LIQUIFIED NATURAL GAS

What is?
- Mixture of Ethane, Propane, Butanes and Pentanes  C2 – C5
- Cryogenic  Teb = − 160°C @ 1 atm (if released it completely evaporates)
- Odourless
- Colourless
- Asphyxiating
- Non-toxic
- Flammable
- Varying composition in time  ageing (because of vaporization it becomes lighter)
- Light, less dense than water and air
Differences between LNG and LPG:
- LNG is a mixture of C2 – C5, it is an intermediate stream and requires further processing
- LPG is a mixture of C3 and C4 and is saleable
Why LNG?
- Flexible mean to transport natural gas, reduces volumes by 600 times
- Transportation and storage
- Market flexibility
- Clean fuel  environmentally friendly
- Higher energy density than NG or CNG
- Higher auto ignition temperature than diesel  safer
- Complete vaporization and dispersion if released in the environment  safer

On/off shore field development

On/off shore pipelines
UPSTREAM

Gas/Liquid treatment
Liquefaction units
LIQUEFACTION
LNG storage and marine infrastructure
PLANT Floating alternative

Membrane technology
LNG
MOSS technology
TRANSPORTATION

Marine infrastrucure and LNG import

Floating alternative
LNG MPORT Regassification units
TERMINAL
Liquefaction plant
What is?
- Huge and complex refrigerator = heat exchangers + refrigerating cycles
- Gas with high P and ambient T  liquid with low T ( −160°C) and ambient P
- Production > 3 MTPA (Million Tonnes Per Annum)

Contaminants?

Substanc
Maximum concentration
e
CO2 50 – 100 ppm To avoid freezing
Water 1 ppm
Benzene 4 ppm
Pentanes 1500 ppm
To avoid gels
H2S 4 ppm
N2 1% To fulfil pipeline gas specifications
C2 + As desired
Hg As minimum as possible Because it is not a valuable product
To increase Heating Value
Feed gas must be pre-treated with: To avoid reaction with aluminium alloys
- Acid gas removal
- Dehydration
- Mercury removal
NGL must be recovered and then it can be sent to liquefaction plant.
THERMODYNAMICS
The lower the temperature the greater the energy to cool down the gas:
From + 40°C to – 10°C = 100 kWh
From - 110°C to – 160 °C = 1000 kWh
The higher the pressure, the easier the liquefaction:

The higher the pressure, the higher the critical temperature, hence you need to spend less
energy.
The most efficient technology is the one where heating and cooling curves are as close as
possible, the area between the two curves represents the heat lost during the liquefaction
process.
Liquefaction Process Specific Power = kWh/kg, it is a sort of efficiency, the lower the better. It is
the ratio of total refrigeration compressor power and LNG production rate.
 NG cooling curve

Refrigerant heating curve

Actually, we use mixed refrigerants, which are more efficient. Liquefaction may be divided into
three phases: pre-cooling, liquefaction and sub-cooling.
LIQUEFACTION TECHNOLOGIES
Single component technologies:
1. Reverse Brayton Cycle  specific power = 0.53

Gaseous N2 as refrigerant. It enters the cycle pre-cooled.

Sensible heat is transferred (N2 is not vaporized)
PROS:
- No HC refrigerants  more safe
- Easy start-up and operation
- Compact
CONS:
- No liquid refrigerant  more power is needed
- High refrigerant pressure  compression cost
- High volumetric flow  large pipe diameters
- Non optimized pre-cooling
- Can be used only up to 0.1 MTPA

Improvements:
- Dual N2 expansion = a first Warm Expander is followed by a second Cold Expander. The
second expansion enhances efficiency of the refrigerant cycle.

Feed gas

N2
 2. Reverse Carnot Cascade Cycle  specific power = 0.36

Carnot cycle is the most efficient cycle.

Latent heat is transferred (the refrigerant is
vaporized).
3 refrigeration closed loops:
- Propane
- Ethane and Ethylene
- Methane

The cycle efficiency is higher, the cold and

hot curves are closer.
Used for plant capacity up to 5 MTPA

Mixed refrigerant technologies:

1. Single Mixed Refrigerant Technology  specific power = 0.38

Refrigerant is a mixture of C1, C2, C3, C4,

C5 and N2. It is partially liquefied so also
latent heat is exchanged.
Safer than pure C2, C3, …
Single refrigeration loop.
Reduced equipment compared to
cascade.
Used for plant capacity up to 1 MTPA
 2. Dual Mixed Refrigerant Technology  specific power = 0.33

One mixture for pre-cooling:

C1, C2, C3, C4
One mixture for liquefaction and
subcooling:
C1, C2, C3, N2
The composition is adjusted for
optimization.
Used for plant capacity up to 4.8 MTPA

3. Triple Mixed Refrigerant Technology  specific power = 0.27

Most used technology. It is hybrid since it combines pure refrigerants with mixed ones.
Two lops of refrigeration with different mixtures:
- Propane cycle for NG and mixed refrigerant pre-cooling
- A mixed cycle for liquefaction and sub-cooling
Proven technology up to 3 – 5 MTPA.

As many steps as stages of compressor

Power split
In configuration a, the 1/3 of total power is
required for propane compression while 2/3
is required for MR compression. Usually the
two gas turbines have the same capacity,
hence it will be used a gas turbine able to
sustain the MR compression also for the
propane compression. The second turbine is
fully loaded while the first one not  power
losses.
In configuration b, the power is split equally,
and this allows for full utilization of the gas
turbine power.
 4. AP – X technology
Technology similar to C3 – MR with the addition of a nitrogen expansion loop for final subcooling.
It is composed by:
- Propane loop per NG and MR pre-cooling
- MR for liquefaction and sub-cooling
- Nitrogen for further sub-cooling
Proven technology up to 8 MTPA.

Is there a best liquefaction technology?

Efficiency = heating – cooling curves are as close as possible  Thermodynamics
Ideal refrigeration:
- Infinite number of refrigeration cycle
- Dedicated MR in each cycle
The best option should consider many factors:
- Mixed refrigerant cycles are better than Pure Component ones.
- Multiple Refrigeration Cycle are better than a single cycle.
- Balance CAPEX and thermodynamic efficiency.
- Case by case study = plant capacity, feed gas composition, equipment availability, …

Control philosophy
LNG production rate  available refrigeration duty
LNG temperature  controlled at the outlet, if it increases the feed gas flowrate is reduced
Refrigeration duty  refrigerant mass flow
efficiency of the heat exchange (NG and refrigerant composition)
Liquefaction unit equipment
Rotating equipment:
- Refrigerant compressors and drivers
- Cryogenic pumps
- Hydraulic turbines
Static equipment:
- Brazed Aluminium Heat Exchangers
- Spiral Wound Heat Exchangers
- Propane refrigerator

1. Refrigeration compressor drivers:

Gas turbines
Most used drivers for compressors.
Heavy duty turbines:
- Most common
- Lower efficiency 30 – 35%
- Single shaft, fixed speed  difficult start up, need starter helper
- Double shaft, variable speed  easier start up, higher flexibility
- From 35 MW to 130 MW
Aero-derivative turbines:
- Higher efficiency 40 – 45%
- Lighter
- Large operational flexibility
- Require higher fuel gas pressure  CONS
- Power output is more sensible to ambient temperature  CONS
- Require higher combustion temperature  CONS
- From 35 MW to 100 MW
Electric motors
PROS:
- Higher efficiency
- Lower emissions
- Better maintenance and availability
- Lower layout constraints
CONS:
- Higher CAPEX
- Increase electrical grid complexity
 2. Cryogenic pumps

- Used for LNG transportation.

- LNG must not vaporize when the pump is running  difficult
- Aluminium internals are sensible to deltaT  avoid thermal shocks
- The motor is immersed in the cryogenic liquid, which provides refrigeration for the motor

3. Hydraulic turbines
They are used for the isentropic expansion of high-pressure subcooled fluids. The isentropic
expansion is more efficient than the adiabatic one (JT valves), moreover it provides less flash gas.
4. Cryogenic heat exchangers
Brazed Aluminium Heat Exchangers:
- Aluminium corrugated plates
- Limited space requirement
- Sensible to Mercury
Spiral Wound Heat Exchangers:
- Small diameter tubes around a central mandrel
- Extremely large equipment
- Higher resistance to rapid changes of temperature and pressure
- Aluminium
LNG import terminal
What is?
- LNG liquid at ambient P and T = - 160°C  gas NG at high P and ambient T
- Can be made onshore or offshore on Gravity Based Structures or on Floating Storage
Regassification Units
Plant?
Design based on LNG carrier size and arrival frequency.
Technologically less complex than liquefaction plants.
Lower footprint and environmental impact.

BOG = Boil Off Gas is the vaporized LNG, it can be used as fuel for the regassification facilities or it
can be liquefied and sent back to vaporization. It cannot be put directly into the regassified NG
since its composition is different (it contains only light hydrocarbons) and moreover it is at low
pressure.
Onshore or offshore?
Onshore:
- Located near the coast
- Wide potential connectivity and expandability
- Huge
- Lower OPEX
- More flexibility
- Less layout constraints
Offshore:
- Moored to the shore or to the seabed
- Lower CAPEX and shorter schedule
- Overcome Not In My Back Yard problem  no one will have problems with the location
- Possibility of relocation
- Simplified decommissioning
Gravity Based Structures:
- Only one in the world at Rovigo (Italy)
- It is a fixed concrete structure laying on the seabed
- It also houses LNG storage tanks
- On the structure deck mooring, unloading and regasification facilities are installed

Regasification main equipment

Rotating equipment:
- BOG compressors and drivers
- Cryogenic pumps
Static equipment:
- BOG condensers
- LNG vaporizers

1. BOG compressors
They are necessary to handle BOG flowrate to control storage tanks pressure.
They operate discontinuously, since BOG flowrate is not constant.
2. BOG condensers
They are used to liquify the excess BOG, which hasn’t been used as fuel.
BOG condensation  subcooling and condensing of BOG is promoted by the indirect heat
exchange with the LNG coming from the LP pumps.
3. LNG vaporizers
Heat exchanger with hot water or air or steam as heating mediums.
Different technologies:
- Open Rack Vaporizer = most used technology
sea water as heating medium
counter current contact with hot water
freezing problems
- Submerged Combustion Vaporizer = hot water heated by flue gas as medium
- Intermediate Fluid Vaporizer = sea water and intermediate (C3, C4) mediums
compact and efficient

- Ambient Air Vaporizer = air as medium

only for small scale applications
LNG transportation

LNG carriers are used to transport LNG on long distances. It is a new (less than 60 years) and
complex technology.
Main difficulties are due to cryogenic conditions of LNG:
- Structural typology and material of tanks
- Insulation to minimize BOG
- BOG handling  composition inside the tank changes during the voyage since lighter
compounds are removed as BOG and heavier compounds remain in the tank. BOG can be
fired for ship propulsion or liquified and reinserted inside the tank to maintain the
specifications.
Nowadays 3100 MTOE (Million Tons of Oil Equivalent) of natural gas are required. 325 MTOE are
supplied by LNG. The number of LNG carriers nowadays is 478 ships. It is a market which is still
growing.

Containment system
Membrane tanks
How? Structure made of two membrane barriers separated by two layers of PVC foam used as
insulator. More than one barrier to prevent LNG to reach the hull structure, made of ordinary
steel.
PROS:
- Efficiently withstand cryogenic conditions
- Light
- Minimize deformations due to temperature gradients
- Technologically advanced
CONS:
- Patented technology
- Expensive
- Costly maintenance
- High risk of defects during construction  delicate
- Sloshing***
 - Fatigue life difficult to measure
The main licensors of this technology are:
- Gaztransport = metallic and flat membranes, composed of 36% of Nickel–steel alloy
(INVAR)
prefabricated plywood boxes as filled with expanded perlite as insulators

- Technigaz =primary low carbon content stainless steel membrane, corrugated and flat
secondary composite membrane
prefabricated polyurethane foam as insulators

***
Sloshing = LNG motions induced by ships movement with potential consequences on the
containment system integrity and stability up to ruptures or capsize (ribaltamenti).
Can be prevented by:
- Reducing tank size  possible only in oil tankers, not possible in gas tankers due to
unacceptable increase of BOG.
- Load model improvement  system should transfer loads without damage on the
containment
Independent type B
Designed so that a crack can be detected long before the actual failure. Stress and fatigue
determination at different temperature and pressure is fundamental.
It is a self-supporting spherical tank.
PROS:
- No sloshing
- Spherical shape  no tank filling restrictions
- Low risk of defects during construction
- Fatigue life easy to measure
- No secondary barrier is needed
CONS:
- Huge  poor navigation visibility and manoeuvrability

Independent type C
For small scale applications, designed as cryogenic pressure vessels. Commonly they have
cylindrical shape. No secondary barrier is required. Failure are detected by means of an inert gas
filled in the hold space and detected, in case of leakage, by sensors.
Process aspects
Onboard equipment:
- Loading and discharge (a)
- BOG recovery
- Inert gas/nitrogen production
- Emergency Shut-Down System
- Cargo quantity measurement
- Water management
- Firefighting and spray water

1. Preparation for loading:

Drying and inerting of cargo tanks using inert gas produced onboard. Vapour and oxygen are
eliminated from the cargo environment.
Drying is completed by gassing-up operation: 50 m3/h of LNG are taken from shore and vaporized,
the inert gas in the cargo tanks is replaced with warm LNG vapor. This is done to remove carbon
dioxide and to complete drying of the tanks.
100 – 200 m3/h of LNG from shore are sprayed in the tank allowing tank cooldown for 3 degrees
per hour.
2. Loading operation:
Tanks are loaded with vapour return to shore to avoid unacceptable increase of pressure. 12’000
m3/h of LNG are loaded.
 3. Loaded voyage
BOG is liquefied at sea and loaded back in the tank in order to keep the original LNG composition.
Ageing = change of LNG composition during time due to the differences in the boiling points of
each LNG component.

Vinitial−Vfinal 100
BOR = Boil Off Rate (% day) = ∙
Vinitial days of trip
It measures the percentage of vapour generated per day from the total capacity of the ship. It is
predicted by means of numerical models.
BOR depends on:
- Original composition of the LNG
- Temperature
- Heat transfer rate
- Time
- Operating pressure
- Motion

4. Discharging operation
The tank is discharged without vapour return from shore, a small quantity of LNG is vaporized and
sent to the tanks in order to avoid void.
BOG is liquified at sea and discharged.

Advantages of floating solutions:

- Faster construction
- Simpler solutions for an offshore field
- Autonomous operation
LNG onshore storage and Loading/Unloading System
Depending on LNG quantity different types of storage are possible:
- Large quantities = Fully Refrigerated Storage, storage at bubble point at atmospheric
pressure
- Small quantities = Pressurized Storage, cylindrical tanks that hold pressure during a given
time therefore avoid the need to manage BOG. They can be easily and quickly
manufactured.
Atmospheric Storage, cylindrical tanks built on site, very performant from insulation point
of view but need to have a BOG management system.
BOR = 0.05 % V/day
BOG = commonly compressed and used as fuel gas for plant consumptions
Main goals:
- Guarantee un-interrupted production
- Avoid filled or empty tank condition
- Readiness for loading and unloading

Fully Refrigerated Tanks

Configuration:
- Vertical cylinder with flat bottom and dome roof
- Above ground or in-ground according to the results of risk management
Different types:
- Single containment = one wall to contain the refrigerated fluid, eventual outer wall is
primarily to retain and protect insulation.
- Double containment = double wall tank where both walls are capable of independently
containing the refrigerated fluid. In case of leakage of the inner wall, the outer wall
contains the liquid but is not able to contain the BOG.
- Full containment = double wall tank where both walls are capable of independently
containing the refrigerated fluid and BOG.

Inner shell = 9% Ni-steel

Outer shell = concrete
Wall insulation = perlite

- Membrane = double wall tank where both walls are capable of independently containing
the refrigerated fluid and BOG. Better distribution of loads.

Inner shell = stainless steel

Outer shell = concrete
Wall insulation = Polyurethane Foam
System architecture

In the picture the export terminal is represented.

Rundown header = pipeline coming from liquefaction plant. It is very long and it can be subjected
to surge***.
***
Surge = sudden flow interruption generates an uncontrolled pressure wave which can cause
movements or damages to pipes.
1. Holding mode
The terminal is not loading nor unloading any LNG carrier, in order to keep the system cold and
prevent thermal stresses the stored LNG is circulated through the loading lines using the drain
drum. BOG from the storage tank and the drain drum is sent to a compressor and used to run
plant facilities.
BOG formation is mainly due to:
- Heat losses in pipes, tank and pumps
- Rundown header flash
- Tank displacement
Roll – over phenomenon = rapid release of a large amount of LNG vapours from a storage tank,
caused by stratification and leading to potential over-pressurization.
There are two separate layers with different density and
composition. From the upper layer BOG is formed because of
heat losses, while in the lower layer no BOG is formed due to
the hydrostatic head of the above layer.
As the densities of the two layers approach equilibrium, they
might mix releasing the BOG retained by the lower layers.
To avoid roll-over:
- Provide continue mixing
- Monitoring instrumentation and prediction tool
- Pressure relief valves sized for this scenario
 2. Loading mode
Ships tanks are loaded with vapour return to shore to avoid unacceptable increase of pressure.
The vapour coming from the ship is sent, together with the BOG from the storage tank and the
drain drum, to compression and firing.
LNG as Fuel – small/micro scale plants
What is small scale?
Plant with capacity < 1 MTPA.
Why use LNG as fuel?
- High energy density
- Flexible  heating, cooking, power generation, vehicles, chemical feedstock, …
- Market availability, saleable commodity
- Transition fuel to low carbon energy
- Environmentally more friendly than other fossil fuels  less emissions
- Many economic incentives
- Reduces the knock risk, lighter hydrocarbons increase the octane number and the
tendency to auto-ignite.
LNG is widely used to power container ships, since they cannot help consuming much fuel, the
only way to reduce emissions is to use a cleaner fuel than heavy oils. Nowadays there are 119
LNG-powered ships in operation, over 150 ordered.
Which are the main barriers?
- Poor economics of the initial LNG distribution: need for new infrastructures, the actual
number of ships and trucks is limited. People need to spend a lot of money and invest in
this sector.
- BOG
- Expensive LNG system and supply infrastructures
- LNG tanks cannot be directly integrated within the ships hull due to their size, you need to
build new ships
- Need to create new engines
Fuel supply?
- Truck-to-ship transfer = LNG truck is directly connected to the ship.
PROS: limited investment cost for operators
CONS: limited capacity of tracks, only small sized vessels

- Shore-ship = LNG is supplied from the ship to an intermediary tank or small station.
PROS: good option for ports
CONS: limited space (per ormeggiare)

- Ship-to-ship = high flexibility, the main barrier is high investment cost.

Small plants vs big plants?
Small plants have:
- Simpler liquefaction technology
- Electric motors or gas turbines  easier to fit environmental requisites
- Pressurized LNG Storage Tanks or Atmospheric ones
 - Less BOG formation  there is no need to treat it, no BOG handling facilities
- Bigger plot area/plant capacity ratio

LNG storage types?

Pressurized Tanks
- Cylindrical tanks
- Possibility to hold pressure during a given time, therefore avoiding the need to manage
BOG
- Modular construction
- Limited evaporation rate due to the limited exchange area
- Limited storage capacity
Atmospheric Flat Bottom Tanks
- Cylindrical tanks
- Expensive
- Very good insulation
- Need BOG management
- High safety
- High capacity