CHAPTER 2

LNG Properties and Composition

Methane (CH4)
85% -99%
Nitrogen (N2)

Ethane (C2H4)
Butanes (C4H10)
Propane (C3H8)

2.1 LNG Composition

The composition of natural gas varies depending on the gas source

and type of processing. Pipeline quality of natural gas typically
contains 85% to 99% methane (CH4). It also contain ethane (C2H6),
propane (C3H8), some butanes (C4H10), and trace amounts of heavier
hydrocarbons. Nitrogen (N2) is often present, as well.

The process can also be designed to purify the LNG to almost 100%
m e t h a n e . C o m p o s i t i o n o f e a c h h y d r o c a r b o n c o n ta i n e d i n L N G d i c t a t e s
the actual density or specific gravity of LNG. The more the heavier
hydrocarbons are present, the higher the density of the LNG becomes
and the greater its calorific value.

Typical Composition

Methane 85% to 98%

Ethane 5% to 0.1%

Propane 3% to 0%

Butane+ 1% to 0%

Nitrogen 3% to .5%

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2.2 Cryogenic characteristics
L N G i s a c r y o g e n i c l i q u i d . C r y o g e n i c l i q u i d s a r e g e n e r a l l y c o n si d e r e d
those at temperature –75OC. At atmospheric pressure, LNG boils at
approximately –161OC. Other common cryogenic liquids are hydrogen,
oxygen, helium, and nitrogen. Table 1 shows the relative boiling point
of some cryogenic liquids. LNG is one of the “warmer cryogen”.

One of the most interesting phenomenon about the materials used in

cryogenic designs, is that they get stronger with the colder
t e m p e r a t u r e s . S t a i n l e s s s t e e l , a l u m i n u m , b r a s s , a n d te f l o n a l l h a v e
h i g h e r t e n s i l e a n d y i e l d s t r e n g t h s a t c r y o g e n i c te m p e r a t u r e s t h a n t h e y
do at room temperatures.

Liquid Boiling point (OC)

1. Ethane -88
2. Ethylene -104
3. LNG -161
4. Oxygen -183
5. Argon -186
6. Nitrogen -196
7. Hydrogen -253
8. Helium -269

Table 2.1 Cryogenic liquids and their respective boiling

temperature

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2.3 Odor Characteristics
LNG has no odor. The odorants added to natural gas to give its
characteristic odor are removed before liquefaction because they
s o l i d i f y a t L N G t e m p e r a t u r e s a n d d i s r u p t t h e l i q u e f a c ti o n p r o c e s s .
Consequently, odor can not be used to detect a LNG leak unless
special efforts have been made to odorize the LNG. The odorants
added to give odor to LNG is “mercaptan”.

Although some methods for odorizing LNG have been studied,

odorants are not usually added to LNG for the following reasons:

 Detection is typically accomplished with combustible gas detectors.

 O n l y l i m i t e d t e s t i n g h a s b e e n c o n d u c t e d t o d e t e r m i n e t h e c o n d i ti o n s
under which LNG odorants are detectable.

 Techniques for adding LNG odorants need improvement.

 Odorants detectable at very low level may cause undue concern.

 Odorants residue deposited on or around an LNG system will result

in odor always being present and, as such, greatly diminishing its
effectiveness.

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 Wind direction
Too lean

Flammable Over-rich
Over-rich

LNG Spill

Fi gure 2.1 Flammabl e vapor zone – a l iquefi ed gas spil l

2.4 Flammability Limits

Burning a fuel requires an ignition source and proper concentrations of
fuel and oxygen. Flammability limits expresses the amount of a fuel
that must be present in air for the fuel to burn (assuming air contains
21% oxygen). The lower and upper flammability limits for methane in
air are 5% and 15% by volume, respectively. In a closed tank, the
percentage of methane is nearly 100%, thus, cannot ignite.

Methane leaking from a tank in a well ventilated area is likely to

r a p i d l y d i s s i p a t e t o l e s s t h a n 5 % . B e c a u s e o f t h i s r a p i d d i s s i pa t i o n ,
only a small area near the leak would have the proper concentration
for ignition. In a closed, poorly ventilated room, the chance of
collecting enough fuel in the air for ignition increases significantly.

The heavier hydrocarbons have lower flammability limits than

methane, causing the lower flammability limit of LNG to decrease with
increased concentrations of heavier hydrocarbons.

Should liquefied gas be spilled in an open space, the liquid will rapidly
evaporate to produce a vapor cloud which will gradually disperse
downwind. The vapor cloud or plume is flammable only over part of its
area. The situation is illustrated in figure 2.1

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2.5 Auto-ignition Temperature and Ignition Energy
The auto-ignition temperature of a substance is the temperature to
which its vapor must be heated to ignite sponteneously. This
temperature depends on factors such as the air-fuel mixture and
pressure. The average auto-ignition temperature for pure methane at
atmospheric pressure is 595OC.

The auto-ignition temperature of LNG varies with composition: as the

concentration of heavier hydrocarbons in LNG is increased, the auto-
ignition temperature is lowered.

In addition to ignition from heat, natural gas can also be ignited from
the energy in a spark. Practically speaking, most sparks have enough
e n e r g y t o i g n i t e a f l a m m a b l e m i x tu r e o f m e t h a n e i n a i r . B e c a u s e s t a t i c
from clothing may have sufficient energy to ignite natural gas, some
people recommend that workers do not wear synthetic clothing (e.g.
n y l o n ) , w h i c h i s m o r e l i k e l y t o g e n e r a t e s t a t i c s p a r k s th a n n a t u r a l
fibers.

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2.6 Flash Point
The flash point of a liquid is the lowest temperature at which that
liquid will evolve sufficient vapor to form a flammable mixture with air.
High pressure liquids such as liquefied gases have extremely low flash
points as seen form Table 2.2. However, although liquefied gases are
never carried at a temperatures below their flash point, the vapor
spaces above such cargoes are non-flammable since they are filled
entirely with vapor cargo and are thus safely above the upper
flammability limit.

Liquefied Gas Flash Point Flammability Auto-ignition

Range temperature
(OC)
(% by vol. In (OC)
air)

Methane -175 5% - 15% 595

Ethane -125 3% - 12.5% 510

Propane -105 2.1% - 9.5% 468

Butane -60 1.5% - 9% 365

Ethylene -150 3% - 34% 453

Propylene -108 2% - 11% 453

T able 2.2 I g ni tion pr opert i es for li quef i ed gases

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2.7 Heat of Vaporization
Latent heat of vaporization is the heat required by a substance when
c h a n g i n g f r o m a l i q u i d to a g a s . T h e c o o l i n g e f f e c t o f w a t e r
evaporating off skin is an example of this. In liquids, molecules have
much greater attractive forces holding them together than in gases. To
form to a gas, the attractive forces of the liquid are overcome by
absorbed heat. This absorbed heat or heat of vaporization, is 220
B t u / l b . ( 1 2 2 k c a l / k g ) f o r m e t h a n e a t s e a l e v e l , a tm o s p h e r i c p r e s s u r e .

The heat of vaporization contributes to cold burns because, in addition

to the initial low temperature of the liquid, the vaporizing LNG absorbs
heat from its surroundings. Thus, the potential for burns is greater for
cryogenic liquid than for an equivalent temperature in vapor phase.

2.8 Boiling Point

At sea level atmospheric pressure, methane boils at –160OC. An
increase in storage pressure raises the boiling point. In pressurized
LNG storage vessels (at approximately 2.4 barg), methane boils at
about minus -149OC. .

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2.9 Density and Specific Gravity
Density is the mass of a substance per unit volume and is commonly
m e a s u r e d i n k i l o g r a m s p e r c u b i c c e n t i m e t e r ( k g / c m 3 ) . S p e c i f i c g r a v i ty
is the density of a substance compared to the density of a standard
substance, usually water or air, depending on whether the comparison
is with a liquid or a gas. A gas with a specific gravity greater than 1.0
is heavier than air. Conversely, a gas with a specific gravity less than
1.0 is lighter than air and will easily disperse in well-vented areas.
The density of methane at atmospheric pressure and temperature of
16OC is about 0.67 kg/Nm3 (0.424gr/cm3 ) or a specific gravity of 0.55.
Overall, the density of natural gas is nearly the same as methane; thus
natural gas dissipates easily through the air. Vapors from gasoline and
diesel fuels have specific gravity greater than air and therefore do not
dissipate as rapidly as natural gas.

The density of methane (and natural gas) increases as temperatures

decreases. This behavior affects the dispersion of a cold vapor cloud.
At temperature below –107OC the density of methane is greater than
that of air at the assumed ambient temperature of 16OC. Thus, cold
LNG vapor is likely to accumulate in low areas until warms. A cloud of
LNG vapor and air will likely remain in contact with the ground even
after it has warmed substantially because it is mixed with cold, heavy
air.

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 F i g u r e 2.2 LN G W e at he r i n g

2.10 LNG Weathering

LNG may weather (become enriched with heavier hydrocarbons) as
LNG in storage boils-off due to the heat leak into the storage tank.
The boil-off is virtually only methane and nitrogen, leaving behind the
heavier hydrocarbons.

I n a d d i t i o n t o t h e a m o u n t o f L N G r e m o v e d , o t h e r f a c t o r s th a t a f f e c t t h e
significance of weathering include the percentage of heavier
hydrocarbons in the initial LNG.

Significant weathering is more likely occurred in tanks stored with little

cargo (e.g. less than a quarter of a tank). It may take a full tank many
weeks, or longer to undergo any significant weathering.

T h e e f f e c t o f w e a t h e r i n g i s m o r e p r o n o u n c e d d u r i n g b a l l a s t v o y ag e .
This is because the volume of liquid is much less, therefore
weathering is accelerated. One result of weathering is that spraying is
less effective for cargo tank cool down.

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 Figure 2.3 Stratificati on

2.11 Stratification
During normal operation Boil-off gas (BOG) is consumed by the boilers
and tank pressure is maintained. However when a cargo tank is sealed
the pressure will rise 5-10 KPa within 30 minutes. This is due to
Stratification.

Heat enters the tank through the tank walls and warms the LNG. The
warmer liquid rises along the tank walls to the top. At the top of the
rising liquid changes direction to horizontal. As the current moves
along the surface the LNG cools and sinks.

At the top of the tank evaporation causes a thin chilled layer of LNG.
The current passes its heat to this thin layer as it travels along the
surface. This causes evaporation and maintains the layer. This layer
acts as a buffer between the warmer current and the vapor above the
saturation vapor temperature is maintained.

However, when the tank is sealed, evaporation is suppressed. The

layer is destroyed and the warm current is exposed. The result is the
sudden rise in pressure. Figure 2.3

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 Fi gure 2.4 Roll -Over

2.12 Roll Over

Roll over is caused when two types of LNG with different specific
gravity are stored in the same tank. The liquids will form two layers in
the tank with the lighter liquid on top of the heavier. If heat enters the
tank it causes weathering on the top layer. That is the lighter
components evaporate away and the specific gravity increases.
However, the components do not evaporate from the lower level. If
these process is allowed to continue the two layers will reach the
same specific gravity. At this point the two layers will suddenly mix.
This is called Roll-Over.

Evaporation which has so far been suppressed in the lower layer will
be allowed and great quantities of BOG are created. The created BOG
may exceed the capacity of the relief valve causing back pressure
which may damage or destroy the tank.

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F i g ur e 2 .5 Ch a r a c t e ri s t i c s of M e t h a ne

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Fi gure 2.6 Char acteri stics of Methan e

Vapor press ur e D iagram

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Figur e 2 .7 L imit s of Fl amma bi lit y for Mixture o f Met h ane and
N 2 G as and NG

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Figur e 2 .8 Li mit s of Flammabil it y f o r Mi xtur e of Me thane/ Air
and N 2

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 Gas Density (kg/m3)

Fi gure 2.9 R ela ti on Bet w een T empera ture and Spe cif i c
G rav it y of CO 2 , O 2 , A ir, C H 4 , I n ert Gas, and NG

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Figur e 2 .1 0 Rel at ion Be tw ee n Tem perat ure a nd Speci f ic
G rav it y of CO 2 , O 2 , A ir, C H 4 , I n ert Gas, and NG

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Figure 2.11 LNG M a te r i a l s a nd Fl ui ds D a t a o f V a p o r
Pre ssure / T em pe rat u re for M et ha ne

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2.13 Summary
Summarizing some of the properties of LNG:

1. Natural gas is only combustible in concentrations of 5% to 15%

in air.

2. LNG has a very low boiling temperature (-160OC) at atmospheric

pressure, however, as cryogenic liquids go LNG is fairly warm.
Liquid nitrogen, oxygen, argon, carbon monoxide, hydrogen and
helium are all considerably colder.

3. At ambient temperature and pressure, the LNG will vaporize and

expand about 600 times.

4. LNG weighs about 424kg/m3 at the conditions listed in item 2.

That is about 42% the weight of water.

5. LNG is odorless and colorless. It looks much like boiling water

when placed in a beaker. Because it is odorless, odorant needs
to be added after it is vaporize and before it is injected into a
gas distribution system.

6. LNG must be vaporized before it can be ignited. Neither LNG,

nor its vapor, can explode in an unconfined environment.

7. In the vapor state, when still very cold (as around a large spill),
the gas is heavier than air and as such will hug the ground in the
immediate area of the spill. The cold gas will condense any
water vapor in the air causing a visible white cloud. Purely by
c o i n c i d e n c e , t h e v i s i b l e l i m i ts o f t h e c l o u d r o u g h l y a p p r o x i m a t e
the lower flammability limit of the gas mixture.

8. A light breeze will heat the vapor and rapidly dissipates the gas
harmlessly into the atmosphere. Methane need only be warmed
to –107 OC to become buoyant in air.

9. LNG is not toxic, however, if it displaces air in an enclosed

space it can cause asphyxiation.

10. Volumetric reduction to about one six hundredth (1/600) of gas

a t t h e n o r m a l t e m p e r a t u r e d u e t o l i q u e f a c t i o n . T h i s is
a d v a n t a g e o u s t o s to r a g e a n d t r a n s p o r t a t i o n .

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11. A liquid in the state of boiling point. When equilibrium between
gas and liquid is destroyed by rise of temperature or fall of
pressure, the liquid will immediately start boiling.

12. Upon leaking into air, it rapidly evaporates and forms white
vapor cloud by the condensation of moisture.

13. LNG will stay at near constant temperature if kept at constant

pressure. This phenomenon is called “auto-refrigeration”. As
long as the steam (LNG vapor boil off) is allowed to leave the
kettle (tank), the temperature will remain constant.

14. T a n k p r e s s u r e w i l l n o t r i s e d u e t o b o i l - o f f ( e v a p o r a t i o n ) le a v i n g
the tank.

15. LNG will require use of suitable material for cryogenic

temperature, considerations towards expansion and contraction
due to the change in temperatures, structural design with due
regard to thermal stress, effective heat-insulation system,
precaution against damage caused by low temperature.

16. High dielectric power and extremely poor electric conductivity. It

can be easily be charged even by static electricity.

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