GAS TANKER MANUAL

DOCUMENT NO.: NYKSM/GAS/01

CHAPTER 3: PROPERTIES OF LIQUEFIED GASES
VERSION 1.00, DATED 01/01/06
Page 1

3. INTRODUCTION TO GAS TANKERS

3.1 PHYSICAL PROPERTIES

The physical properties of a liquefied gas depend on its molecular structure. Some
compounds have the same molecular formula but a different arrangement within the
structure. These different compounds of the same basic substance are called ISOMERS
for example N-BUTANE & ISO-BUTANE.

The single most important physical property of a liquefied gas is its saturated vapor pressure/
temperature relationship. This property governs the design of the containment system
suitable for each cargo.

Liquefied Gases:
A gas is a collection of molecules moving freely in space. In a closed container the speed
at which the molecules move depends upon the energy available or the temperature of the
gas. If the gas is cooled down (chilled), the speed at which the molecules move will decrease
and, eventually, they will combine to form a liquid.

A liquefied gas is the liquid form of a substance which, at ambient temperature and at
atmospheric pressure, would be a gas.

The IMO for the purposes of its Gas Carrier Codes relates saturated vapour pressure to
temperature and has adopted the following definition for the gases carried by sea:

Liquids with a vapour pressure exceeding 2.8 bar absolute at a temperature of 37.8°C
In other word a liquefied gas is to give the temperature at which the saturated vapour
pressure is equal to atmospheric pressure i.e. the liquid’s atmospheric boiling point.

Physical Properties of some liquefied gases:

LIQUEFIED GAS Vapour Pressure at 37.8°C Boiling point at atmospheric

(bars absolute) pressure(°C)
Methane Gas -161.5
Propane 12.9 -42.3
n-Butane 3.6 -0.5
Ammonia 14.7 -33.40
Vinyl Chloride 5.7 -13.80
Butadiene 4 -5.00
Ethylene Oxide 2.7 10.70

On the bases of the above IMO definition, ethylene oxide would not qualify as a liquefied
gas.
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CHAPTER 3: PROPERTIES OF LIQUEFIED GASES
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CHAPTER 3: PROPERTIES OF LIQUEFIED GASES
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LPG Production:
Liquefied Petroleum Gas (LPG) is largely given name for propane, butane or mixture of
the two. These products are extracted from natural gas or crude oil streams during the
initial processing, and it is obtained during the refining of crude oil.

The vapour of both propane & butane are heavier than air. Propane vapour forms 270
times that of liquid & butane 230 times or in other words a single drop of propane liquid will
occupy 270 times space when in vapour form & butane will occupy 230 times.

Chemical & Physical properties of Liquefied gases:

Hydrocarbons are substances whose molecules only contain only hydrogen & carbon
atoms. The molecule can be in various arrangements and products may be gases, liquid
or solids at ambient temperature and pressures, depending upon the number of the carbon
atoms in the molecular structure. Generally, those hydrocarbons with up to four carbon
atoms are gaseous state at ambient conditions and comprise the hydrocarbon liquefied
gases. Hydrocarbons with five up to twenty carbon atoms are liquid at ambient conditions
and those more carbon atoms are solid.

As per the bonding of carbon atoms they form saturated hydrocarbons (CnH2n+2) like,
methane (CH4), propane (C3H8) & butane (C4H10), and unsaturated hydrocarbons like
ethylene (C2H4), propylene (C3H6) & butadiene (C4H6)

Molecular structure of saturated hydrocarbon (single bonds):

Molecular structure of unsaturated hydrocarbon (double bonds):

 GAS TANKER MANUAL
DOCUMENT NO.: NYKSM/GAS/01
CHAPTER 3: PROPERTIES OF LIQUEFIED GASES
VERSION 1.00, DATED 01/01/06
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Molecular weight of propane is about 44 and that of butane is about 58, which means that
they are heavier than air. Molecular weight of air is calculated to be about 29, therefore
propane is about 1.5 times and butane is 2 times as heavy as air. These gases if leaked
into atmosphere will accumulate in low places. Therefore, extensive detection of gas in
low places when leakage is found is necessary.

Gas leaking from the upper deck may flow into the engine room compartment by way of
accommodation openings when there is no wind. Therefore closing of entrances and
portholes on upper deck during cargo operations is required.

Propane and butane in liquid phase are both about 0.6 in specific gravity, which is half as
heavy as water.

Therefore, if water is contained in the cargo, it will settle down to the tank bottom and can
cause danger to cargo pump.
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DOCUMENT NO.: NYKSM/GAS/01
CHAPTER 3: PROPERTIES OF LIQUEFIED GASES
VERSION 1.00, DATED 01/01/06
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Flammability:
A correct proportion of mixture of air & hydrocarbon is required ignite a hydrocarbon gas.
When the concentration of a hydrocarbon gas in air below which there is insufficient
hydrocarbon to support combustion is called as Lower Flammability Limit (LFL) and when
the concentration of a hydrocarbon gas in air above which there is insufficient air to support
combustion, is called as Upper Flammability Limit (UFL).

Flammable Range (or Explosive Limit):

Explosive limit is the limit of concentration of gas in air by which explosion occurs if ignited.
There are upper Explosive limit (upper flammable limit) and Lower Explosive limit (Lower
Flammable Limit), that means no explosion n occurs if there is too rich gas or too lean gas
in air.

Their LEL being about 2% means that there is only 2% of gas in air, explosion can occur.
As their specific gravity is greater than air, explosive mixture will be accumulate at lower
places on deck.

Explosive limit with Air (%)

Lower Limit Upper Limit
Propane 2.37 9.50
n-Butane 1.86 8.41
Explosive limit /or range changes as the contents of the gas mixture changes.

Other Properties:
Propane, butane & LPG are colourless and odourless gases. These are transported at
both their liquid & gas phases, however, if the gas is seen in air, different coefficient of
refraction makes it to like haze, even though these are colourless gases.

Therefore if gas is emitting from vent riser it can be clearly observed from the wheelhouse
with the help of binoculars, enabling the ship personnel to detect gas emission. Pure
propane & butane are odourless, however commercial products are stenched enabling
detection in case of leak.

Propane & butane are not very toxic, but they are harmful if inhaled. These gases normally
do not react with water but forms a greasy type solid called hydrate.
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CHAPTER 3: PROPERTIES OF LIQUEFIED GASES
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3.2 CHEMICAL PROPERTIES

Chemical compounds with the same chemical structure are often known by different names.
The alternative names given to the same compound is called a synonym. The table below
gives a list of the synonyms of the liquefied gases against each common name and its
simple formula. The more complex compounds tend to have a larger number of synonyms
than the simple compounds.

Synonyms of liquefied gases

Common Name Simple Formula Synonyms
Methane CH4 Fire damp; marsh gas; natural gas; LNG
Ethane C2H5 Bimethyl; dimethyl; Methyl Methane
Propane C3H8
n-Butane C4H10 Normal Butane
i- Butane C4H10 Iso-Butane; 2-Methlypropane
Ethylene C2H4 Ethene
Propylene C3H6 Propene
Common Name Simple Formula Synonyms
a-Butylene C4H8 But-1-ene; Ethyl ethylene
b- butylene C4H8 But-2-ene; dimethyl ethylene; Pseudo butylenes
y-butylene C4H8 Isobutene; 2-Methylprop-2 -ene
Butadiene C4H6 b.d.; bivinyl; 1,3 butadiene; butadiene 1-3; bivinyl; biethylene;
erythrene; vinyl ethylene.

Isoprene C5H8 3-methyl - 1,3 butadiene;

2-methyl - 1,3 butadiene;
2-methylbutadiene - 1,3

Vinyl Chloride CH2CHC1 Chloroethene, Chloroethylene; VCM

Monomer
Ethylene oxide C2H4O Dimethylene oxide; EO; 1,2 epoxyethane; Oxirane
Propylene oxide C3H6O 1,2 epoxy propane; methyl oxirane; Propene oxide
Ammonia NH3 Anhydrous ammonia; ammonia gas; liquefied ammonia;
liquid ammonia

Note: Commercial propane contains some butane; similarly commercial butane contains some propane.
Both may contain impurities such as ethane and pentane, depending on their permitted commercial
specification.
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Saturated hydrocarbons
The saturated hydrocarbons methane, ethane, propane and butane are all colorless and
odorless liquids under normal conditions of carriage.
They are all flammable gases and will burn in air and/or oxygen to produce carbon dioxide
and water vapor. As they are chemically non-reactive they do not present chemical
compatibility problems with materials commonly used in handling. In the presence of
moisture however, the saturated hydrocarbons may form hydrates.
Sulphur compounds such as mercaptans are often added as odourizer prior to sale to aid
the detection of these vapors. This process is referred to as stenching”. Mercaptans are
considered to be hazardous in some forms and must be handled with care when on board
the vessel.

Unsaturated hydrocarbons
The unsaturated hydrocarbons ethylene, propylene, butylene, butadiene and isoprene
are colorless liquids with a faint, sweetish characteristic odor. They are, like the saturated
hydrocarbons, all flammable in air and/or oxygen, producing carbon dioxide and water
vapor. They are chemically more reactive than the saturated hydrocarbons and may react
dangerously with chlorine. Ethylene, propylene and butylene do not present chemical
compatibility problems with materials of constructions, whereas butadiene and isoprene,
each having two pairs of double bonds, are by far the most chemically reactive within this
family group. They may react with air to form peroxides which are unstable and tend to
induce polymerization. Butadiene is incompatible in the chemical sense with copper, silver,
mercury, magnesium, aluminium and monel. Butadiene streams often contain traces of
acetylene which can react to form explosive acetylides with brass and copper.
Water is soluble in butadiene, particularly at elevated temperatures. The figures quoted
are for the purpose of illustration only. On cooling water-saturated butadiene the solubility
of the water decreases and water will separate out as droplets which will settle as a layer
on the bottom of the tank, for instance, on cooling water-saturated butadiene from +15°C
to + 5°C approximately 100 ppm of free water would separate out. On this basis, for a
1,000m tank, 100cc of free water would require to be drained from the bottom of the tank.
On further cooling to below 0°C this layer of water would increase in depth and freeze.
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Chemical gases
The chemical gases commonly transported in liquefied gas carriers are ammonia, vinyl
chloride monomer, ethylene oxide, propylene oxide and chlorine. Since these gases do
not belong to one particular family their chemical properties vary.
Liquid ammonia is a colorless alkaline liquid with a pungent odor. The vapors of ammonia
are flammable and burn with a yellow flame forming water vapor and nitrogen, however,
the vapor in air requires a high concentration (16-25 per cent) to be flammable, has a high
ignition energy requirement (600 times that for propane) and burns with low combustion
energy. For these reasons the IMO Codes, while requiring full attention to the avoidance
of ignition source, do not require flammable gas detection in the hold or inter-barrier spaces
of carrying ships. Nevertheless, ammonia must always be regarded as a flammable cargo.

Ammonia is also toxic and highly reactive. It can form explosive compounds with mercury,
chlorine, iodine, bromine, calcium, silver oxide and silver hypochlorite. Ammonia vapor is
extremely soluble in water and will be absorbed rapidly and exothermically to produce a
strongly alkaline solution of ammonium hydroxide. One volume of water will absorb
approximately 200 volumes of ammonia vapor. For this reason it is extremely undesirable
to introduce water into a tank containing ammonia vapor as this can result in vacuum
condition rapidly developing within the tank.

Since ammonia is alkaline, ammonia vapor/air mixtures may cause stress corrosion.
Because of its highly reactive nature copper alloys, aluminium alloys, galvanized surfaces,
phenolic resins, polyvinyl chloride, polyesters and viton rubbers are unsuitable for ammonia
service. Mild steel, stainless steel, neoprene rubber and polythene are, however, suitable.

Vinyl chloride monomer (VCM) is a colorless liquid with a characteristic sweet odor. It is
highly reactive, though not with water, and may polymerize in the presence of oxygen,
heat and light. Its vapors are both toxic and flammable. Aluminium alloys, copper, silver,
mercury and magnesium are unsuitable for vinyl chloride service. Steels are, however,
chemically compatible.

Toxide and propylene oxide are colorless liquids with an ether-like odor. They are flammable,
toxic and highly reactive. Both polymerize, ethylene oxide more readily than propylene
oxide, particularly in the presence of air or impurities. Both gases may react dangerously
with ammonia.

Cast iron, mercury, aluminium alloys, copper and alloys of copper, silver and its alloys,
magnesium and some stainless steels are unsuitable for the handling of ethylene oxide.
Mild steel and certain other stainless steels are suitable as materials of construction for
both ethylene and propylene oxides.
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NITROGEN PADDING IS REQUIRED

Chlorine is a yellow liquid which evolves a green vapor. It has a pungent and irritating
odor. It is highly toxic but is non-flammable though it should be noted that chlorine can
support combustion of other flammable materials in much the same way as oxygen. It is
soluble in water forming a highly corrosive acid solution and can form dangerous reactions
with all the other liquefied gases. In the moist condition, because of its corrosivity, it is
difficult to contain. Dry chlorine is compatible with mild steel, stainless steel, monel and
copper. Chlorine is very soluble in caustic soda solution which can be used to absorb
chlorine vapor.

3.3 PRINCIPLES OF REFRIGERATION

See Appendix I for the basic components in a simple refrigerator.

Cold liquid refrigerant (liquid gas cargo) is evaporated in an evaporator coil (cargo tank)
which being cooler than its surroundings draws heat to provide the latent heat of
vaporization. The cool vapor is drawn off by a compressor which raises both the pressure
and the temperature of the vapor and passes it to the condenser.

The pressure of the vapor having been increased the vapor now has a temperature of
condensation greater than the temperature of the condenser cooling fluid (sea water).

The vapor is condensed to a high pressure liquid and the sensible heat of de-superheating
the vapor together with the latent heat of condensation is removed via the condenser
coolant which is warmed up in the process.

The high pressure liquid then passes through an expansion valve to the low pressure side
of the cycle, in doing so flash evaporates to a mixture of cold liquid and vapor. The mixture
passes to the evaporator (cargo tank) to continue the cycle.

3.4 CRITICAL TEMPERATURES & PRESSURES

The critical pressure of a gas is the pressure required to compress a gas to its liquid state
at its critical temperature.

Critical temperatures and pressures are listed in the table of Physical Properties. For the
carriage or storage of ethane or ethylene as a liquid some additional refrigeration is required
often in the form of a cascade system.
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CHAPTER 3: PROPERTIES OF LIQUEFIED GASES
VERSION 1.00, DATED 01/01/06
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3.5 BASIC THERMODYNAMIC THEORY

Cargo and Deck Officers must be familiar with Basic Thermodynamic Theory. Section
13.4 and A3.5 of the Tanker Safety Guide - Liquefied Gas, dealing with the most important
points and these sections are to be read in conjunction with this manual.

3.6 CARGO INFORMATION

The IMO Codes require that the following information is available to every ship and for
each cargo:
• A full description of the physical and chemical properties necessary for the safe
containment of the cargo;
• Action to be taken in the event of spills or leaks;
• Counter-measures against accidental personal contact;
• Fire-fighting procedures and fire-extinguishing agents;
• Procedures for cargo transfer, gas-freeing, ballasting, tank cleaning and changing
cargoes;
• Special equipment needed for the safe handling of the particular cargo;
• Minimum inner hull steel temperatures;
• Emergency procedures;
• Compatibility;
• Details of the maximum filling limits allowed for each cargo that may be carried at each
loading
Temperature, the maximum reference temperature, and the set pressure of each relief
valve.
This above information is usually obtained from the cargo material safety data sheets
(MSDS). Refer to the appendix for the ‘Cargo data sheets’ for Propane and Butane.
The Master is to request the correct technical name of the cargo to be loaded as soon as
possible before loading. If the cargo is not adequately covered by a data sheet, he is to
obtain sufficient additional information necessary for its safe carriage.
The Master and all those concerned are to use the data sheet and any other relevant
information to acquaint themselves with the characteristics of each cargo to be loaded. If
the cargo to be loaded is a mixture (e.g. LPG), information on the composition of the
mixture is to be sought; the temperature and pressure readings in the shore tank can be
used to verify this information.
If the information necessary for safe carriage is not available, loading is to be refused;
loading must also be refused if a cargo has to be inhibited but no certificate is available.
Special note is to be made of any contaminants that may be present in the cargo, e.g.
water.