Liquid Cargo Notes

DEVELOPMENT OF TANKERS
Carriage of oil in barrels in conventional cargo ships

Construction of vessels to carry oil in bulk
Use of longitudinal divisions and transverse bulkheads to form tanks
Location of machinery aft
Increase in size to ULCCs
Transportation of liquefied gas and chemicals in bulk
Pollution problems and explosion/fire hazard leading to international
controls
The development of SOLAS And MARPOL
Increasing use of training to improve safety and reduce pollution
The STCW Convention and Chapter V of that Convention
The development of double-hull tankers
The implementation of the International Safety Management (ISM)
code

CHEMICAL TANKERS

Sea transport of chemicals started with the chemical
industries rapid growth in the year after World War Two
At first, chemicals were transported in bottles or drums on dry
cargo ship; larger quantities were shipped in bulk in the deep
tanks of these ships
As the worlds demand for chemicals increased, the need for
a new type of seagoing ship became evident
The first chemical tankers were converted war-built American
oil tankers (T2 tankers)
Conversion work usually included:
adding bulkheads to provide more and smaller
tanks
extending the line system
Installing additional cargo pumps

The first conversion of this type was done in 1948 on
the R.E. Wilson. of 9073 tons gross tonnage
In addition to these converted, relatively big chemical
carriers, smaller tankers specially designed and
constructed for the carriage of acids e.g. sulphuric
acid, were built during the early 1950s, the cargo tanks
of which were made of special alloy steel, strengthened
for cargo densities up to 2.0 kg/l
In order to carry chemicals of high purity and sensitive
to contamination, coating techniques were developed
for cargo tanks of mild steel.

The first real chemical tanker specially designed
for the carriage of liquid chemicals in bulk was
the Norwegian M/T Lind, delivered in 1960; this
was the first tanker equipped with stainless cargo
tanks
A modern chemical tanker has a large number of
cargo tanks and is designed for carriage of a wide
variety of cargoes
The cargo-tank section on these modern ships is
normally divided into some stainless steel tanks
and some coated mild-steel tanks, each of which
is normally equipped with deep well pumps and a
separate piping system.

GAS CARRIERS

Gas shipping began in the late 1920s
The earliest ship were designed to carry liquefied gas
in pressure vessel at ambient temperature
The first cargoes on the market were butane and
propane
Development of refrigeration techniques and metals
suitable for low temperature made it possible to
carry liquefied gas at temperatures low than ambient

Around 1959, semi-pressurized ships entered
the market and liquefied gas was now
transported under lower pressure, which was
made possible by lowering the temperature

By 1963, fully refrigerated ships for LPG, LNG
and certain chemical gases were in service,
carrying cargo at atmospheric pressure

CHEMICAL TANKERS- IMO SHIP TYPE

1. IMO Ship Type 1 is a chemical tanker intended for the transportation
of products considered to present the greatest overall hazard, and
Type 2 and Type 3 for products of progressively lesser hazards. The
quantity of cargo required to be carried in a Type 1 ship should not
exceed 1,250 m3 in any one tank.
2. IMO Ship Type 2 is intended to transport products with appreciably
severe environmental and safety hazards which require significant
preventive measures to preclude escape of such cargo. The quantity
of cargo required to be carried in a Type 2 ship should not exceed
3000 m3 in any one tank.
3. IMO Ship Type 3 is a chemical tanker intended to transport products
with sufficiently severe environmental and safety hazards. These
products require a moderate degree of containment to increase
survival capability in a damaged condition. There is no filling
restriction for chemicals assigned to Ship Type 3.
CARGO CONTAINMENT SYSTEM
GAS CARRIERS
FULLY PRESSURIZED GAS CARRIERS
LPG carriers fitted with two or three horizontal, cylindrical
or spherical cargo tanks and have capacities up to 6,000
m
3
. However, in recent years a number of larger-capacity
fully pressurized ships have been built with spherical
tanks, most notably a pair of 10,000m
3
ships, each
incorporating five spheres. Fully pressurized ships are still
being built in numbers and represent a cost-effective,
simple way of moving LPG to and from smaller gas
terminals.

Semi-pressurized ship
These ships carried gases in a semi-pressurized/semi-
refrigerated state
ship owners' choice by providing high flexibility in cargo
handling.
These carriers, incorporating tanks either cylindrical,
spherical or bi-lobe in shape, are able to load or discharge
gas cargoes at both refrigerated and pressurized storage
facilities.

Ethylene carriers
are the most sophisticated of the Gas tankers
able to carry most liquefied gas and ethylene at its
atmospheric boiling point of -104C.
Features cylindrical, insulated, stainless steel cargo
tanks
able to accommodate cargoes up to a maximum
specific gravity of 1.8 at temperatures ranging from a
minimum of -104C to a maximum of +80C and at a
maximum tank pressure of 4 bar.

Fully refrigerated ship
built to carry liquefied gases at low temperature
and atmospheric pressure.
Prismatic tanks enabled the ship's cargo carrying
capacity to be maximized
thus making fully refrigerated ships highly suitable
for carrying large volumes of cargo such as LPG,
ammonia and vinyl chloride over long distances.
Independent tanks with rigid foam insulation are
the most common containment system utilized
TANK TYPES
Integral Tanks- form a structural part of the ship's hull
and are influenced in the same manner and by the
same loads that stress the adjacent hull structure.
Membrane Tanks - are non-self-supporting tanks which
consist of a thin layer (membrane) supported through
insulation by the adjacent hull structure. The
membrane is designed in such a way that thermal
and other expansion or contraction is compensated
for without undue stressing of the membrane
Semi-membrane tanks are a non-self-
supporting tanks in the loaded condition and
consist of a layer, parts of which are supported
through insulation by the adjacent hull
structure whereas the rounded parts of this
layer connecting the above mentioned
supported parts are designed also to
accommodate the thermal and other
expansion or contraction
Independent tanks are self-supporting; they do not form part of the ship
hull and are not essential to the hull strength.

Type A Independent Tanks prismatic and supported on insulation-
bearing blocks typically consisting of wooden chocks and located by
anti-roll chocks located at the top of the tank inside the void space
and anti-flotation chocks located inside the void space usually just
above the double bottom tanks. The tanks are normally divided by a
centerline liquid-tight bulkhead;. When these cargo tanks are
designed to carry LPG (at -50C), the tank is constructed of fine-
grained low carbon manganese steel or even stainless steel. The
hold space (void space) in this design is normally filled with dry inert
gas or Nitrogen but may be ventilated with air during a ballast or gas
free passage. The Conch design has been developed for carriage
of LNG (at-163C). The material for these cargo tanks has to be
either 9% nickel steel or aluminum. The maximum Allowable relief
vapour setting (MARVS) is < 0. 7 bar.

Type B Independent Tanks are generally spherical and
welded to a vertical cylindrical skirt, which is the lone
connection to the ship's main hull. The hold space (void
space) in this design is normally filled with dry inert gas or
Nitrogen but may be ventilated with air during a ballast or
gas free passage. A protective steel dome covers the
primary barrier above deck level, and insulation encloses
the outside of the primary barrier surface. This
containment system has been used for carriage of LNG.
The material of construction is either 9% nickel steel or
aluminum. The maximum Allowable relief vapour setting
(MARVS) is < 0. 7 bar.

Type C Independent Tanks are deck pressure
vessels or cylindrical pressure tanks mounted
horizontally on two or more cradle-shaped foundations.
The tanks may be fitted on, below or partly below deck
and be both longitudinally and transversely located.
Lobe-type tanks are commonly used at the forward end
of the ship, to improve the poor utilization of the hull
volume. This containment system is used for LPG and
in Ethylene carriers. The material, if used for the
construction of tanks designed to carry ethylene, is 5%
nickel steel. The maximum Allowable relief vapour
setting (MARVS) is > 0. 7 bar.

HYDROCARBONS
A hydrocarbon is a natural compound that
contains hydrogen and carbon. Hydrocarbons are
classified as organic and can have single
(saturated), double or triple (unsaturated) bonds
between the carbon atoms. Most hydrocarbons
occur naturally in crude oil. Crude oil is the
decomposed organic matter formed by millions
of years of heat and pressure under the earth's
crust. The hydrocarbons found in oil are typically
called fossil fuels and are the primary source of
the world's energy.

HYDROCARBONS
Sources of Hydrocarbons
Fossil Fuels (Crude Oil & Natural Gas)

Crude Oil is a mixture of hydrocarbons ranging
from those which are partly gaseous under
normal atmospheric conditions to those which
are liquid and solid.

The petroleum remaining after the removal of products
such as methane is termed crude oil

HYDROCARBONS
HYDROCARBONS
CHEMICAL CARGO

A chemical tanker is primarily designed for the
carriage of dangerous chemicals in bulk and
in addition to the cargoes listed in the IBC
Code, chemical tankers may carry a wide
variety of other liquid products which would
normally be considered to be unrelated to
chemicals.

CHEMICAL CARGO

Cargoes in chemical tankers may be divided
into 4 groups as follows:
petrochemicals
alcohols and carbohydrates
vegetable and animal oils and fats
inorganic chemicals

PETROCHEMICALS
organic products derived wholly or partly from
crude oil, natural gas or coal.
Examples of petrochemicals:
solvents
aromatics
intermediates or refined products

CHEMICAL CARGO
The group of alcohols and carbohydrates
includes products which may be produced
by fermentation, such as:
liquor
wine
molasses
CHEMICAL CARGO
Fermentation
is the process of extracting energy from
the oxidation of organic compounds, such
as carbohydrates, using an endogenous electron
acceptor, which is usually an organic compound.

VEGETABLE & ANIMAL OILS- are products derived from seeds
of plants and from the fat of animals, including fish. They are
insoluble in water and oily or greasy to the touch. Their
composition is quite different from mineral oils, which are
almost completely composed of hydrocarbons. Fats or oil
containing saturated fatty acids are generally in the solid form
and are required in the manufacture of soap and margarine,
while fats or oils containing unsaturated fatty acids usually are
liquid at room temperature.

Examples of vegetable and animal oils and fats:
soya bean oil
cottonseed oil
lard and lard oil
beef and mutton tallow
whale oil
sardine oil
cod oil
CHEMICAL CARGO
Inorganic chemicals are products which are not
of organic origin. These are carried in large
quantities because they are virtually utilized by
every manufacturing industry. Although other
petrochemicals are carried in bulk this deals
specifically for mineral acids which is sometimes
called heavy chemicals

Examples of inorganic chemicals are:
sulphuric acid
phosphoric acid
nitric acid
caustic soda

CHEMICAL CARGO
Most cargoes in chemical tankers belong to the group
petrochemicals
Chemical tankers may also carry petroleum products
such as those normally carried in oil tankers
Dedicated service usually means that the tanker is
dedicated for a certain type of chemicals, transporting
the same type of cargo on each voyage
A chemical tanker engaged in parcel service moves a
variety small lots of chemicals between a number of
ports. Chemical tanker is a cargo ship constructed or
adapted and used for the carriage in bulk of any liquid
product listed in Chapter 17 of the IBC Code.

CHEMICAL CARGO
ACID and BASE
ACID
the term acid was first used in the seventeenth century; it
comes from the Latin root ac-, meaning sharp, as in
acetum, vinegar. Some early writers suggested that acidic
molecules might have sharp corners or spine-like projections
that irritate the tongue or skin.
An acid is a substance that yields an excess of hydrogen ions
when dissolved in water.
A characteristic sour taste (think of lemon juice!);
ability to change the color of litmus from blue to red
react with certain metals to produce gaseous H
2

react with bases to form a salt and water

BASE
The word alkali is often applied to strong inorganic bases. It
is of Arabic origin, from al-kali ("the ashes") which refers to
the calcined wood ashes that were boiled with water to obtain
potash which contains the strong base KOH, used in soap
making. The element name potassium and its symbol K (from
the Latin kalium) derive from these sources
The name base has long been associated with a class of
compounds whose aqueous solutions are characterized by:
bitter taste
A soapy feeling when applied to the skin;
ability to restore the original blue color of litmus that has been turned
red by acids
ability to react with acids to form salts
react with certain metals to produce gaseous H
2

ACID and BASE
A base is a substance that yields an excess of
hydroxide ions when dissolved in water.

An acidic substance is one whose molecular
unit contains at least one hydrogen atom that
can dissociate, or ionize, when dissolved in
water, producing a hydrated hydrogen ion and
an anion."

ACID and BASE
ACID and BASE
Understanding pH

Let's begin with the words acidic and basic as extremes which describe
solutions as hot and cold are extremes which describe temperature. Just
as mixing hot and cold water evens out the temperature, mixing acids
and bases can cancel their extreme effects and is then considered
neutral.

The pH scale can tell if a liquid is more acid or more base, just as
the Fahrenheit or Celsius scale is used to measure temperature.
The range of the pH scale is from 0 to 14 from very acidic to very
basic. A pH of 7 is neutral. A pH less than 7 is acidic and greater
than 7 is basic. Each whole pH value below 7 is ten times more
acidic than the next higher value. For example, a pH of 4 is ten
times more acidic than a pH of 5 and a hundred times (10 X 10)
more acidic than a pH of 6. This holds true for pH values above 7,
each of which is ten times more basic (also called alkaline) than
the next lower whole value. An example would be, a pH of 10 is
ten times more alkaline than a pH of 9.

LIQUIFIED GAS CARGO
Liquefied gas is the liquid form of a substance
which at ambient temperature and atmospheric
pressure would be a gas.

Liquefied gases are those substance having a vapour
pressure exceeding 2.8 bars absolute at a
temperature of 37.8C and certain other substances
specified in the Gas Code.

TYPES OF GAS CARGOES
LNG is liquefied natural gas from which impurities
are removed (e.g. Methane)
LPG is a common name for petroleum gases,
mainly propane and butane. LPG is produced from
two sources:
1. from crude oil processing in refineries, or as a by-product
of chemical plants
2. from natural gas streams or from crude oil at or close to
production points

LIQUIFIED GAS CARGO
Liquefied ethylene gas (LEG) is produced by cracking of
LPG

Chemical gases are a group of liquefied gases produced
through a chemical process
Chlorine, ammonia and vinyl chloride monomer (VCM)
as examples of chemical gases
Certain other substances in the borderland between
liquefied gas and chemicals are carried on gas tankers
Acetaldehyde and propylene oxide as examples of such
cargoes

LIQUIFIED GAS CARGO
METHODS BY WHICH GAS IS LIQUIFIED
1. Liquefaction by removal of heat
-Liquefaction of gas cargoes on ships other than fully
pressurized ships is done by removal of heat
- The heat to be removed from the cargo is called latent
heat of condensation
2. Liquefaction by pressurizing

Gas carrier is a cargo ships constructed or adapted and
used for the carriage in bulk of any liquefied gas or other
products listed in the table of chapter 19 IGC Code
LIQUIFIED GAS CARGO
CHARACTRIESTICS OF CARGO
States of Aggregation- A substance (matter) can present itself to us in three
different forms or phenomena. These are called states of aggregation. The three
forms are:

The solid or crystalline state -There is a strong attraction between the
molecules of the substance. Therefore, these molecules are closely together in
more or less fixed positions, e.g. in a crystal. A solid substance has its own form
and volume.

The liquid state -The powers of attraction between the molecules are much
smaller, so that the mutual distances are bigger, and the molecules can move
with respect to one another. Although there is still a connection, the liquids do
not have a form of their own and they are movable; they do have their own
volume.

The gaseous state-There are hardly any powers of attraction between the
molecules which move completely free in respect of one another. They have no
form of their own, no volume of their own; a gas completely fills the container
in which it is present; therefore so to speak, takes on the form and volume of
this container.

The stage of aggregation of a substance
depends on pressure and temperature. At
high pressures and low temperatures we
usually have to do with solid substances; low
pressures and high temperatures stimulate
the existence of gases.

THE HYDROCARBON STRUCTURE
crude petroleum as discharged at the well head is a mixture
of about one thousand of different hydrocarbon molecules
the molecules are termed light or heavy according to
the number of carbon atoms forming the molecule
very light molecules such as methane, butane and propane
tend to be gaseous under normal atmospheric conditions
very heavy molecules such as asphalt and bitumen tend to
be solid under normal atmospheric conditions
intermediate molecules such as petrol (motor spirit) and
diesel oil tend to be liquid under normal atmospheric
conditions
THE HYDROCARBON STRUCTURE
very light gaseous molecules such as methane are
extracted at the well head
the petroleum remaining after the removal of products
such as methane is termed crude oil
crude oil is a mixture of hydrocarbons which under
normal atmospheric conditions are gaseous, liquid and
solid
an oil refining process termed distillation, crude oil is
split into a number fractions
each petroleum fraction has a range of physical
properties specified to itself


DISTILLATION - is a method of separating mixtures
based on differences in volatilities of components in
a boiling liquid mixture. It is used to separate crude
oil into several specific fractions.

How does distillation works in Petroleum refinery?
Since crude oil is a raw material and unusable. It undergo
through the process of distillation to produce different
fractions (or products such as gasoline etc.) Crude oil is
heated and the different fractions are pulled out by their
vaporization temperatures or commonly called as boiling
point.

CRACKING - cracking is the process whereby complex
heavy hydrocarbons such as heavy gas oil that is
produced from distillation are broken down into light
hydrocarbons such as gasoline.

Why do we have to crack petroleum products when it
already underwent the process of distillation?
In the early days of crude oil refining, the process cracking do
not exist, it was later used during the world war 2 1940s due
to the high demand of the US for gasoline. Scientist were
challenged how can a greater proportion of gasoline be
extracted from the crude oil than that obtain from distillation
process alone. Scientist look for any products other than
gasoline which are drawn from the crude oil, studied their
molecules and found a way to change them into gasoline
hence the result was CRACKING

Characteristics of Cargo
VOLATILITY - is the tendency of a substance to vaporize.
Volatility is directly related to a substance's vapour pressure. At a
given temperature, a substance with higher vapour pressure
vaporizes more readily than a substance with a lower vapour
pressure. Volatile petroleum has a flashpoint below 60
o
C (140
o
F), as
determined by the closed-cup method of testing.
VAPOR PRESSURE - The pressure of the vapour that is
formed above its liquid or solid is called the vapour pressure.
Vapour pressure is a force exerted by the gaseous phase of a
two phasegas/liquid or gas/solid system.

TRUE VAPOR PRESSURE (TVP)
is a common measure of the volatility of petroleum
distillate fuels.
the bubble point vapor pressure is the equilibrium vapor
pressure of a mixture when the gas/liquid ratio is
effectively zero. It is the highest vapor pressure which is
possible at any specified temperature.
As the temperature of the of a petroleum mixture
increases, its TVP also increases. If the TVP exceeds
atmospheric pressure the liquid commence to boil.
TVP of a petroleum mixtures provides a good indication of
its ability to give rise to gas.
TVP differs slightly with RVP.

REID VAPOR PRESSURE (RVP) -
is a way to measure how quickly fuels evaporate; it's often
used in determining gasoline and other petroleum product
blends. The higher a fuel's RVP, the more quickly it
evaporates. The more quickly a fuel evaporates.
It is determined by the ASTM test method D323,is widely
used in the petroleum industry to measure the volatility of
petroleum crude oil, gasoline and other petroleum products.

American Society for Testing and Materials (ASTM)
Is an international standards organization that develops and
publishes voluntary consensus technical standards for a wide range
of materials, products, systems, and services
Flashpoint
the lowest temperature at which a liquid gives off
sufficient vapour to form a flammable mixture with air
near the surface of the liquid. The flash point temperature
is determined by laboratory testing in a prescribed
apparatus. There are two methods: either by closed
method in the closed cup (c.c.) or by open method- in the
open cup (o.c.)
Melting Point
the temperature at which the states of aggregation is
changed from solidifying to melting .If the TVP exceeds
atmospheric pressure, the liquid begins to boil.

Boiling Point
the temperature at which the vapour pressure of a liquid is
equal to atmospheric pressure.

Flammability
When a petroleum is ignited it is the gas progressively given off
by the liquid which burns as a visible flame. The quantity of gas
available to be given off by a petroleum liquid depends on its
volatility which is frequently expressed for purposes of
comparison in terms of Reid Vapour Pressure RVP). A more
informative measure of volatility is the True Vapour Pressure
(TVP) but unfortunately this is not easily measured. It is referred
to in this guide only in connection with venting problems with
very volatile cargoes, such as some crude oils and natural
gasoline.

Auto-ignition temperature
The lowest temperature to which a solid, liquid or gas
requires to be raised to cause self-sustained combustion
without initiation by a spark, flame or other source of
ignition. The auto-ignition temperature of vapors of fuel
and lubricating oils are much lower than those of the
vapors from more volatile petroleum liquids. Fuel and
lubricating oils are thus more liable to ignite if they are
allowed to fall or sprayed on hot surfaces despite the
absence of external flame or spark. Care must also be taken
to avoid rags soaked in fuel or lubricating oil coming into
contact with hot surfaces
Reactivity
The accidental mixing of one chemical product with
another inside a cargo tank or pipe may result in a vigorous
chemical reaction. Binary combinations that generate
significant heat or produce gas can be very hazardous to
personnel and property. In rare cases the reaction of two
components (even though non-hazardous) may produce a
product which is significantly more flammable or toxic
than the original materials. Even the water washing of
cargo tanks and slop tanks containing residues of certain
substances may produce dangerous reactions. Dangerous
reactions are polymerization, oxidation, mutual reactions
between chemicals.
Toxicity
It means a poison in the Greek language (toxikon).Toxicity is the
ability of a substance to cause damage to living tissue, impairment of
the central nervous system, illness or in extreme cases death when
inhaled, ingested or absorbed through the skin.

Corrosivity
Corrosion hazards are dangerous to Personnel and to metal. Some
liquid cargoes are so corrosive that in contact with the skin will
completely or partly destroy living tissue. Less corrosive liquids may
only be irritating to the skin but can result in serious damage to the
eyes. Corrosion is the etching or attack of metals on the surface.
Corrosion can have different causes and it can present itself in many
manifestations. Consequently, both personnel and metals have to be
protected against activity of corrosion.
TOXICITY and OTHER HAZARDS
Toxicity in General
Most of the cargoes on tankers have some hazardous properties.
Poisoning may occur orally, through inhalation or by skin contact.
Poisoning may be acute or chronic. Exposure to oil, chemical or gas
can have acute or chronic effects on a persons health.

ACUTE EFFECT (SHORT TERM) - defined as effect of single exposure
of short duration to relatively high concentration of vapor.
CHRONIC EFFECT (LONG TERM)- defined as accumulative effect of
prolonged exposure to relatively low concentrations of vapor over a
long duration of time.

The vapour from some cargoes may have both acute and chronic effects,
whilst others may have one or the other more prominent

The toxicity of a substance is difficult to measure and that it
is therefore rated on the basis of studies performed on
animals and extrapolated for the human body.

Hazard to human health by oral intake LD
50
(laboratory mammal):
Highly hazardous.. less than 5 mg/kg
Moderately hazardous.. 5 50 mg/kg
Slightly hazardous....... 50 500 mg/kg
Practically non-hazardous... 500 5000 mg/kg
Non-hazardousgreater than 5000 mg/kg
Threshold limit value (TLV)- The time-weighted average concentration of a
substance to which workers may be repeatedly exposed, for a normal 8-
hour workday or 40-hour workweek, day after day, without adverse effect.

The term TLV has been in use within the industry for a number of years and
is often expressed as a Time Weighted Average (TWA). The use of the term
Permissible Exposure Limit is becoming more commonplace and refers to
the maximum exposure to a toxic substance that allowed by an appropriate
regulatory body. The PEL is usually expressed as a TWA, normally averaged
over an eight hour period, or as a Short Term Exposure Limit (STEL),
normally expressed as a maximum airborne concentration averaged over a
15 minute period. The values are expressed as parts per million (ppm) by
volume of gas in air (ISGOTT 16.1).

TLV examples: Acetic acid 10 ppm, Benzene 10 ppm plus skin absorption,
Chlorine 1 ppm, Nicotine 0.07 ppm plus skin absorption, n-Pentane 600
ppm, Toluene 100 ppm plus skin absorption
Odor Threshold- This is specific concentration of
liquids vapour when you can feel the odor of that
liquid with your nose.

For example, PHENOL the odor threshold is 0.05 ppm
but ACRYLONITRILE the odor threshold is several
hundred ppm varying with individuals.

You have all the time to remember that the absence of
smell/odor should never be taken to indicate the absence of
gas. METHANE has no odor, for example
Cargoes also may be harmful to the environment
There are five points under which Marpol Convention was
developed and adopted:
1. Marine pollutants discharged into the sea are rigorously
controlled and are only permitted under the specific condition
depending on the type of ships and their tonnage.
2. There are special areas where all discharge are controlled or
prohibited.
3. Each state is obliged to provide port reception facilities for the
reception and treatment of polluting substances.
4. Each master must have on board a special record book which
must be kept up to date, specifying all cargo loading and unloading
operations.
5. Consequently, the designs of ships, as well as, their equipment
must, in the future, satisfy those very specific requirements
FIRE HAZARDS

Essential Elements to Start a fire:
oxygen
flammable material (fuel)
source of ignition (heat)

Sometimes it is represented as a so called fire triangle, and also as a fire
ring having three sectors which are named as a oxygen. flammable
material and ignition source. When flammable vapour is mixed with
oxygen (usually from the atmosphere) an explosive mixture may be
produced. The ability of petroleum to generate flammable vapour is a
major for starting a fire. The ability to vaporize is volatility

The quantity of gas available to be given off by a petroleum liquid
depends on its volatility which is frequently expressed for purposes
of comparison in terms of Reid Vapour Pressure (RVP): the higher
the RVP the higher volatility. The RVP test is related with a standard
apparatus and in a closely defined way. RVP is useful for comparing
the volatilities of a wide range of petroleum liquids. The volatility
(i.e. the tendency of the liquid or petroleum product to produce
gas) is characterized by the vapour pressure. There is also a
tendency for this gas to re-dissolve in the liquid, and an equilibrium
is ultimately reached with a certain amount of gas evenly
distributed throughout the space. The True Vapour Pressure (TVP)
or bubble point vapour pressure is the equilibrium vapour pressure
of a mixture when the gas/liquid ratio is effectively zero. As the
temperature of a petroleum mixture increases its TVP also
increases and more vapors of liquid is produced.

Volatility increases with temperature and
reaches a maximum at the boiling
temperature of the petroleum
The concentration of hydrocarbon vapour present
in air is used to define flammable range:
Gas: UFL: LFL:
Propane 9.5 2.2
Butane 8.5 1.9
Pentane 7.8 1.5

The flammability diagram When an inert gas is added to a
hydrocarbon gas/air mixture the result is to increase the
lower flammable limit hydrocarbon concentration and to
decrease the upper flammable limit concentration.
The flashpoint of an oil indicates the lowest temperature as
which the oil will give off sufficient hydrocarbon vapour to form
a flammable gas mixture with air near the surface of the oil.
Therefore, we can say that flash point is also the upper
temperature explosive limit only for the many kind of crude oil.
Only the vapour from a flammable material will combine with
oxygen to produce fire. An explosive mixture may be produced
when chemical cargo vapors are mixed with air. An explosion
can be described as a sudden, violent event accompanied with
noise and fire which has a destructive effect on its
surroundings.

Explosion can be distinguished as follows:
physical explosion - a sudden expansion, mostly of
a gas, whereby pressure increase can no longer be
caught by the (closed) drum (steam boiler
explosion, explosion of a cylinder with
compressed nitrogen);
chemical explosion -a rapid, exothermic, chemical
reaction, mostly accompanied with temperature
and pressure increase and the setting free of
gases, whereby energy is supplied by the reaction
Static electricity can arise when two dissimilar materials (solids,
liquids or gases) come in contact and charge separation occurs at
the interface.
When two different materials, suited for the purpose, are brought into
contact with each other in a certain way, an electric charge will develop in
each of the materials. These charges are of the same size, but is positive
and negative: so, the sum of both charges is nil. These electric charges,
which stay behind on the material, are called static electrical charges, and
we are here dealing with the phenomenon of static electricity. This in
contrast with the best-known form of electricity which expresses itself in
electric currents in conductive materials. When these materials are
separated, an electric field develops between the positive material and
the negative material. The accumulated electricity will try to discharge
itself in order to neutralize the electric field. An electric field can also
develop when an electrically charged material approaches a non-charged
material. Discharge often takes place in the form of sparks which,
generally, have sufficient energy to ignite explosive vapour/air mixtures.

Corrosive liquids can become flammable and produce
flammable gases when in contact with certain materials
HYDROGEN GAS (H
2
) is EXPLOSIVE e.g.!

A mixture of vapour and air will only ignite and burn if its composition
is within the flammable range.
Within the flammable/explosive range, if a heat source is introduced,
then it will result in a fire.
Sources of ignition as:
direct heat
mechanical sparks
chemical energy
electrical energy
electrostatic discharge

Static electricity can cause sparks capable of
igniting flammable mixture
List of causes of electrostatic charge generation
as:
flow of liquids through pipes or filters
setting of solids or immiscible liquids through a liquid
ejection of particles or droplets from a nozzle
splashing or agitation of a liquid against a solid surface
vigorous rubbing together and subsequent separation
of certain synthetic polymers

Electrostatic charges:
Person and objects: walking over poorly conductive surface, charged clouds (fog),
touching of charged objects
Particles or droplets
Examples: steam hoses, water hoses, sandstorms, hail
Liquids:
Depending on: electrical conductivity, liquid flow, solid particles (rust, sludge
etc.)
Some tanker operations can give rise to electrostatic charge generation examples of
such tanker operations:
cargo pumping
COW
cargo tank cleaning
cargo tank steaming, etc.
Certain cargoes are accumulators of static electricity because of their low
conductivity
Light distillates: Pure Hydrocarbons, Xylene, Toluene, benzene, heptanes;
Propane
Crude oil Acetone

The three essentials necessary for a fire to commence, may
be represented by the side of a triangle, and the complete
triangle represents a fire or an explosion. The way to
prevent a fire is to prevent the formation of such a triangle.
The removal of any side of the fire triangle will extinguish
the fire. Removal of the flammable material is usually not
possible with petroleum in bulk. It is essential to keep
ignition sources away from cargo area, where flammable
vapors are likely to be present. It is essential to avoid the
entry of flammable vapors into areas where ignition
sources are present, such as living accommodation, engine-
room, galley, etc. The use of inert gas in cargo tanks can
reduce the oxygen content below that necessary to
produce a flammable mixture.
If content of oxygen is reduced flammable range
is reduced, too.
Starving a gas fire by stopping the source of gas
leak may be the most effective way to control a
gas fire. Covering the surface of a flammable
material with a blanket of inert material will
prevent oxygen from making contact with the
vapors from the flammable material. Water in
sufficient quantity can provide cooling. Compared
with oil and other hydrocarbons, some liquid
chemicals have unusual properties with regard to
fire-fighting procedures.

Toxicity of inert gas
The main hazard associated with inert gas is its low oxygen
content, but that it may also contain toxic gases

The main toxic constituents of inert gas:
low oxygen content
carbon monoxide has a TLV TWA of 50 ppm
nitrous gases:
nitrogen monoxide (NO), TLV of 25 ppm (vol.)
nitrogen dioxide (NO
2
), TLV of 5 ppm (vol.).

Lead poisoning is a medical condition caused by increased
levels of the heavy metal lead in the body. Lead interferes
with a variety of body processes and is toxic to many organs
and tissues including the heart, bones, intestines, kidneys,
and reproductive and nervous systems. It interferes with
the development of the nervous system causing potentially
permanent learning and behaviour disorders.
Many petroleum cargo contains lead that are poisonous.
Poisoning may occur:
Orally
Skin contact
Inhalation

Most of the cargoes on tankers have some hazardous
properties.It may pose health , fire and environmental
hazards

HEALTH HAZARDS
1.skin contact with liquid petroleum
2.ingestion (swallowing) of liquid petroleum
3.inhalation (breathing) of liquid petroleum
4. oxygen deficiency
5. toxicity of inert gas
6. presence of lead in petroleum cargo

Skin Contact
Many petroleum products, especially the more
volatile ones, cause skin irritation and remove
essential oils from the skin, leading to dermatitis. They
are also irritating to the eyes. Certain heavier oils can
cause serious skin disorders on repeated and
prolonged contact.
Direct contact with petroleum should always be
avoided by wearing the appropriate protective
equipment, especially impervious gloves and goggles
Ingestion
The risk of swallowing significant quantities of
liquid petroleum during normal tanker and
terminal operations is very slight. Petroleum has
low oral toxicity to man, but when swallowed it
causes acute discomfort and nausea. There is then
a possibility that liquid petroleum may be drawn
into the lungs during vomiting and this can have
serious consequences, especially with higher
volatility products such as gasoline and kerosene.

Inhalation
The main effect of petroleum gas on personnel is to
produce narcosis. The symptoms include headache and
eye irritation, with diminished responsibility and dizziness
similar to drunkenness. At high concentration these lead to
paralysis, insensibility and death.
The vapors from some chemicals are toxic by inhalation
The human body can tolerate concentrations somewhat
greater than the TLV for short periods. The following are
typical effects at higher concentrations

Concentration % LEL Effects
0.1% vol. (1,000 ppm) 10% Irritation of the eyes within
one hour.
0.2% vol. (2,000 ppm) 20% Irritation of the eyes, nose
and throat, dizziness and
Unsteadiness within half an
hour.
0.7% vol. (7,000 ppm) 70% Symptoms as of drunkennes
within 15 minutes.
1.0% vol. (10,000 ppm) 100% Rapid onset of drunkenness
which may lead to
unconsciousness and death if
exposure continues.
2.0% vol. (20,000 ppm) 200% Paralysis and death occur
very rapidly.
Oxygen deficiency
The oxygen content of air is 21% by volume (21.7%)
The reasons of oxygen deficiency in an enclosed space
could be:
an inert atmosphere
displaced oxygen due to presence of cargo vapour
Combustion
chemical reactions
Rusting
drying paint


SYMPTOMS OF OXYGEN DEFICIENCY
At levels below about 19%:
general indisposition
headache
dizziness
sleepiness
noises in the ears
nausea
vomiting

MATERIAL SAFETY DATA SHEET (MSDS) this may have
several names such as Cargo Data Sheet (CDS) or
Product Safety Data Sheet (PSDS).
it is intended to provide workers and emergency
personnel with procedures for handling or working
with that substance in a safe manner, and includes
information such as physical data (melting point,
boiling point, flash point, etc.), toxicity, health effects,
first aid, reactivity, storage, disposal, protective
equipment, and spill-handling procedures. MSDS
formats can vary from source to source within a
country depending on national requirements.

MSDS
Section 1 Materials and Company Identification
Chemical name; CAS Registry number; Date prepared
Identification of Company and its contact details

Section 2 Material composition and information on Ingredients
Composition of mixtures; TLV or max. Exposure concentration of that cargo to the person
and recommended max. exposure limits

Section 3 Hazards Identification
Health effects when in contact by skin/eye, inhaled or ingest; carcinogenetic of materials

Section 4 - First Aid Measures
Treatment for exposure inhalation, ingestion, eye contact and skin contact

Section 5 - Fire Fighting Measures
Fire and explosion data
Provides basic instructions for addressing fire situation
Provides extinguishing medium to be used

MSDS
Section 6 Accidental Release Measures
Procedures for cleaning up and cites specific regulations surrounding chemical
spills

Section 7 Handling and Storage
Provides information regarding safe storage and safe usage of materials

Section 8 Exposure Controls and Personal Protection
Types of protective equipment to be used
Administrative controls and type of shower or eyewash facility to be available

Section 9 Physical and Chemical Characteristics
Includes chemical information as boiling point, etc; physical attributes such as
physical state appearance and odor
MSDS
Section 10 Stability / Reactivity
Indicates stability materials, what causes instability, incompatibilities
and if hazardous decomposition products are possible
Also includes conditions to avoid

Section 11 Toxicological Information
Includes information about reproductive effects and toxic effects

Section 12 Ecological Information
Provides information on the effects of the materials to animals and
plants

Section 13 Disposal Considerations
Appropriate waste disposal methods

MSDS
Section 14 Transport Information
Provides basic shipping requirements, shipping name and
classification, packaging requirements and quantity
limitations

Sections 15 Regulatory information
Cites pertinent EPA And OSHA regulations; rules and
regulations governing the materials

Section 16 Others
Cites references used for construction of the document
May indicate author of document and provide legal disclaimer

ENVIRONMENTAL HAZARDS
Pollution is inconvenience or damage, caused by human
activities, animals, plants and to our environment as a whole,
by spreading of hydrocarbons and chemical compounds to air,
water or lend

Crude oil tankers, product tankers and chemical tankers
are chiefly responsible for marine pollution
about 700,000 tons a year
dry docking (30,000 tons)
non- tanker accidents (20,000 tons)
Cargoes in tankers may be harmful to the
environment in different ways:
blanket the surface interfering with the oxygen
exchange between the sea and the atmosphere as
result
blanket the seafloor interfering with growth of
marine life as result
toxic into the sea food
deposition on tidal mud flats.

Most chemicals carried represent a pollution risk:
bioaccumulation
damage to living resources
human health harm
reduction of amenities
Hazards caused to the environment, covering the effect on
human and marine life from the release of oil, chemicals or
gases
bioaccumulation of substances are liable to produce tainting of
seafood
Bioaccumulation to significant extent substances can produce a hazard
to aquatic life or human health
damage to living resources
hazard to human health by skin and eye contact or inhalation
Effect that the specific gravity and solubility of the cargo
have on the hazards to the environment in the event of a
spillage
more heavier than sea water substances sinks
more lighter than sea water substances floats
non soluble floating substances spread on a huge area
producing a vapour cloud
if a fully refrigerated liquid is spilled the rapid evolution of
vapour occurs
spillage of a liquid gas from a pressure vessel:
the high pressure at release quickly falls to ambient, and this
results in extremely rapid vaporization. This is called flash
evaporation.

The effect of the cargo vapour pressure and
atmospheric conditions on the hazards to the
environment:
TVP of different liquid cargoes depends on the ambient
temperature: temperature increased TVP also
increases
If TVP exceeds atmospheric pressure, the liquid
commence to boil, producing vapour in air mixtures
(vapour cloud)
VAPOUR + AIR FLAMMABLE

REACTIVITY HAZARDS
Chemical cargo may react in a number of
ways, such as:
with itself (self reaction)
with air
with water
with another cargo
with other materials

REACTIVITY HAZARDS
Polymerization, is self reaction. Polymerization is
a chemical reaction whereby two or more
molecules of the same substance monomer
combine with one another, so that a new
compound polymer develops of the same gross
composition as the original monomer, however,
with a double or multiple molecular weight.
Example: n(CH
2
CH
2
) (CH
2
CH
2
)n
Ethylene Polyethylene

REACTIVITY HAZARDS
Polymerization
is the formation of larger molecules as a result of
self-reaction
Polymerization takes place when a single molecule
(a monomer) reacts with another molecule of the
same substance to form a dimer.
This process can continue until a large-chain
molecule is formed, possibly having many
thousands of individual molecules (a monomer).

REACTIVITY HAZARDS
POLYMERIZATION
The process may be catalyzed by the presence of
oxygen (or other impurities) or by heat transfer
during cargo operations.
During the transport the polymerization reactions
have to be prevented to avoid problems such as
heat generation, formation of a layer of solid
polymer on the inner side of the roof of the cargo
tank, formation of solid particles which block the
pumps, etc.

REACTIVITY HAZARDS
POLYMERZATION
may be catastrophic to the ship, and when
transporting such liquids it is important to monitor
the temperature of the cargo at certain intervals.
A rise in temperature may indicate that a reaction
is in progress, and some measures should be taken
to bring the situation under control.
Such liquids will normally be added an inhibitor
and may require Inerting, and the shipper should
give a clear loading instruction and voyage
instruction in relation to control of inhibitor.
REACTIVITY HAZARDS
INHIBITOR

one that inhibits:
an agent that slows or interferes with a chemical
action
a substance that reduces or suppresses the
activity of another substance (as an enzyme)

REACTIVITY HAZARDS
Inhibitors
slow the rate of reaction. Sometimes they even
stop the reaction completely. You could use an
inhibitor to make the reaction slower and
more controllable. Without them, some
reactions could keep going and going and
going. If they did, all of the molecules would be
used up.

REACTIVITY HAZARDS
REACTIVITY HAZARDS
REACTIVITY HAZARDS
The combination of an element
with oxygen is called an oxide,
and the phenomena which is
produced by this oxidized
compound is an oxidation
reaction.

REACTIVITY HAZARDS

Auto-oxidation
is a chemical reaction whereby the
substance itself produces the oxygen for
oxidation. But auto-oxidation reactions are
started by oxygen from the air.

REACTIVITY HAZARDS

Some substances can combine with water or
can be decomposed by water, as a result of
which either a hazardous situation arises or
the quality of the product strongly changes, or
products develop which cause a corrosion of
materials. In this case, contamination with
water must be prevented.

REACTIVITY HAZARDS

To avoid dangerous chemical reaction between
different kinds of cargoes there is the cargo
compatibility chart.

HAZARDS ON GAS CARRIER
Low temperature ( frost bite)
liquefied gas cargoes are transported at or
close to their boiling point
the boiling temperatures of these cargoes
range from 162
o
C for methane to 0
o
C for
butane
these low temperatures can cause brittle
fracture if cold cargo comes in sudden contact
with metals

Asphyxia
Oxygen deficiency in an enclosed space can occur with
any of the following conditions:
When large quantities of cargo vapour are present
When large quantities of inert gas or nitrogen are present, and
Where rusting of internal tank surfaces has taken place.

For the above reasons, it is essential to prohibit entry
to any space until an oxygen content of 21 per cent is
established.

Flammability
an explosive mixture may be produced when most
cargo vapors are mixed with air
All liquefied gases transported in bulk by sea, with
the exception of chlorine, are flammable.
The vapors of other liquefied gases are easily
ignited. The exception to this is ammonia which
requires much higher ignition energy than the
other flammable vapors.

Toxicity
is the ability of a substance to cause damage to living tissue,
including impairment of the nervous system. Illness or, in extreme
cases, death may occur when a dangerous gas or liquid is
breathed, taken orally or absorbed through the skin.

the vapors from some liquefied gas cargoes are
toxic by inhalation
some toxic gases carried in gas tankers can be
absorbed into the body through the skin

Chemical Burns
some gases are caustic and can damage human tissue
(the skin, lungs, throat and eyes.) The effect is more
known as chemical burns (corrosive/irritant).
can be caused by ammonia, chlorine, ethylene oxide
and propylene oxide.
The symptoms are similar to burns by fire, except that
the product may be absorbed through the skin causing
toxic side-effects.
Chemical burning is particularly damaging to the eyes.

Symptoms of a Chemical Burn
A burning pain with redness of the skin
An irritating rash
Blistering or loss of skin
Toxic poisoning

Otherwise, the treatment is as for burns, details of which
are contained in the IMO Medical First Aid Guide.
On some gas carriers deck showers and eye baths are
provided for water dousing; their locations should be
known.

HAZARD CONTROL
Information of cargo to be handled should be
available and essential
ICS, Tanker Safety Guide
MSDS
IMDG Code, IBC Code & BCH Code
ICS, Safety in Oil Tankers
ICS, Safety in Chemical Tankers
SIGTTO, Liquefied Gas Handling Principles on Ships and
in Terminals
ISGOTT
MARPOL

HAZARD CONTROL
ICS
International Chamber of Shipping
IBC Code
International Code for the Construction and Equipment of Ships
Carrying Dangerous Chemicals in Bulk (chemical tanker built on or after 1
July 1986)
BCH Code
IMO Code for the Construction and Equipment of Ships Carrying
Dangerous Chemicals in Bulk (chemical tanker before 1 July 1986)
ISGOTT
International Safety Guide for Oil Tankers & Terminals
SIGTTO
Society of International Gas Tanker and Terminal Operators
HAZARD CONTROL
IGC Code
International Code for the Construction and
Equipment of Ships Carrying Liquefied Gases in Bulk
applies to gas carriers constructed on or after1 July
1986.
Gas carriers constructed before that date should
comply with the requirements of the Code for the
Construction and Equipment of Ships Carrying
Liquefied Gases in Bulk or the Code for Existing Ships
Carrying Liquefied Gases in Bulk.
HAZARD CONTROL
All cargoes can be handled safely by showing
the greatest care throughout operation and by
following standing instructions at all times
Chief Officers Standing Order
Company Operations Manual
MSDS
IMO Publications

HAZARD CONTROL
Precautions to avoid health hazards
strict control of entry into pump-room, cargo
spaces and other enclosed spaces
proper procedures to be followed before entry
into enclosed spaces
use of adequate protective clothing
thorough cleansing of personal clothing after
contact with cargo

HAZARD CONTROL
Permit to work should be issued and should
be specific as to date, time, space and nature
of work to be done
Continuous monitoring of the atmosphere in
working spaces for toxic gases
Continuous ventilation to prevent accumulation of
flammable and/or toxic vapor

HAZARD CONTROL
Gas Measuring Equipment

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DEVELOPMENT OF TANKERS

Carriage of oil in barrels in conventional cargo ships

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