A VIDEOTEL PRODUCTION

The Physics of Liquefied Gases

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The Physics of Liquefied Gases

A VIDEOTEL PRODUCTION The Producers would like to thank the following for their help with this programme: Bibby-Harrison Management Services Ltd BP Shipping Ltd BV United Gas Carriers Calor Gas Ltd Chevron Shipping Dorchester Maritime Ltd The Institute of Marine Engineers ITS Testing Services Ltd SIGTTO

CONSULTANT: PRODUCER: DIRECTOR: PRINCIPAL PRINT AUTHOR:

CHRIS CLUCAS ROBIN JACKSON GEORGE BEKES ROBIN JACKSON

Warning: Any unauthorised copying, hiring, lending, exhibition diffusion, sale, public performance or other exploitation of this video is strictly prohibited and may result in prosecution. COPYRIGHT Videotel 1999 This video is intended to reflect the best available techniques and practices at the time of production, it is intended purely as comment. No responsibility is accepted by Videotel, or by any firm, corporation or organisation who or which has been in any way concerned, with the production or authorised translation, supply or sale of this video for accuracy of any information given hereon or for any omission herefrom.

Videotel Productions The Physics of Liquefied Gases

CONTENTS
Introduction Module 1: Module 2: Module 3: Module 4: Module 5: Module 6: Module 7: Module 8: Module 9: The Properties of Gases The Gas Laws Sensible and Latent Heat Enthalpy Pressure Relationships The Mollier Chart The Laws of Thermodynamics Cargo Systems Two Stage Compression Refrigerated Systems Summary

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Videotel Productions The Physics of Liquefied Gases

THE PHYSICS OF LIQUEFIED GASES

Introduction
In recent years there has been a rapid growth in the shipment of cargoes of liquefied gas. Both LNG (liquefied natural gas) and LPG (liquefied petroleum gas) are now shipped between continents in considerable quantities. Ammonia and other chemical feedstocks are also carried in liquefied form. The ships that carry these cargoes are obviously very different from the vessels that carry containers and dry cargoes. It is essential that those who sail on them have a clear understanding of what is involved if they are to carry these cargoes safely and efficiently and without affecting their specification. Training in basic physics as it relates to the safe carriage of liquefied gases in bulk is mandatory under the requirements of the IMO International Convention on Standards of Training, Certification and Watchkeeping for Seafarers 1995 (STCW95). This training is compulsory for Masters, Chief Engineers, Chief Officers, Second Engineers and any other Officer responsible for handling of bulk liquefied gas cargoes. This training package complies with the STCW95 requirements and looks at the basic physics involved in carrying the main liquefied gas cargoes as this can help us understand how to ensure that we avoid any problems. The package can be used for group training or individual self-study. The programme is presented in a lecture format and is broken up into distinct modules. It is suggested that you refer to the relevant section of this booklet as you finish viewing each module. It is not advisable to view the whole programme in a single session.

1. The Properties of Gases

A gas is a collection of molecules flying around in space. If we were to add up the volume of each individual molecule it would be quite insufficient to fill the space which contains them. As the physicist Oliver Lodge summed it up: A gas is something in chaotic movement which is bounded by the surfaces of the container around it. In fact the very word gas comes from the Greek for chaos. Within a container, we can think of gas molecules or atoms as balls, bouncing off each other and off the surface of the container. Their speed of movement depends on the energy level or temperature of the gas. As we cool the gas down, the speed decreases and eventually the molecules will stick together so that the gas becomes a liquid. This liquid is bounded by the lower surfaces of its container but the upper surface reflects gravitational attraction. Cooled still further the molecules will stick together even more closely and form a solid. This has completely self-contained boundaries and is self-defining. So by condensing a volume of gas and turning it into a liquid, we can reduce its volume many hundreds of times. This is the basis of transporting gases in liquid form. For example, propane gas occupies approximately 250 times the volume of propane liquid at 15C . Much work was done on the subject of gases at the beginning of the 19th Century. The Irish scientist, Robert Boyle, for example, measured the volume of a gas while he varied the pressure on it, keeping the temperature constant. The French physicist, Jacques Charles, kept the pressure constant and then measured the volume while varying the temperature. He found that as the temperature rose, the volume increased in a straight line relationship. Although scientists then could not produce extremely cold temperatures, the graph showed that, in theory, there would be a very low temperature when the volume of gas was zero.

Videotel Productions The Physics of Liquefied Gases

Volume

x
B

C -273.15C 0K -100C 173.15K 0C 273.15K 100C 373.15K Temperature

C is the point where the extension of the line AB meets the temperature scale in degrees Celsius. This point is the start of the absolute temperature scale.

Illustration of Absolute Temperature Repeating these experiments with a variety of gases showed that whatever the gas, the temperature at which the volume became zero was the same. This temperature was defined as the absolute zero of temperature. The absolute scale was named in honour of the physicist Lord Kelvin and this temperature scale is given the origin point of zero degrees Kelvin. The Kelvin scale has the same interval degrees as the Celsius scale but the zero point is 273 degrees below zero Celsius. It is not entirely clear what happens to atoms at the absolute zero of temperature. It can only be approached, never actually reached.

Videotel Productions The Physics of Liquefied Gases

2. The Gas Laws

The work of the early scientists on gases resulted in a number of Gas Laws which defined the relationships between different properties of the gas. Boyles Law, for example, states that Pressure x Volume is constant if the gas is held at constant temperature. P x V = a constant

Pressure, P Pressure, P

PPxV = constant x V = constant

Volume, V Volume, V Illustration of Boyles Law

Videotel Productions The Physics of Liquefied Gases Charles Law states that Volume divided by Temperature is constant if the pressure is constant. V/T = a constant

Volume, VV Volume,

V V ==constant constant T T

Temperature,TT Temperature,
Illustration of Charles Law

Videotel Productions The Physics of Liquefied Gases The Pressure Law, sometimes referred to as the Constant Volume Law, states that Pressure divided by Temperature is constant if the volume is kept constant. P/T = a constant

Pressure, Pressure, P P

P = constant P = constant T T

Temperature T Temperature, T
Illustration of Pressure Law Another scientist who contributed a great deal to our understanding of this area was the Italian, Amedo Avogadro. In the early 19th century he proposed that the volume of a gas could be related to its mass. At zero degrees Celsius and one atmosphere pressure he found that for different gases, a volume of 22.4 litres always held a quantity of gas equivalent to its molecular weight in grams. Avegadro defined these conditions as normal temperature and pressure or NTP. So 16 grams of methane or 44 grams of propane occupied the same volume at NTP. Furthermore, Avogadro proposed that this volume contained the same number of atoms or molecules for any gas - a number he calculated as 6.023 x 1023. He defined this quantity as a mole, (from the Latin for a large number of molecules), and defined the volume occupied by a mole of a gas at NTP as the molar volume. Note that Avogadros hypothesis is independent of mass units - so it is possible to define a molecular number and volume for kilograms, pounds and so on. However, the gram-mole is the most commonly used, so it is the unit assumed if no other is stated. By putting these various Gas Laws and Avogadros hypothesis together, it is possible to derive a General Gas Equation that relates the pressure, volume and mass of a gas to its temperature. PxV=nRxT n is the number of moles of the gas and R is called the Universal Gas Constant. 5

Videotel Productions The Physics of Liquefied Gases The other law which describes the behaviour of gases is known as Daltons Law. Dalton found that if he took a mixture of gases which did not react with each other chemically, then the pressure they exerted in a closed container was independent of the mixture - that is each gas behaved as if the other components of the mixture were not present. This can be simply illustrated for a mixture of hydrocarbon gases as: P = p1 + p2 + p3 + p4 + .... where P is the total pressure of the mixture, p1 is the partial pressure of the methane present, p2 is the partial pressure of the ethane present, etc. Finally, we need to be clear that in calculations involving the gas laws, we use absolute units of pressure, whereas in general industrial practice we measure pressures relative to atmospheric pressure. So gauge pressure shows pressure above atmospheric pressure and the absolute pressures used in gas law calculations are 1 atmosphere higher than gauge pressures.

3. Sensible and Latent Heat

The carriage of liquefied cargoes also requires us to understand what happens if and when these liquids change phase - that is cool down and become solids or heat up and become gases. Lets consider the example of water.
Sensible heat Latent heat of fusion (355 kj/kg) Sensible heat (420 kj/kg) Latent heat of vaporisation (2260 kj/kg) Superheating

STEAM

TEMPERATURE C

100

WATER
0

ICE
HEAT

Behaviour of Water When Heated Ice, the solid form of water exists from a temperature of absolute zero -273C. If we start to add heat we can use a thermometer to measure the rise in temperature. This heat can be measured or sensed so is defined as sensible heat. But at 0C, although the rate of heating remains constant, the temperature has stopped rising. This is because the energy being put in to the ice is being used to break up the bonds between the ice molecules and form the more loosely bonded liquid we call water. Because this heat input cannot be sensed, it is called the latent heat and because the ice is melting it is called the latent heat of fusion. As the water is heated, the movement of the water molecules steadily increases. The temperature rises and so we have more sensible heat. At 100C the molecules start to fly off into the space above the liquid surface and the water boils. For the molecules to move into the gas phase, the interaction between the liquid molecules has to be overcome and this requires more latent heat energy - the latent heat of vaporisation. Once all the water has been converted into steam then this itself can be heated further. It becomes a superheated gas. When the gas is in equilibrium with the liquid we call the gas saturated. When we are handling gases on board ship, however, we need to consider not just the temperature but also the volume and pressure. These define the total heat content of the gas or its enthalpy. 6

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4. Enthalpy Pressure Relationships - The Mollier Chart

In our example of water we know that the transition temperatures - the freezing and boiling points - are 0C and 100C respectively at atmospheric pressure. But these temperatures can be altered by changes in pressure. For instance, on board ship we often reduce the pressure and then boil sea-water to distil it and obtain fresh water at jacket water temperatures. Conversely in steam boilers or autoclaves, the pressure is increased and the boiling point is raised. Furthermore, the latent heat of vaporisation varies according to whether the boiling is being undertaken at reduced or increased pressure. When the relationships of enthalpy against pressure are plotted on a chart the resulting diagram is known as a Mollier Chart. This is an essential aid to understanding what may happen when we liquefy or condense our cargo gases. A simplified version of a Mollier Chart is shown below.
0C 50C 90C 100C Critical point 50 40 30

SUPERHEATED VAPOUR SUB-COOLED LIQUID

Constant temperature

line

Dr y

LIQUID/VAPOUR MIXTURES

rat e

Sat u

Satura t

ed va

pour li

d li

10

6 5

Latent heat

0.2

0.4

0.6

Enthalpy: Simple Mollier Chart The diagram plots the enthalpy along the x-axis and the absolute pressure on the y-axis. From the bottom left a curved line runs up towards the right, levels off and then turns down again to the x-axis. The left hand portion of the line represents the saturated liquid line and the right hand portion the saturated vapour line. In the region between and below these curves there is a mixture of liquid and vapour. The transition point, at the top, is called the Critical Point. The horizontal distance between the curves denotes the latent heat at a particular pressure and this decreases as the pressure increases until, at the Critical Point, it becomes zero. The other lines shown within the envelope run through points with the same dryness fraction. The figures show the fraction of gas in the mixture - i.e. 0.4 means that 40% of the mixture is liquid and 60% gas. To the left of the saturated liquid line there will be sub-cooled liquid and to the right of the saturated vapour line will be super-heated vapour. 7

0.8

Pressure (bar Absolute)

20

nes s

(x)

qui d

ne

Videotel Productions The Physics of Liquefied Gases The dashed lines are lines of constant temperature and by looking at these it is clear that at certain temperatures it is not possible to liquefy a gas just by increasing the pressure. The gas must first be cooled to the critical temperature or below. For some of the cargoes commonly carried, such as ethylene and ethane, this critical temperature is in the ambient range.

5. The Laws of Thermodynamics

In using the cargo systems on board we also need to understand some of the laws of thermodynamics. There are four of these laws although only three concern us here. The Zero(th) Law introduces the concept of thermal equilibrium between bodies. It states that:If a body A is in thermal equilibrium with body B, and body B is also in thermal equilibrium with body C, then body A is also in thermal equilibrium with body C.

The First Law introduces the concept that heat and work are equivalent. It states that:The heat lost from a source is equal to the total heat gained and work done on the bodies that receive that heat. The Second Law introduces the concept of directional heat flow. It states that:Heat always flows from a hot body to a cooler one.

6. Cargo Systems
With an understanding of the Gas Laws and the Laws of Thermodynamics we can follow the operation of a simple cargo system on board a liquefied gas ship. A simplified cycle is shown below.
Cargo vapour

Liquid separator Compressor

Sea water

condenser 4 5 collecting vessel

cooling

1 cargo tank

Expansion valve

SingleSingle stage direct compression cycle Stage Direct Compression Cycle 8

Videotel Productions The Physics of Liquefied Gases The cargo tank contains cold liquid. Although it is insulated, some heat will still come through from outside. This is a consequence of the Second Law of Thermodynamics. This heat will overcome the latent heat of vaporisation and so some of the cargo will boil off. The vapour formed will raise the pressure in the tank. The vapour is drawn off and passed to a compressor. The work done by the compressor raises the temperature of the vapour according to the First Law of Thermodynamics. This temperature rise is necessary so that it becomes hotter than the cooling medium that is subsequently used to cool it again. The hot gas or vapour now passes to a condenser where it is cooled by sea water. The removal of heat means that the molecules slow down and the vapour condenses to form a warm liquid. This liquid is also under pressure. The liquid is then passed through an expansion valve that reduces the pressure. This results in a partial evaporation which causes the temperature of the bulk liquid to fall back down to tank temperature. So cold condensate is returned to the tank. (These valves are sometimes referred to as Joule-Thompson valves after the physicists who discovered the cooling-expansion phenomenon.) It is important to note that the Joule-Thompson expansion results in cooling because the small amount of gas generated absorbs its latent heat of vaporisation from some of the liquid. The real cooling effect of this cycle is the removal of sensible heat and the latent heat of vaporisation from the full flow of gas as it is condensed and cooled. In summary, we can see that the heat flowing into the tank has been returned to the environment via the sea-water, together with the additional work done by the compressor. This can also be followed on the Mollier Chart.

4
Pressure Pressure (absolute) (absolute)

5 1
Enthalpy Enthalpy Mollier Chart: Single Stage Direct Compression Cycle Point 1 represents the vapour in the dome of the tank. As it passes to the compressor it picks up some heat (Point 2). The compressor raises the temperature and pressure of the gas to Point 3. It is then cooled and condensed and becomes a saturated liquid (Point 4) in the condenser. The expansion valve then produces cold liquid with a proportion of vapour and this is returned to the tank (Point 5). This is the same cycle as that of a domestic refrigerator but on the ship the working fluid is the cargo boiloff. If the cargo were totally pure it would be easy to use a Mollier Chart but in reality, few cargoes are chemically pure and in cases such as LPG, the cargo is usually a mixture of several hydrocarbons. This can give rise to problems due to the preferential evaporation of the compound with the lower boiling point. 9

Videotel Productions The Physics of Liquefied Gases

-40 -40

-50

Gas

-50

-60 Temperature C

-60

-70

Liqu

id

-70

-80

-80

-90 0 4 22 50

-90

100

MOLE % ETANE Pressure = 1.1 bar (A); Mole % propane = 100 - Mole % ethane

MOLE % ETANE

Propane - Ethane Equilibrium Diagram For example, take a cargo of liquefied propane that contains 4% ethane. When the cargo vaporises, however, the gas will contain 22% ethane. Variations like this can affect the mass flow through the compressor. This in turn affects the cooling performance of the system. Ethane also raises the condensing pressure. So increasing proportions of ethane will effectively reduce the plants cooling capacity. Knowing the composition of your cargoes will help you understand how plant performance can vary.

7. Two Stage Compression

The single stage system we have just described has certain limitations. For example, if the cargo tank pressure is low and the sea-water temperature is high, the compressor has to do much more work to make the cycle operate - in other words it will need a high compression ratio. But as the Compression Ratio in a typical compressor is increased, the valve performance becomes less efficient.
1.0 0.9 Efficiency 0.8 0.7 0.6 0.5 0.4 1 2 3 4 5 6 7 8 9 10 11 12 Compression Ratio

Effect of Compression Ratio on Valve Efficiency Effect of Compression Ratio on Valve Efficiency

10

Videotel Productions The Physics of Liquefied Gases To overcome this problem, it is normal to split the compression into two stages.
1st stage compressor 3 Cargo vapour 5 Liquid separator 2 7 1 4 2nd stage compressor

Intercooler
Condenser Cargo tank

Sea water

Expansion valve 8 Liquid return Collecting vessel

cooling

Two stage direct Compression Two Stage Directcompression cycle Cycle

The principle is the same as before with cargo vapour from the tank passing to the first and second stage compressors. It may be necessary to cool the suction vapour entering the second stage compressor by passing it through an intercooler fed by cold liquid on its way back to the cargo tank. However, care must be taken not to cool this vapour too much or otherwise there could be liquid entering the second stage compressor. The Mollier Chart shows the process with the numbers on the Chart corresponding to those on the diagram of the plant.

6 5 4

Pressure Pressure (absolute) (absolute)

3 8 1
Enthalpy Enthalpy

Schematic mollier chart Schematic Mollier Chart: TwoTwo Stage Direct Compression cycle stage direct compression Cycle

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8. Refrigerated Systems
In many ships carrying refrigerated cargoes, the cargo cooling is actually performed by an intermediate refrigerant such as R22. This enables us to reduce the pressure gradient across the cargo vapour compressor. The refrigerant circulates in a separate, closed cycle in which it is condensed by sea water. This system is known as the Cascade Cycle.
Cargo liquid separator Cargo vapour Cargo vapour compressor R22 Liquid separator

Cargo condenser

5 1
Liquid

8 4

Cargo Cargo Tank tank

R22 Compressor Sea water R22 Collecting vessel R22 condenser cooling

10

Cascade Cycle

The Mollier Charts can again be related to the plant, with one chart representing the cycle for the cargo, the other the cycle for the refrigerant.
Cargo R22

4
Pressure Pressure (absolute) (absolute)

3 5 1 2
Pressure Pressure (absolute) (absolute)

9 10 6
Enthalpy Enthalpy

Enthalpy Enthalpy Mollier Chart: Schematic mollier chart Cascade cycle Cascade Cycle

12

Videotel Productions The Physics of Liquefied Gases This system involves more machinery and is more complex but it is needed for cargoes such as ethylene or ethane being shipped through areas where the temperature of the sea-water is higher than the Critical Temperature of the cargo. The relationship between pressure and temperature of the cargo is particularly relevant in this context. The graph below shows the relationship between absolute pressure and boiling point for various liquefied gases.

SATURATED VAPOUR PRESSURE (Kg/cm2 absolute) - LOG SCALE

70 60 50 40 30

CRITICAL TEMPERATURE/CR

ITICAL PRES SURE LINE

20

MET HAN E

YLE N

ETH ANE

ETH

10 9 8 7 6 5 4

IDE LOR

PR

OP

YL

EN E

PAN E AM MO NIA

PRO

1 -160 -140 -120 -100 -80 -60 -40 -20 0 20 40 60 80 100 TEMPERATURE (C)

Pressure vs Temperature - Various Liquefied Gases For butane, for example, the boiling point at atmospheric pressure is approximately 0Celsius. When the temperature rises to about 45 Celsius, the pressure is increased to approximately 4 bar absolute (or 3 bar gauge). For propane the atmospheric pressure boiling point is approximately -42Celsius and at about 0Celsius the pressure rises to about 4.5 bar absolute (or 3.5 bar gauge). The temperature at which a liquid gas turns into vapour is often called the saturation temperature to differentiate it from the term boiling point - which is most often used to specify vaporisation at atmospheric pressure. For world-wide trade at sea, the maximum temperature for sea is assumed to be 32Celsius, and for the ambient air, 45Celsius. So it can be seen from the chart, that to keep polypropylene cargoes liquid at those temperatures, the pressure in the tank needs to be about 19 bar absolute, (or 18 bar gauge). The graph also shows that cargoes such as methane, ethylene and ethane will always be above their critical temperatures in high ambient conditions so they must be cooled below the critical temperature in order to liquefy them. Pressure alone will not achieve this liquefaction. So these cargoes are always transported in cryogenic conditions at atmospheric pressure, about -104Celsius for ethylene, and -160 Celsius for methane. 13

BUT

YLE

NE

VIN

YL

CH

BU

TA N

Videotel Productions The Physics of Liquefied Gases

As we mentioned earlier in the context of LPG mixtures, the fact that the cargoes are seldom pure can cause complications due to differential evaporation. Its quite common, for example, to leave a small quantity of cargo or heel in a tank at the end of a discharge. This may be used to keep the tank cool or, in the case of LNG ships, used for fuel during the ballast voyage. If this heel is allowed to evaporate using natural evaporation, the lighter components will be drawn off first and, as time goes on, the heel will contain more of the heavier components. This process is known as flash vaporisation or weathering.
Lighter components

Spray liquid rundown (heavier components)

Spray liquid vaporizes gives off lighter components Liquid Heel boils off (lighter components first)

Heat enters through insulation

Weathering WEATHERING or Flask Vaporization OR FLASK VAPOURIZATION To prevent this happening it is necessary to pump some of the liquid into a heat exchanger and evaporate it all in one go. This is known as batch vaporisation. The heat that penetrates the insulation and enters the cargo tank can also produce another physical phenomenon known as Stratification.

Boil off removed Heat transfer BOIL OFF Hot layer

Co n cu vect rre io nt n

Heat enters through insulation

STRATIFICATION Stratification

14

Videotel Productions The Physics of Liquefied Gases The heat causes the liquid near the tank surface to heat up very slightly - perhaps by no more than 1 or 1.5Celsius. But this warming reduces the density of the liquid so that it rises to the top of the liquid in the tank and forms a warm layer at the liquid surface. This promotes evaporation of liquid from the surface. The bulk of the liquid in the tank is not affected. In certain cases, temperature differentials can cause more severe effects although the instance quoted here happened in a shore tank and is unlikely to occur on board ship. The tank was initially filled with a light LNG mixture. Subsequently a heavier LNG from a different source was also added. The heavier layer lay at the bottom and the two fractions remained very separate. As the boil off was drawn away from the upper layer, this became richer in heavier components and its density increased. At the same time, the lower layer gradually warmed up and its density decreased. A point was reached when the layer on top was heavier than the layer below and the layers spontaneously rolled over. This caused a massive increase in the rate of evaporation and lifted the tank roof. As the roof had been designed to relieve under excess pressure, no mechanical damage was caused, but a potentially hazardous situation had occurred. On board ship, procedures may be specified for circulation of the cargo using the pumps to ensure that if cargoes, which are nominally the same but have come from different sources, are loaded in the same tank, then this unstable roll-over situation does not occur.

BOILING OFF LIGHTER LIQUID LAYER HEAVIER LIQUID LAYER WEATHERING: DENSITY INCREASES THERMAL EXPANSION DENSITY DECREASES

HEAT

HEAT

HEAT

SUDDEN ROLL OVER, CAUSING MIXING & MASSIVE VAPORIZATION

Roll Over

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9. Summary
The safe carriage of liquefied gas cargoes on your ship requires careful observance of all the appropriate regulations and safety requirements defined in the IGC Code, Marpol Annex II, SOLAS Chapter II, the ICS Liquefied Gas Tanker Safety Guide, and elsewhere. The Cargo Data Sheets also carry much vital information. In this booklet and the accompanying programme we have described some of the basic physics that should help you to understand the physical behaviour of the cargoes and cargo systems and help you to avoid any mishaps. The key aspects to remember are: The various Gas Laws and the derivation of the General Gas Equation. The concept of Sensible and Latent Heat and the transitions between the phases of matter. The meaning of Enthalpy and the use of the Mollier Chart. This makes it clear that a gas cannot condense until it is below its critical temperature. The Laws of Thermodynamics and their application in cargo systems. The various systems used to achieve compression and liquefaction. The possible consequences of carrying gas mixtures with components that evaporate at different rates. For further information you may also wish to refer to the following training packages available from Videotel: The Chemistry of Liquefied Gases An Introduction to Liquefied Gas Carriers

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