO-) (54 %)

Toxitv: Moderate, avoid splashes in the eyes. See ref (1), (4), (16).

Contamination : Chlorides (seawater, salt) is a serious contaminant (may cause corrosion to stainless steel). Max
permissible chlorides contents (as Cl) are usually 100-200 ppm.

Even minor amounts of salt remaining on a stainless steel tank wall after cleaning may, in combination with acid
remains, cause pitting corrosion.

Keep seawater and marine atmosphere away from stainless steel tanks !

Tank condition prior to loading : Tanks to be free of previous cargoes. Tanks to have been finally rinsed with fresh
water. Tanks need not necessarily be dry but no traces of seawater can be accepted.

Stainless steel tanks should be free of any solid matter, rust flakes etc, or objects under which crevice corrosion may
occur.
Inspect the tanks closely before and after loading/discharge and note, or repair by grinding or welding, any corrosion
attack from previous cargo.

Tank cleaning (specifically stainless steel tanks). Tank cleaning after phosphoric acid should preferably be carried
out by the use of fresh water, but in any case the washing should end with a thorough fresh water rinse. No cleaning
agents needed.

Problems may be met in sediments accumulated on the tank floor. They can usually be washed out by manual
hosing. After agreement with the receiver fresh water sediment washings 'may be allowed to be discharged into the
cargo shore tanks (provided the dilution effect is considered acceptable). Personnel entering an un-cleaned tank
should wear a protective suit and a breathing mask.

Sediments are in some instances washed out by means of recirculated phosphoric acid taken from the discharge
stream.

The fresh water used for washing purposes may be slightiy alkaline by the addition of soda (neutralises acid remains
and reduces corrosion in the fresh water tanks when evaporated water is being used).

Cargo handling : Prior to loading: check the specification of the cargo to be loaded against charter party or contract,
with particular regard to the chloride contents, fluorides and the contents of sediments.

If the cargo temperature is high (say 40-50 degr. C) one should be careful not to accept excessive contents of
chlorides (and fluorides). High contents of iron and aluminium counteract to a certain degree the corrosiveness due
to excessive chlorides.

Commercial phosphoric acid contains particles of gypsum and various phosphates in suspension. This matter has a
tendency to settle out on the tank bottom as a clay-like sediment, sometimes in considerable amounts. A drop in
temperature during the voyage will accelerate the fall-out of sediments. Similarly newly produced acid will have a
higher fall-out rate. Some ships have circulation systems whereby the acid can be held in movement with much less
fall-out as a result.

Spillage of acid in pump rooms may cause corrosion problems, Pump room bottoms may be epoxy coated as a
protection and pumps provided with drip pans. Wash out pump room bilges; some soda solution may be added to
neutralise any spilt acid.

Materials : Stainless steel of high molybdeniurn-low carbon (max 0, 05 %) are normally resistant to phosphoric acid
provided chlorides contents and temperatures are within normal specifications, see above. Common types are AISI
316 L, AISI 317 1-, SIS 2353-

Rubber lined tanks are common ashore and are also used on some ships. Chloroprene (Neoprene) is then suitable as
it is durable against sun radiation, ozone and accidental spills of oil. Natural rubber is frequently used in tanks
ashore.

Gaskets of PTFE/blue asbestos, envelope PTFE, rubber,' asbestos and rubber can be used.

STYRENE MONOMER

Toxity: Moderately toxic, see ref (1), (4), (16).

Contamination : Styrene polymerises under the influence of light, oxygen, heat, rust etc, Polymerisation can be
observed as a discolouration and also as deposits on tank surfaces.

Copper with alloys may also cause discolouration.

Tank condition prior to loading: Tanks must be dry and clean and free from all loose rust. Heating coils must be
blind flanged. Insert blind flanges against other cargoes.

Cargo handling- Maximum transport temperature 32 0 C

Styrene must not be placed in bulkhead contact with heated cargoes. Cool the deck by hosing seawater over it on
very hot days

Styrene has an inhibitor added against polymerisation. The inhibitor, being consumed with time, may fall out in
cases of low temperatures. Adding inhibitor is a job for specialists.

The inhibitor is usually tert butyl catechol (TBC) which is added to a concentration of ca 15 ppm. The contents
should not be permitted to go below 8 ppm. A check on contents of the inhibitor can be made by means of a colour
comparison and a reference scale.

A check on the amount of polymerisation can be made by mixing 1 part of styrene with 3 parts of methanol. If the
mixture remains a clear liquid or shows an only slightly bluish shadow, the product is probably intact.
Polymerisation can be observed as a whitish shadow.

The shipper sometimes requires styrene monomer to be transported with inert gas blanketing.

Tank cleaning. Tanks must be washed immediately after discharge with cold water. If washing cannot be carried out
it is adviseable to keep the tank filled with cold water until washing can take place. Sometimes polymerised material
has to be removed manually. In the final cleaning detergents or solvent cleaners must be used. Final steaming may
be necessary to remove remaining odours. Chlorethane can be used for cleaning valves, glands etc.

Demand a certificate of inhibition from the shipper!

SULPHURIC ACID, CONC

Toxity: Strongly aggressive to human tissue. See ref (1), (4), (16).

Tank condition prior to loading : Tanks dry and clean. Cargo piping drained free of -water.

Cargo handling : Use full protective suit (oilskin type), gloves, long rubber boots, protective goggles and a helmet,
when handling hoses, taking ullages etc.

Sulphuric acid may react violently to a number of products (e g water, caustics, some polymerisable products) see
data in ref (1) and Appendix 3. Sulphuric acid must not be placed with bulkhead contact to such cargoes or in tanks
being part of the side shell or bordering filled ballast water tanks.

Never introduce water into sulphuric acid! An eruption of acid may follow.

Conc sulphuric acid (above approx 94-96 %) does not attack steel. Diluted acid is strongly corrosive to mild steel
and also to stainless steels.
Fill the cargo tanks as much as expansion margin permits. Moisture in the air may cause diluted acid on the
tank walls with corrosion as a consequence.

Keep pump room bottoms free from acid spills. Hose down and drain any acidous bilge water. Add some
alkaline water (soda added) to the bilges, this will reduce corrosion. Litmus paper can be used as a check on
acidity of the bilges.

Tank cleaning_: After discharge the tank bottoms and piping should be filled with water immediately and the
whole tank thoroughly washed with cold water. It is a question of rapidly reducing the acid concentration to
harmlessly low values.

A final rinsing with alkaline (with soda added) water is advantageous.

Materials: Mild steel and stainless steels are resistant to conc sulphuric acid (94 -95 %)

At the moment there are no tank coatings available which are resistant to sulphuric acid .
Flange gaskets of asbestos/rubber type are acceptable. Asbestos/ PTFE (Teflon) gaskets or envelop
PTFE-gaskets are preferable.

TOLUENE, XYLENE

Toxitv : Moderate, see ref (1), (4), (16

Contamination : Discolouration from previous cargoes. Xylene ''nitration grade'' is sensitive to contamination
by chlorides (salt).

Tank condition prior to loading: Loose rust should be removed as it may contain residues of previous cargoes. Rust
in itself is acceptable.

Before xylene ''nitration grade'' the tanks should be rinsed with fresh water.

The tank inspector may make a ''presence of hydrocarbon test", see Chapter 8. 06, 8. 07, 8. 08. In case of doubt the
ship's officers can make these tests themselves before hand.

To obtain the necessary degree of cleanliness methods outlined in 7. 044, floatation, may have to be used.

Cargo handling : In order to avoid cargo evaporation losses these products should not be placed close to heated
cargoes.

Blank off heating coils.

Materials : Zinc silicate coatings are resistant to toluene and xylene. Epoxy coatings are normally considered
non-resistant or have time limitations, check with the coating manufacturer. In any case epoxy coatings must be
very well cured and aged.

Epoxy tar coatings are non-resistant and may discolour the cargoes.

Stainless steel tanks: no restrictions.

Common flange gaskets of asbestos/rubber type can be considered resistant. Expansion glands in cargo piping,
spindle boxes etc may have to be repacked with PTFE impregnated asbestos after some time in service.

VEGETABLE OILS

Data: See ref (1). As examples can be mentioned:

Solidifying Melting
temp degr. C temp degr. C

Cottonseed oil 1 -10

Groundnut oil
Capok seed oil 11,5
Coconu oil 15 - 21 20 - 28
Linseed oil - 8 ~ - 15
Olive oil
Palm oil 24 - 40
Palm kernel oil 26 - 30
Soya bean oil - 8 ~ - 15 22 - 31
Sunflower seed oil
Tung oil (Chinese 3 31
wood oil)

Specific gravities in the range 0, 91-0,95.

Toxitv: These products are non-toxic. There have been accidents, however, when tanks have been entered just after
completed discharge. There are indictions that the lack of oxygen may have been the cause. Oxidising oils may be
more dangerous in this respect. Ventilate well!

Contamination: Odour and remains from previous cargoes may be a serious contaminant. Strongly smelling products
(methanol, octanol, molasses etc) rnay lessen the value of edible products considerably.

Discolouration may result due to overheating from heating coils with a too high surface temperature.

Vegetable oils may be contaminated and become toxic if the are carried in zinc silicate coated tanks under incorrect
conditions (see below).
Vegetable oils may increase their contents of free fatty acids abnormally and turn rancid if:
- The tanks are poorly cleaned from previous cargoes (bacteria from vegetable or animal oils)
- The cargo is carried at an unnecessarily high temperature
- The ullage space (air) is unnecessarily large
- Sun radiation, light or heat is applied onto the cargo.

Tank condition prior to loading: Normally vegetable oils are carried in coated tanks. Uncoated mild steel tanks must
be free from rust.

In order to remove odours the tanks may have to be steamed.

Cleaning by means of soda or any other cleaning agents is normally required. Finally a fresh water rinse.

Manual cleaning may be necessary in awkward corners etc. Tank inspectors will scrutinise very carefully! Capok
seed oil in particular requires well cleaned tanks.

Heating coils to be tested prior to loading.

Independent surveyors are usually called in to certify tank cleanliness. In some cases tightness tests are required.
They are often carried out with air at about 0, 1 kp/cm *2 (1 m water head) with tank boundaries etc tested with soap
water.

Cargo handling : Insert blind flanges against cargoes of a different nature.

Never load vegetable oils adjacent to toxic cargoes ! Insert blind flanges, which are necessary for separation!

Heat the cargo according to instructions from the shipper. Heat with great caution in order not to burn the cargo, in
particular soya bean oil, cottonseed oil, capok seed oil, linseed oil, tung oil. Adjust the admission of steam, not to
return condensate !

Do not heat more than instructed. In certain cases one voyage temperature and another discharge temperature is
stipulated (e g capok seed oil: voyage 11-13 degr. C, discharge 24-30 degr. C). Increase heating very slowly!

During the voyage there will, usually and normally, be an increase in the amount of free fatty acids (FFA). Prior
to loading the amount of FFA should be determined by an independent surveyor and the result documented. The
vessel may be held responsible for an abnormal increase in FFA-contents. The increase- in FFA will be greater,
the higher FFA-contents there are at the beginning.

The following vegetable oils normally require heating: cottonseed oil, coconut oil, palm oil, palm kernel cii.
Other vegetable oils may require heating at low ambient temperatures.

Tank cleaning after vegetable oils-: See also Chapter 7. It is important that cleaning is commenced immediated
.L

after discharge. If the tank is filled with ballast water for a period of time the cleaning may become much more
difficult.

Observe the cleaning routine for drying oils: Start the cleaning with cold water (e g castor seed oil, cotton seed
oil, linseed oil, ground nut oil, tung oil, soya bean oil and sunflower oil).
Materials : Epoxy tank coatings generally have a good resistance against vegetable oils. Zinc silicate coatings
may be affected by the cargo and the cargo suffer a zinc pick up if vegetable oils have a too high contents of
free fatty acids.

Usuallv 2, 5 % of free fatty acids are tolerated, for short voyages up to 5 %. Palm oils and coconut oils should
not be carried in zinc silicate coated tanks.
The Nigerian Produce Marketing Board gives the following general guidance for the carriage of vegetable oils (FFA
means free fatty acids):

HEATING INSTRUCTIONS FOR PALM OIL

1) Ship's coils must be completely covered by the oil on completion of loading.

2) No heat shall be applied until the average temperature of the oil has fallen till 95 0 F. for oil up to and including
6% FFA and 105 degr.F for oil exceeding 61 % FFA. Heat should then be applied to maintain these temperatures
until the sixth day prior to arrival at port of discharge.

3) As from the sixth day prior to arrival at port of discharge, temperature should 'be raised steadily (not more
than 5 degr. F in 24 hours) in order to reach but not exceed the following average temperatures on discharge:
125 degr. F for oils up to and including 61% FFA and 135 degr.F for oils exceeding 61 % FFA on shipment.

4) During the winter months, namely from November to April inclusive the foregoing temperatures my be increased
by 5 degr.F.
5) Top and bottorn ternperatures should be maintained as equal as possible.

6) SPECIAL WARTNING - A sudden increase in temperature must be avoided as it will almost certainly result in
damage to the oil.

7) These instructions may be varied only by official wireless or written notification. Details of any amendment-s
and the authority responsible must be duly recorded.

8) At the time of loading the correct and true FFA of the oil loaded must be stated on the loading and carriage log.
APPENDIX 6

Excerpt from:

IMCO : “ Code for the Construction and Equipment of Ship’s

Carrying Dangerous Chemichals in Bulk
APPENDIX 7

Exerpt from :

MEDICAL FIRST AID GUIDE FOR USE IN

ACCIDENTS INVOLVING DANGEROUS GOODS

Reprinted by the permission of the Inter – Governmental Maritime

Consultative Organization